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CHAPTER 2

2. GENERAL PHYSICAL, CHEMICAL AND MECHANICAL


CHARACTERISTICS
OF CONSTRUCTION MATERIALS
6.1. Terminology
Construction materials represent all the natural or artificial
materials, used in the buildings realization process.
Construction material category includes from soil and natural
stone to composite materials, used in the building structures and in their
finishing works, as well even in some endowments.
Sustainability (durability) of constructions depends on three factors:
Rational conception of the main structure by design;
The sustainability of the materials that make up the construction;
Exploitation and maintenance of the building.
The sustainability (durability) of a construction material
defines its quality to not change the properties under mechanical
loads and physical or chemical agents actions supported in
service.
Choosing a construction material, corresponding to a field of use
(a part of the building) must therefore be based on knowledge of its
properties.
To be identified and compared the properties to be expressed in
value.
Value that expresses a property of a material, which is a
criterion for its use in a field is called technical characteristic of the
material.
The technical characteristic of the materials is determined in
the laboratory, through analysis and testing.

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The analysis consists in the materials decomposition in its


constituent parts to determine their existence (qualitative analysis) or
their relative amount (quantitative analysis).
Analysis can be physical or chemical decomposition as the
material is made by physical or chemical methods.
The
testing involves the
technical
characteristics
determination of the material without changing its structure and
composition by supposing the material to physical, chemical and
mechanical loads.
The testing involves, therefore making the determination on
material in the state in which it will be in operation in the construction
element.
Laboratory analysis and testing run on specimens of material
which are denominated as follows:
Probe, if is irregular geometric shape or feature in any form
(granular material);
Sample, if it has regular geometric shape and material is extracted
or prepared before bringing it into work;
Kernel, if it has regular geometric shape and is extracted from the
construction element made;
6.2. Principles for determining the technical characteristics
Representativeness of samples
To achieve a building used as a rule, large amounts of materials
that may have varying degrees of homogeneity (compositional
variation, structural failure, etc.) and samples for determining volume are
small in comparison with the material they are taken. To represent the
entire volume (lot) of material, samples should be extracted (taken) from
several areas of the materials volume.
Usually the testing methods can not perfectly reproduce the
actions that the building element will support in exploitation.
Typically, sampling is usually done by applying a statistical survey,
which should eliminate operator influence in the choice of sampling
sites. Such material is mixed extract until smooth, resulting in the primary
sample with sufficient volume to represent the entire batch of material.
The technical characteristics determination should be done
according to the following principles:
The probes are realized in two steps:

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- Primary probe realized by materials mixing extracted from


different zones of the entire lots volume (according to statistical
sounding rules).
- Determination probe realized by primary probes reducing using
methods based on statistical sounding rules (quarters method) to obtain
the determination necessary volume.
The technical characteristic is expressed as an average (statistical)
of the individual values obtained from the executed determinations
simultaneous on many determination probes (probes series) realized from
the same primary probe. The probes number from the series and the
maintaining criterions of the individual experimental results for the
average values computing, are according to the repartition statistical
rules applicable to the material and to the technical characteristic
(considered as a statistical variable).
The determination methods must ensure the results reproducibility,
so, for the same material, each laboratory must obtain the same
experimental result. This principle is applied in practice, by the settlement
of all the necessary operations for the testing and in according with it the
elimination or control, as determination imposed parameters, of the
entire factors witch can influence the technical characteristic, but dont
depend on the material (humidity, temperature, testing time, increase
speed of the load or strain speed etc.).
The probes preparation method has an especial importance.
Taking into account that the perturbing factors in this stage are the
temperature and the air humidity, is imposed that the probe to be
maintained in the environment with the temperature and humidity
imposed for a minim duration, as the entire material from the probe to
rich these parameters and the maxim testing duration to be limited. In
the cases when the testing parameters are not explicitly provided, the
materials temperature has to be (203)0C and the humidity to
correspond to one of the two limit states:
The dried at constant mass state is obtained by probes drying
in the oven at a (1055)0C temperature until at two successive
weightings mass decreasing are not registered, state when the
material can be considered as totally free water - less.
Saturated state is obtained by probes immersion in water until
at two successive weightings mass increasing are not registered,
state witch corresponds to a materials possible maxim humidity.

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To control the influence of materials temperature before


determining the laboratory performance, the sample must be kept for a
period at a normal environments temperature imposed precisely and
controlled.
For dried samples, after the removal from the oven, they are
immediately placed in a desiccator with calcium chloride) (CaCl 2),
where she maintained until cooling.
The obtained technical characteristics interpretation is done in
comparison with the limit values imposed by the Technical Norms for
each type of material and its using field, limits establishes according to
the statistical correlations between the technical characteristics
obtained in the lab and the observations on the materials behavior in
service. The incadration condition of the technical characteristic in the
limits allowed by the norm and the exploitation conditions becomes
sufficient only if the materials punere in opera technology and the
exploitation conditions are respected, as the taken into account.
Even in they are in interdependence relations, the materials
technical characteristics can be classified as follows:
Physical characteristics regarding the materials structure and
their behavior to the environment factors.
Mechanical characteristics expresses the materials behavior in
mechanical loads.
1.2. Physical Characteristics
Densities
Density is the mass of volumes unit.

m
Vx

[kg / m 3 ]

(1.1)

Depending on how it is considered volume Vx corresponding to


the materials mass, the density can be:
- Absolute density - or real (r) corresponding real volume (Vr)
represented by the pore-free material (consisting only of the constituent
particles);
- Apparent density (a) - corresponding to the volume occupied by a
material in space (made up of constituent particles and pore volume
included in the structure);

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- Bulk density (g) - due to the bulk volume (Vg) which represents the
volume occupied in a given volume of a granular material.
- Stack density (s) corresponding to the stacks volume (Vs) (form by
elements witch have regular geometrical shape), including the voids
between the elements.
Density is one of the most important physical characteristics of
building materials, allowing global assessment of other technical
features. In the design, bulk density and measuring the pile self-weight of
construction elements.
1.3. Structural characteristics
Material structure, in terms of solid matter distribution and pores, is
expressed as: compactness, porosity and voids volume.
Compactness (C) is the proportion of the volume (Va) is occupied
by the volume of material constituents (Vr ).
V
V
(1.2)
C r a ; C% r 100
Va
Va
Compactness is directly related to strength, which should be even
higher with greater compactness of the same material.
Porosity (P) is the proportion of pore volume occupies the volume
of a solid body and may be apparent or open it consists of open pores
(that communicates with the outside) and is composed of pores closed
when not communicate with the outside.
C + C P = 1% + P% = loo%
(1.3)
The porosity and apparent porosity in particular, are in inverse
relationship with the durability of a material, the apparent porosity is as
large as lower mechanical resistance and resistance to environmental
factors but the lower closed porosity is much greater capacity better
thermal insulation.
The voids volume (Vvoid) is the proportion that the volume of grains
participating in the gaps in the bunch formation volume of granular
material.
The value of goals is important when making materials resulting
from the agglomeration of granules - concrete and mortar.
Granularity expresses the relative content of different size granules
of a granular material.

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Granularity is determined by size analysis through a process of


sifting and fragmentation of granular material in the sorts.
Granularity is expressed graphically grain curve (Fig. 1.2).
100
90

Percent passing [%]

80
70
60
50
40
30
20
10
0
0

Di-1
material
material
material
material

Di

Sieve size [mm]

Dmax

srac n parte fin


monogranular
bogat n parte fin
discontinuu

Fig.l.2. Curve of grain


For a granular material to form a skeleton with a minimum amount
of voids, it is necessary that the volume of voids created by larger grains
to be occupied by smaller grains and so on.
1.4. Behavior of materials to water
In a solid material, water can be found in the following forms:
- Free water, absorbed into the capillaries and can move under
the action of gravity, and capillary pressure;
- Physically bound water - water wettability, adsorbed on the solid
phase;
- Chemically bound water - substances enter into the structure.
Influence of water on the properties of construction materials is
complex manifested a physical and chemical.
In terms of physical influence of water has the following action:
- Positive temperature conditions, adsorbed water will change the
status of efforts to produce changes in volume and the decrease of
mechanical

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- In conditions of negative temperatures, by freezing the pore


water, which is accompanied by volume increase occurring cracks and
crevices and then repeat deployments.
In terms of chemical, natural water can cause corrosion is a
chemical solution deposition or change the appearance of the building
element. Behavior of building materials to water can be judged by the
following technical characteristics:
Water absorption (of) what is the maximum relative amount of
water that can absorb a solid material under certain conditions of
pressure and temperature.
Humidity (W) represents the relative amount of water absorbed by
a solid material under certain conditions of pressure and temperature.
Water absorption therefore represents the maximum moisture that can
get a story.
Humidity and water absorption may lead to modification of
technical specifications and create a feeling of discomfort.
Water permeability is a property of solid material to allow passage
of liquid or vapor through the structure and is evaluated by:
Permeability index, which is the amount of water (in liters) passing
through a sample material with an area of 1m2 and a thickness of 1m for
one hour at constant temperature and pressure.
Since the determination of the permeability is difficult in practice,
using a complex installation, determine the degree of permeability.
The degree of water permeability is the maximum pressure in
contact with one side of the sample, for which, within the normal time on
an opposite side of the sample spots not dampening.
Since the water in the structure of a material reduces its
mechanical resistance, wetting coefficient is defined.
Softening coefficient expresses the relative reduction of the
material mechanical resistance due to the presence of water in its
structure.
Negative Influence of freeze-thaw temperatures are assessed by
repeated weight loss and reductions in strength.
Freeze-thaw resistance, called gelivity expresses the ability of a
material that is found in a state saturated with water, resistant to
temperature negative and positive alternative.

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1.5. Behavior of materials under the action of heat


Construction materials have a different behavior as their structure
is such inorganic-mineral - or organic.
1.5.1. Behaviour of organic materials in the heat action
By melting temperature, the solid inorganic material volume
changes occur resulting in changes in density, namely reducing porosity
and increasing compactness.
Temperatures above the melting temperatures below the gap thanks in particular to the presence of impurities - cause partial melting
of the material partially filling the pores of the liquid phase and reducing
porosity.
The process is called rolling clinquerisation if porosity is reduced to
between 2% and 8% respectively vitrefication if porosity of the material is
reduced to values below 2%.
Increase further the proportion of melt temperature makes the
material begins to grow and viscous-plastic to deform under its own
weight. If the process occurs at temperatures above 1580 C, and
refractory materials are called if it occurs at temperatures below 1580
C, the materials are called fuses.
1.5.2. The behavior of the organic material to the action of heat
Such as organic materials subject to heat decomposition is
characterized by the phenomenon of heat, resulting in gaseous
products that contribute to the combustion process.
For materials such as organic define the following characteristics:
- Flash point - what is the temperature at which the material
ignited a fire source;
- Inflammability point - what is the temperature at which a material
ignites even if no source of fire.
After heating the behavior, such as organic materials are classified
as:
- Uncombustible - not ignite and burn not even in the heat source
(they are destroyed by melting);
- Hard combustible - which ignite and burn as long as the source of
fire works;
- Combustible - that light source under the action of fire and burn
and after its removal;
- Inflammable - that light and heat action even in the absence of
fire source.
Present classification is used to determine the fire resistance of
buildings.

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1.5.3. Thermophysical characteristics


The main thermophysical characteristics of materials of
construction are:
Thermal deformations of the materials for which the assessment is
necessary to know are the thermal expansion coefficients (linear and
volumic).
The temperature at which a material get softened so that the
construction element may lose the stability by a viscous deformation is
called softening point.
The insulation ability of a material is appreciated by the thermal
conductivity coefficient.
The coefficient of thermal conductivity () is the amount of
heat that passes through a body thickness of 1 m, an area of 1m2,
for one hour, when the temperature difference between the body
faces is 1K.
In the case of porous materials, heat transfer by conduction is so
(in nearly close) and convection (through transmission fluid). In this case
the experimentally determined thermal conductivity coefficient is called
equivalent coefficient of thermal conductivity.
Thermal insulation capacity of materials is the better value as the
equivalent thermal conductivity coefficient is smaller and it is obtained
from porous materials or layers of granular materials (in bulk) that shows a
lot of small goals.
1.6. Mechanical properties of construction materials
If a body is actioned by an external load and its displacement is
hindered, the body structure arise effort and strain to be determined by
mechanical tests.

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10

If forming structural units are located at distances which can


interact when the load is suspended, domestic efforts will be able to
reduce their equilibrium distances, the body returns to its original form.
The deformations which cancels at the suspension of external
load is called elastic deformation (strain).
If forming structural units are located at distances greater than
their spheres of interaction, internal efforts will not bring them to their
original positions, leaving the body deformed by external force
suspension.
The deformations that not cancel at the suspension of
external load are called plastic or residual deformation.
The state of separation of structural units over the extent of their
interaction is as local discontinuities produce a material called
microcrack - or rearranging particles into new equilibrium positions.
Plastic deformations that occur in absence of any structural
rearrangement of the particles without microcracks are called
viscous deformation.
The internal stress in a point of the body as structures
response to a strain produced by an external load is called a
unitary effort (stress).
Stress is evaluated as:

F
A

where: F - active force


A - sectional area of the body
In order to analyze the effects of stress S in relation to the
plane P of the load, is considered effort in the direction
perpendicular vector components (normal) section plane, called
the unitary normal stress - , that plan included in the section called
unitary tangential stress - .

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11

Stress will oppose the removal or proximity of the two parts of the
section, while efforts will be opposed lunecrii mutual tangential
sections.
The mechanical testing involves subjecting the mechanical
action of external forces of a sample representative of a material
to its partial or total rupture.
Internal force per unit area () that arises in a body, its
structure in response to the action of external forces is called the
unitary effort (stress) or internal stress.

Strain () is the proportion of changes in the size of a body due


to external mechanical action.
The purpose of mechanical testing is to determine the mechanical
strength of a material (R) which may represent the maximum stress or
stress value at which deformations become so large that threaten the
stability of the construction element.

Depending on the application of loads, mechanical tests can be:


- Static testing - at which loading is applied progressively;
- Dynamic testing - on which load is applied suddenly (shock).
- Cyclic testing

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12

1.6.1. Static compression test


To determine the static compressive strength specimens using
cubic shape, square-based right prism, cylinder.
Trying to run the presses that can develop very large forces up to
5oo tf through two flat and parallel.

Fig. 1.3. Compression test


Specimen subjected to compressive force will suffer clipping the
direction perpendicular to the direction of force and elongation. On the
surface the bearing friction will occur that will impede the free

deformation of the specimen and thus will deform state efforts. This test is
called the friction test.
Compressive strength is determined by the relationship:

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13

Fmax
A0

(1.4)

where:
F = maximum force recorded during the test, N;
Ao = initial area of the specimen perpendicular to the direction of
force in mm2.
Static compression test bodies may take the form: cubic. prismatic
and cylindrical.
Size of the test results of friction will depend on:
Geometry of specimen (specimen form) as follows:
- The ratio between height and the cross section determines the
outcome of the large pieces and smaller cubic prismatic specimens;
- Determines the shape of the specimen cross-sectional results of
increasingly larger as the number of sides is greater.
It follows therefore that for the same material, samples of sections
equivalent resistances obtained on prismatic specimens (RPR) will be
lower than those obtained on cylindrical specimens (Rcil) that are smaller
than those from the cubic specimens.
Specimens volume, as the specimen volume is higher, lower
compressive strength results. This influence is explained by increasing
probability of existence of structural defects with increasing specimen
volume.
For cubic specimens, the most commonly used, the results
obtained on the sample side 10 cm will be 10% higher than those
obtained on the sample side 20 cm.
1.6.2. Static tensile test
Tensile strength of most building materials is lower than
compressive strength, is significantly influenced by initial state
microfisurare material structure, whereas areas not involved in the
response structure microcracks in tensile forces.

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14

Fig.1.4. Static tensile test


Static tensile test can be done in three variants (Fig. l.4)
- Axial tension (RT)
- Tensile bending (R TI)
- Splitting tensile (RTD)
1.6.3. Dynamic Tests
Dynamic tests are executed on materials that will support the
operation, dynamic action (moving loads, shock, vibration, etc.)..
Applying a force shock loss is achieved by a body (hammer, hammer) of
known mass. at certain heights. Mechanical action is assessed by the
energy that is consumed for the destruction of material evidence.
1.6.4. Non-Destructive Testing
Non-Destructive Testing is based on establishing correlations
between physical-mechanical characteristics of materials and a host of
features that can be measured from outside material (velocity of
propagation of ultrasound, hardness change, mitigation of radiation,
etc.) With different devices.
Nondestructive methods has some advantages compared with
the test methods involves the destruction of evidence, namely:
- Tested construction elements are not destroyed, which allows
either repair damage, or running multiple tests;
- Allow execution of tests "in situ" on elements of construction;
- Determination of structure defects;
- Running fast.
Nondestructive testing methods are however also disadvantages
because relying on statistical correlations between features, can give a

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15

series of errors that, in some cases make the results obtained are
considered only.

CHAPTER 2

2. SUBSTANCES STRUCTURE
Building materials are generally well-defined, from chemical and
physical point of view, mixtures of substances.
Substances properties of are determined by the atoms types
present in the structure, the bonds type established between them or
between the constituents and physical state.
Substances have different characteristics as a result of chemical
composition, structure and mode of presentation, but all are simple or
complex compounds of atoms.
2.1. Chemical elements
The atom (from the Greek athomos - that can not be
separated) is the smallest part of a chemical element that can
exist either alone or in combination with similar particles of the
same element.
Atoms have the following characteristics:
Presents a complex structure
Has small dimensions (<10-9 m)
Can exists as independent
Are electrically neutral
Chemical element is the substance that can not be
decompounded into simpler substances by usual chemical or
physical procedures and which can form, by chemical
combination, the compounded substances.
109 chemical elements are known of which 91 (natural) can be
found in nature and the remaining 18 were put out in the laboratory
(artificial).

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Chemical elements or elements are substances consisting of a


single type of atoms, having the same atomic number.
To understand and explain physical and chemical properties of
construction materials is sufficient to mention that the atoms represents a
complex system composed of a nucleus, having positive electric charge
and an electronic shall with negative electric charges.
The structure of atoms was the scientists and philosophers topics
since ancient times.
The first who introduces the concept of atom was Democrit, who
argued that atoms are characterized by the properties that distinguish it:
Essential properties (primary): size, shape, mass, energy
Secondary properties (determined by human senses): odor,
color, temperature.
In 1911, Rutherford proposed an atomic model consisting of a
nucleus (positively charged) around which the electrons are gravitating
on circular orbits (with negative electrical charge)
Quantic model of atoms (Nils Bohr), now accepted, means that
around the nucleus, on well-defined distances, the electrons forming the
electronic pulsating cloud, with ununiform density on radial direction, are
rotating.
In the atoms nucleuses (where the entire atoms mass is
concentrated) exits the nucleons: protons "p" (particles with positive
electric charge and mass of 1.672 x 10-27 kg) and neutrons n (particles
having the mass equal with the protons but without electrical charge),
mesons, liptons etc.
The atoms are characterized by:
Mass number "A" equal to the number of nucleons from the
nucleus.
Atomic number or serial number "Z" equal to the number of
protons from the nucleus.
A X atoms nucleus structure is noted with the symbol
X; example : 1,0001 H hydrogen atom ; 23,00
11 Na oxigen atom .
Electronic pulsating cloud (electronic coating) is composed of
electrons placed at defined distances from the nucleus, with rotational
movement around it in space called orbital and around his own ax,
movement called spin.
A
Z

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In 1913, Nils Bohr, believes that the electrons are rotating around
the nucleus by circular trajectory, and Arnold Sommerfeld in 1916 shows
that the trajectory is in the form of an ellipse with the nucleus located in
one of the ellipses focal.
Orbital is the region of space where the probability of occurrence
of a given electron having a well defined energy is maximum.
Electrons are particles having the mass of 9.1108 x 10-31kg
(1/1837 from the of protons mass) and negative electrical
charge and in an atom, equal with the number of protons.
Electronic shell of atoms is composed of a fixed number of
electronic layers. Each electronic layer is characterized by the principal
quantum number "n" that defines the layers energy and is conventional
noted, from the nucleus outward, with the symbols K, L, M, N, O, P, Q or
Arabic numerals from 1 to 7. In one layer can coexist maxim 2 x n2 (2, 8,
18,...) electrons. Because in energy level can only a maximum number of
electrons can be found than, electrons in addition are placed in the next
energy level outwards. The structure of atoms - energy layers and
particles in the nucleus are schematically presents in fig.2.1.

Fig. 2.1. The scheme structure of atoms


In each electronic layer electronic substrates are existing which
are characterized by the orbital quantum number "l" instead defining the
orbits shape the electrons place in the electronic layer; the maximum

CHAPTER 2

number of electrons in a substrate having the orbital quantum number


l is 2(l + 1), (2, 6,10 ...). Substrate is noted by s, p, d, f, g.
Electronic substrates are divided into atomic orbitals or energy
states characterized by the magnetic quantum number "m" that defines
the spatial orientation of the electronic cloud (the direction where the
electronic cloud is elongated when an atom is subjected to external
electric or magnetic exterior field). Magnetic quantum number can
have all the whole values including 0 between -1 and +1; (-10+1).
The quantum numbers can define the electronic configuration of
an atom by the "electronic formula" or the "layers quantum formula" in
the form:
n x lx
(2.1)
where:
n layers number (1 for K, 2 for L, 3 for M)
l - substrate (s, p, d, f, g)
x - number of electrons from the substrate
In the electronic formula the numbers show the layers number, the
letters the substrate, and the superscript the number of the electrons from
the substrate.
For example:
H = 1s1 - 1 K layer, a substrate and an electron in the substrate
O = 1s2, 2s2, 2p4 - 2 layers K and L, a substrate s in K layer with 2
electrons, two substrates (s and p) in L layer with 2 electrons in s subtrate
and 4 electrons in the p substrate
Na = 1s2, 2s2, 2p6, 3s1 - 3 layers K, L, M, a K-layer substrate with two
electrons, two s and p layer substrates with two electrons in the substrate
L s and six p electrons in the substrate and a substrate to start with
an M electron.
Electron shell structure for an atom is expressed by the formula E in
which the first digit indicates the layer number, the letters indicate the
substrate and that substrate electronic number exponent (H = 1 s1, s2 O
= 1, 2s2, 2p4).
Formula electronic position indicating element in the periodic time
and group and hence the physicochemical properties. The period is
given by the maximum principal quantum number (the number of
electronic layers (H p1, p2 from O, p3 to Na) and group, the sum of the
exponents of the same number (H group I, group VI A, group I Na ).
Electrons in stars, and orbital substrates to the following rules:
The principle of minimum energy in atoms with more electrons,
they are in sequential order growth in the orbital energy.

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Exclusion principle (Pauli's) in an atom no two electrons can have


all four quantum numbers identical.
N + l sum rule, the electrons are placed in layers and substrates in
order of increasing numerical value of the sum n + l.
Hund's rule, a second electron enters the orbital with the same
energy level only after all the orbitals have one electron energy levels.
The layer farthest from the nucleus of the atom energy called
energy level can last up to two electrons to find a single layer of atoms
with a maximum of eight electrons in electronic atoms with electronic
layers.
The existence of the last energy level of eight electrons or two
electrons if the energy level of atoms with one electron configuration is
called closed.
Marginally lower than the electronic layers were always closed
electronic configuration.
Atoms that have a closed electronic configuration are well
balanced, being stable under normal conditions, ie, they are able to
combine chemically. Among the elements known only six have the final
energy level closed electronic configuration, forming group noble gases
(He, Ne, Asr, Kr, Xe, Rn), except He who has the last energy level (K) a
doublet all other electrons ends with a closed electronic configuration of
eight electrons, octet).
Atoms that have the energy level achieved last closed electronic
configuration and have a tendency to make the capture of electrons to
achieve octet doublet or electron transfer or peripheral, remains stable
following the electronic layer, these atoms have the property to
combine chemically.
The number of electrons that an atom can give full or put together
to form closed electronic configuration is called valence.
Mono valence atoms may be so, divalent ... heptavaleni energy
level with the last 1.2 ... 7 valence electrons.
Atoms can combine with each other only in proper proportion to
their valence. Thus, a monovalent atom AI can not be combined with an
IIA divalent or trivalent atom only in the proportions AI2 AIII AII,
respectively AI3AIII and can not give a bivalent atom with a trivalent
atom than the combination AII3AIII2.

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Atomic mass (molecular) relative to the amount of times the mass


of an atom is greater or less than the mass of carbon atom 12 (126C)
The amount of a given atom which can combine with a hydrogen atom
is called chemically equivalent.
The chemical
equivalent.

calculations

and

working

with

mole

gram

The amount of the substance in kg (g) relative atomic mass


number equal to the substance is called mole.
A gram equivalent is the amount of substance in grams which can
be combined with 1.008 g of hydrogen.
Regardless of pressure and temperature, one mole of any
substance contains the same number of molecules, Avogadro's number
(NA = 6.23 x 1023molecule/mol).
Classification of elements (atoms) has concerned scientists since
ancient times, using different criteria such as similarity, behavior, weight,
etc.
Berzelius (1808) divides items into 2 categories: metals and
nonmetals.
Dobereim, taking account of chemical properties, group them into
groups of three, which he called triads.
Chancourtois (1833), places items in order of increasing atomic
masses in a spiral around a cylinder and found that the elements
located on the same generation have similar properties.
Mayer and Odling (1864) take into account the valences and
atomic mass and properties observed after each repetition of the sixth
element.
Mendeleev (1869) proposed the periodic table of elements that
form long and short form version (1871), approaching - the law is the
definition of the periods, after which the properties of elements are
periodic functions of their atomic mass.
Mendeleev arranged the elements in horizontal rows (periods) in
order of increasing atomic weights from hydrogen and returning as soon
as it appeared another element with similar properties, where
appropriate element not found a vacant spot left assuming that there
was discovered. He obtained such vertical rows (groups) of items with
similar properties.

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Moseley (1913) states that the properties of monotone increasing


frequency varies depending on which property is the atomic number
elements (Z) and the number of orders or the place it occupies in the
periodic table element, which is both time and number of protons and of
electrons in atoms.
Analyzing a modern classification of elements according to their
atomic number (Table 1.1) is identified to:
seven periods (horizontal rows, marked with Arabic numerals
1,2,3) and three small periods of 2 and 8 elements and four times higher
by 6:32 p.m. elements, the last incomplete (with six natural elements and
the rest synthetic);
eight groups (vertical rows, marked with Roman numbers I, II, III)
of which seven elements are chemically active, with similar
characteristics in each group and zero valent group elements (energy
level have the last closed electronic configuration ) chemically stable.
It contained 92 items grouped as natural and synthetic or Transuranium
rest (the last naturally occurring element is uranium), total 109 elements
known today).
Each period begins with a monovalent element and ending with a
zero-valent element (inert gas).
For small periods (1,2,3) formed seven groups of active elements and a
group of stable elements.
From large groups to form subgroups that comprise the elements
with characteristics similar items in small groups called major subgroups
(denoted by Ia, IIa ...) and subgroups that contain elements that have
only certain similarities with the items in small groups - sub-sub . (Denoted
by Ib, IIb ...)
Elements of secondary subgroups make the transition (transition)
between elements of two main subgroups and are called transition
elements.
The fourteen additional elements (positions 57 ... 71) of the sixth
period have similar characteristics and are called lanthanides
lanthanum.
Between the seventh and secondary sub secondary sub nine
second remaining elements have very similar chemical properties and
forming a separate group of eighth-payments called ferro metals
(elements of this group are iron and metals from the platinum finish) .

CHAPTER 2

2.2. The relationship between position of elements in the periodic


classification, structure and properties of atomic elements
There is a close link between the position of elements in the
periodic classification, structure and properties of atomic elements,
chemicals and construction materials. Thus, the number of periods in the
periodic classification of electronic layers equals the number of atoms of
that period and the number of groups equals the number of valence
electrons of elements of main groups and corresponding subgroups.
In the period I can not exist only two elements (H, He) because their
atoms have only one energy level (k) with a maximum of two valence
electrons. In periods II and III and the main subgroups of atoms have
large periods 2.3 ... 7 energy levels, and the last more than eight valence
electrons.
Items in the first three main groups and subgroups with one, two or
three valence electrons are electropositive elements, the character of
metals, because they tend to give up valence electrons to create
closed electronic configuration.
Elements of groups V, VI, VII with five, six seven valence electrons
are electronegative nature of nonmetal elements, because they tend to
capture electrons to achieve the closed electronic configuration.
Going through periods of from left to right shows that the elements
gradually change their character, ranging from the electronegativity
electropozitivity. This behavior is explained by the increasing burden of
electropositive core that manifest with a force increasingly more on the
valence electrons.
Along the main groups and subgroups corresponding
electropositive character of the elements is emphasized as increase
energy levels (with the number of periods) so that the valence electrons
are more removed from the core and therefore less attracted to and
more mobile.
This increase electropozitivitii from top to bottom, the main
groups and subgroups and explain the elements of Group IV
electroneutre gradually pass electropositive elements with periods 4,5,6
nonmetal character.
There is also a close relation between the position of elements in
the periodic classification and properties of chemicals and building
materials, such as: character oxidril compounds in different groups can
be hard for the basic elements of Group I and II (the hottest NaOH)
amphoteric character of the elements in Group IV (Al (OH) 3), very weak

CHAPTER 2

acid (Si (OH) 4), countries (H3PO4, H2SO4) and very strong (HCl) for
elements of groups V, VI, VII respectively.
As shown in Table 2.2 combinations alkali earth oxides, Group II of
the periodic system with various other acidic or amphoteric oxides can
position their properties as binders in the group is primary or secondary,
on the basis of this rule may provide behavior of combinations not
studied yet.
Table 2.2.
Period oxide elements
Group II oxides acids
SiO2 Al2O3 Fe2O3 Cr2O3 Mn2O3 SnO2
BCO II
III MgO
IV CaO
IV ZnO
V Sro
V CdO
VI BeO
without binder properties studied, the binder properties studied
2.3. Spread in crust elements
Earth's crust (16 ... 20 km depth) is a major source of construction
materials and raw materials for the construction industry.
The knowledge gained while on the earth's crust allowed to
calculate the percentages involved in the chemical composition of its
various elements. American Geochimitii Clark and Washington made
the first calculations of these percentages and they have called MF,
later called clark-uri.
Clarkurile of medium frequencies is the percentage by weight of
the items involved in crust formation. Items with the highest clarkuri are:
oxygen (47.2%), silicon (27.6%), aluminum (8.8%), iron (5.1%), calcium
(3.6%), sodium ( 2.6%), potassium (2.6%), magnesium (2.1%).
It notes that of the 92 naturally occurring elements in the
intervening eight crust structure with 99.64%, other 84 items are in a very
small percentage, dispersed into other elements or less in the form of
local clusters (veins).

CHAPTER 2

10

Oxygen enters in most combinations (or combinations of oxygen


with silicon oxide) which are able to combine with other metals to form
complex oxides that are of the earth's crust, being found in most
construction materials.
In addition to the oxides in the Earth's crust are also found several
clusters of carbonates, sulfates and chlorides of various metals and
forming the raw material for all industries.
2.4. Ions and their formation
Following the tendency of atoms to achieve closed electronic
configuration through electron transfer or capture disrupts the balance
of electrical charges in their configuration, new configurations are called
ions.
Atoms that have the top floor of a small number of electron
energy (1.2 or 3) have the tendency of valence fail, leaving the closed
electronic configuration of the penultimate level of energy. Following this
process the atoms remain an unbalanced number of positive electric
charge equal to the number of electrons transferred, that is why these
elements consist of atoms of elements called electropositive.
Electrons from the atoms that gives the final energy level formed
positive ions.
Atoms that have the last energy level a larger number of valence
electrons (5.6 or 7) tend to form closed electronic configuration by
electron capture negative charge and thus also unbalanced. Items with
this feature are called electronegative.
Atoms that trap electrons to achieve the closed electronic
configuration on the last level of energy form negative ions.
Items with small table and four valence electrons (such as carbon) did
not yield and does not capture electrons to form closed electronic
configuration, and items made with these atoms are called
electroneutre.
Ions are marked with the symbol of the atom formed having
entered the number and kind of electrical load exponent (H + - positively
charged hydrogen ion, S2-- sulfur ion with two negative electric
charges).
2.5. Interatomic bonds
Naturally occurring atoms in combination (between atoms of the
same elements and atoms of different elements) forming the atoms form
molecules and set free only in the noble gases or metal vapor.

11

CHAPTER 2

Molecules are formed by linking atoms between them through realizing


valence interatomic bonds that can be of type: ionic or electrovalent,
covalent or atomic metal.
Fig. 2.2. Interatomic bonds scheme
Link electrovalena ion or ions an element is established between
electropositive and the electronegative element.
Between negative and positive ions occur in nature electrostatic
attractive forces that depend primarily on the size of electric charge,
being stronger as the electric charge is higher and that is a multiple of
the electric charge of electrons.
Electrovalena interatomic is the weakest link, because the electric
charge of electrons is very small. Link electrovalent is not rigid, ions
having a fixed relative position.
Building materials made of substances electrovalente links have
low mechanical strength and low strain at break (small distance
between the atoms are not able to reconnect), specific breaks, low
chemical stability, etc..
Or atomic covalent bonds are formed by sharing valence
electrons bound to atoms in the molecule, is done as pairs of electrons
belonging to two atoms bound together.
The condition required to achieve a covalent bond is that the
electrons involved in its formation have opposite spins. In this case the
lines of force of the two electromagnetic fields are closed, the two
electrons attract each other forming a very stable couple.
A pair of electrons that form a covalent pooling is marked with a
line (H-H hydrogen molecule formed by sharing a pair of electrons, 0 = 0
molecule of oxygen, formed by sharing two pairs of electrons).
If the atoms that are covalently bound by the same or similar
characteristics, fixed positions to each other, the center of gravity of the
nuclei coincide with the center of gravity of the whole system of
electrons. Thus formed are called nonpolar molecules.
Covalent bonds between different atoms are characterized by
the fact that the electron pair is not located symmetrically in relation to
two linked atoms (center of gravity of the nuclei no longer coincides with
the center of gravity of the whole system of moving electrons to the
atom higher positive electric charge). Molecules thus formed acquire a
polar character, becoming an electric dipole, called a dipole molecule.

12

CHAPTER 2

A molecule dipole (fig.2.3) is characterized by product (d e), called


dipolmomentul molecule where "d" is the distance between the centers
of gravity of electric charges (about 10-8 cm, which is the size of a single
molecule) and " e "is the electric charge.
Fig.2.3. Scheme moleulelor polar and nonpolar

Fig.2.4. Water molecule dipole


Dipolmomentul poliatomice molecules is the result of determined
vector of all polar bonds.
The water molecule (fig.2.4) hydrogen atoms are oxygen atom
legations of covalent bonds at an angle of 1040 hence the dipole
character of water molecules which explains their association and the
hydration process.
Polar covalent bonds are intermediate links between
electrovalen and non-polar covalent, being especially close since
dipolmomentul electrovalen is higher. Polar covalent molecules, like
those formed by electrovalen are moving in the presence of an
electric field.
A particular case is the relationship coordinative covalent bond,
which is accomplished by sharing a pair of electrons that originate from
a single atom, called the donor atom, electron pair accepting another
atom, acceptor atom.
If coordinative bonds are deformed electron cloud between
atoms related links such as garment and covalently linked ionic nature.
Metallic connection is characterized in that it allows some electrons to
move freely from one atom to another occurs only between atoms in
solid or liquid metals.
Metal connection is formed by two electrons ties unravel and
recover continuously between pairs of neighboring atoms. Due to the
small number of valence electrons in metals is not possible to form
covalent bonds, electrons are therefore statistically equally distributed
among all atoms due to greater mobility.
Metal links, not oriented in space and endowed with greater
mobility, atoms, transformed into ions occupy structures that generate
the most compact and low power with high plasticity (can change
shape without suffering mechanical structural damage ). The presence

CHAPTER 2

13

of free electrons of metals give specific characteristics: high electrical


and thermal conductivity, light absorption, compactness, luster specific
appreciable mechanical strength, hardness, etc..
2.6. General aspects of nuclear radiation
The phenomenon of spontaneous emission of elementary particles,
nuclei of light or radiation from a hard core, poar name natural
radioactivity or radioactive decay. The phenomenon of radioactivity is
determined by two basic factors:
nucleus instability caused by excess neutrons against the
protons, ie the ratio N / Z, with value supraunitar;
mass-energy relationship between the initial nucleus, the core
product and the particles emitted.
Radioactivity can occur through several mechanisms:
a) emission partciule have mass number A 82, heavier than the
DB (except saddle Sm-147 isotope). The emission of particles is very high
energy beams to form monoenergetice, very rare, are accompanied by
particles emitted photons
,
b) emission of particles or 2 decay - the emission of negative
electrons and positive flow.
Electrons from the conversion of neutrons (in nuclei) in the proton.
It is characteristic of nuclei with excess neutrons in the N / Z
1.
radiation monoenergetice not. When the ratio N / Z values is small
(slightly supraunitar) and an emission of particles is not possible ,
positron emitting nuclei.
+ decay is found only in artificial radioactive
isotopes, excess energy is taken by neutrinos, v-, v;
c) capture of an electron orbital (K capture) occurs in nuclei with
excess neutrons, but may stabilize by emission of positrons. It captures an
electron to its own orbit of K, the kernel nearest thousand. Photons
leaving the nucleus can be absorbed and produce an electron out of
orbit of the same atom; phenomenon gives rise to secondary particles,
known as internal conversion;
d)
emission of radiation or gamma decay. Each of the three
mechanisms of manifestation of radiation, may or may not be
accompanied by the emission of radiation
.
radiation is
monochromatic electromagnetic radiation flow (flow of photons, neutral
particles) with very high energy. They are emitted by unstable nuclei,
excited, often accompanied by other phenomena of radioactive decay

CHAPTER 2

14

and . Only radiation emitted (photons), the nuclei can return to the
fundamental energy.
The phenomenon of radioactivity is governed only by a law called the
law of disintegration, which is stated as follows: the probability of decay
of a radionuclide per unit time is constant and is independent of external
conditions. Mathematical expression of this law in differential form is:
and the full form is:
N = N0. e- . t
Where:
N = no. radioactive nuclei at the initial time, t = 0;
T = decay time lasts;
= decay constant, or probability of decay, radionucleu own
species.
Radioactive decay is a reaction that follows after a first-order
kinetics and half-life which is a basic feature, t0, 5 (t1 / 2) species-specific
radionuclide. The half-t0, 5 can range from microseconds to billions of
years.
e) spontaneous fission is rare, only nuclei with atomic weight about
232. From this nucleus with mass number smaller nuclei (at least two light
nuclei) without interfering with the external energy.
Interaction of nuclear radiation environment
When nuclear radiation (particles , ,
and neutrons) crosses
the environment, they deplete their energy or by a mechanism monoact
or in a large number of impact processes. Energy given environment
produces a number of effects, among which the most important are the
ionization and excitation.
and
radiation (charged) produce the environment due to
strong ionization process that occurs predominantly by plucking
electrons from atoms and molecules collide with, while losing energy.
Electrons can also plucked their other ionized atoms or molecules.
Ionization process intensity is expressed quantitatively by the number of
ion pairs formed on a tape of the incident trajectory, called specific
ionization or ionization power. This task depends on mass and energy
incident radiation, and on the nature of passage. Ionization power of
particles (A is 4 amu) is considerably higher than that of a particle (A
is 0.00055 amu) at the same energy, for example, produces air particle
50000-100000 ion pairs / cm, and particle, the same energy, only 30300 pairs of ions / cm.

CHAPTER 2

15

radiation (no load) directly collide with the electrons orbit the
atom, transferring energy and throughout, as a result, the electron can
be pulled out and ejected from the atom with a kinetic energy equal to
the difference between the photon energy h
incident and energy
connecting the electron to atom (Ec = h - El). Electron beam produces
an electron plucked secondary.
ionization of atoms under the
influence of radiation is much lower than that produced by radiation
and .
If the energy lost by radiation from the collision energy is less about
the electron, then it can not be torn from the atom or molecule to which
it belongs, has held only that the atom excitation and electron energy
taken the form of heat is dissipated .
Neutrons are particles without electric charge and zero rest mass
interacts with the environment differently from other types of radiation.
They do not interact with orbital electrons of atoms, atomic nuclei but
only in three types of physical processes: elastic or inelastic scattering,
diffusion in the environment and slowing down and capture by nuclei. As
a result, there occurs a direct ionization of the environment, but only
through a secondary recoil atoms displaced by elastic collisions with light
nuclei or particles emitted in the capture reactions.
The maximum distance that a radiation crosses a certain energy in
a given environment is called penetration or distance traveled and
expressed in meters. Example: radiation in air has a pathway 0.0380
m and radiation of several meters.
Be emphasized that while
radiation have a relatively short
distance, depending on the nature, radiation is higher by 1-2 orders of
magnitude, and
radiation and especially neutrons, which run across
any environment, their course has much higher values. Table 1 presents
some characteristics of nuclear radiation.

Table 2.3. The main characteristics of nuclear radiation


The rest mass radiation
others do Energy Burden
MeV penetration distance (m)
Solid in air
4 2 4-40 0 to 0.15 0 to 0.001
5,48.10-4 -1 0-4 0-40 0 to 0.1

CHAPTER 2

16

- (electron) 5,48.10-4 1 0-4 0 to 1.00 0-1


+ (positron) 1.0073 1 000-100 - small
proton 1,0086 - 0-15 0-10 0-1
X - - 1eV - 100 keV 10-10 0-1
- - 10keV - 3MeV 10 to 10 0.1 to 1.00
Others do a = 1.66 .10-27; 1eV = 1,60219.10-19j; 1keV = 103eV, 106eV =
1MeV
Basic quantities and units of measure nuclear radiation
The intensity of nuclear radiation environment interactions are
expressed quantitatively by means of the fundamental quantities
involved.
Human senses do not perceive direct nuclear radiation, but they can be
detected and measured by a variety of media: film, thermoluminescent
substances, Geiger counters and scintillation detectors.
Measurements made with the detectors can be interpreted in
terms of dose of radiation that has interacted with the environment
considered. If the measurements are not possible, for example, when a
radionuclide is deposited in the human body, it is possible to calculate
the radiation dose absorbed by the body, if known activity.
Core activity is the size that characterizes the intensity of
radioactive sources, expressed in number of nuclear decays in unit time
(decays per second). Unit activity is called symbolic becquerel (symbol
Bq) French scholar named after. The multiples are used frequently, such
as megabecqerebul (MBq).
1 Bq = 1 disintegration / second unit in the international system (SI)
Old unit for activity is the curie (Ci)
1 curie (Ci) = 3,7.1010 decays / second
The relationship between these units is as follows:
1 Ci = 3.7. 1010 Bq = 37 GBq (gigabecquerelul)
1 Bq = 2.7. 10-11 Ci = 27. PCI
The activity is proportional to the number of atoms of radioactive
sources, as a result of any quantity of radioactive material can be
expressed in Bq or Ci, regardless of purity, that concentration sources. For
example, one gram of Pu -239 is approximately 2000 MBq activity: it has
issued about 2,000 million particles every second.
A radioactive source gradually alters its activity. The half-life, t0, 5 is
the size of the source expressing decreased activity in half.

17

CHAPTER 2
Table 2.4. Convert Curie - Becquerel
Ci Ci
Bq Bq
kCI (103C) TBq TBq (1012 Bq) Ci
GBq Ci GBq (109 Bq) mCi
mCi (10-3) MBq MBq (106 Bq)
Ci
Ci (10 / 6 Ci) kBq kBq (103 Bq) nCi
nCi (10-9Ci)
PCI Bq Bq
PCI (10-12Ci) MBq MBq (10-3) FCI

Absorbed dose
Various nuclear radiation ( ,
,
) interacts differently with
different materials they pass through. To avoid these biological effects of
radiation, use size D - dose absorbed, which expresses the amount of
energy transferred to unit mass of absorbent material. As a unit, the
system S.I. Gray is used (symbol Gy) after the name of English scholar.
One gray corresponds to a joule per kilogram. Frequently used
Submultiples of gray, such as micrograyul ( Gy)
1 gray (Gy) = 1 J / kg:
Old unit absorbed dose is Radul
1 rad = 100 erg / g
The relationship between these units is as follows:
1 Gy = 100 rad and 1 rad = 10 2Gy (centigray)
Absorbed dose rate can be expressed in: Gy / s, rad / minute, or
rad / day, as it is more convenient.
Equivalent dose
Biological effects of nuclear radiation is different, even at the
same absorbed dose. For example: a gray radiation in human tissue is
more dangerous than a gray radiation
is slower because the
particle electric charge and more than - more energy dissipates along
the journey . To restore all ionizing radiation on an equal basis in relation
to the possibility of negative effects, he introduced a quantity called
equivalent dose, the unit of measure (SI) site is sievert (symbol S ),
named after the scientist Swedish.
Dose equivalent is equal to the absorbed dose multiplied by a
factor of radiation quality, a factor which takes account of how
radiation distributes its energy in the tissue. For example, radiation , -,
and X factor was taken as equal to unity.
Sievert's (S ) is defined as the equivalent dose for tissue exposed to
radiation with quality factor equal to unity when the tissue that absorbed
dose is 1 Gy, so the gray and sievert units are numerically equal.

CHAPTER 2

18

= 1 S = 1 Gy 1j/kg
Typically used sievert's multiples such as M S
Rem is used as the unit's old (Roentogen Equivalent Man) The
relationship between these units is:
S 1 = 100 rem or 1 rem = 1 C S
For example, when a radionuclide is deposited in the human
body, it is possible to calculate the radiation dose absorbed by the
body, if known radionuclide activity.
Knowing the level of radiation in dwellings is important for
determining exposure of the population since most people spend a
great deal of time in confinement (average occupation factor of 0.8 is
statistically determined).
Radiation source is constituted by the main primordial
radionuclides present ubicular the earth's crust, ie 40K. 87Rb and two
series of radioactive elements from 238U and 232Th.
Other natural radionuclides, such as those present in the 238U
series, radionuclides cosmogenici (8H, 7Be, 14C, 22Na, etc..) Sio those
from 238U spontaneous fission (eg 90Sr) can be neglected because their
contribution to the total dose of radiation is small .
Radioactive elements of interest in the building materials are the heavy
metals., 220Rn and 222Rn except that belong to the noble gases.
Gaseous radionuclides, released by construction elements, generates
short-lived progeny, which are incorporated by inhalation and is the
etiologic agent of lung cancer radioindus.
Radiobiological risks resulting from the presence of radioactive
substances in building materials are composed of external radiation
emitting radionuclides produced by drop the items and materials from
internal irradiation from inhalation of radon and its daughter products
accumulate in living quarters.
Absorbed dose rate inside the building depends only on the type
of construction material used and its origin. Construction elements acting
both as a source of irradiation and as suppressors of cosmic and
terrestrial irradiation, intense outdoors.
Evaluation of radiation dose on the whole body of the radioactive
content of building materials.
Indoor absorbed dose rate depends mainly on the activity
concentration of natural radionuclides in building materials. Linking the
radioactive content of the radiation dose is difficult.
The main contributors to the dose of radiation are absorbed from 40K
(35%) 232Th (40%) and 238U offspring (25%). As such, determining the

CHAPTER 2

19

concentrations of these radionuclides is sufficient to estimate the


absorbed dose in air.
Values are calculated but only one indicator that allows
comparison between them of building materials in terms of their ability
and not an accurate irradiation, by calculation, the dose would be
received in homes constructed of these materials.
The data obtained allow classification of the materials investigated in
terms of the potential risks posed by radiation.
When expressing concentrations of 40K, 226Ra and 232Th in Bq /
kg when the relationship is satisfied:
It is estimated that the increase over the background level of
absorbed dose to the gonads, inside the home.
The external radiation, is less than 1.5 mGy / year, the allowable
amount.
Materials that do not satisfy this relationship to be considered
separately, indicating, where appropriate, limiting their use according to
the proportion falling in all buildings or parts of structures or, when
appropriate, prohibit their use.
2.7. Interparticulare bonds
Between molecules, particles and atoms with stable atomic
structures can collectively establish links interparticulare or van der Waals
forces.
Van der Waals forces are determined by the initial attraction
between electrons and nuclei of a molecule elements of adjacent
molecules, forces that are not fully compensated by the repulsive forces
between electrons, nuclei that same atoms.
Intermolecular interaction mechanism depends on the nature of
interatomic bonds offending molecules manifested by:
guidance forces (Keeson) that occur between polar molecules
that attract the opposite ends having been a molecular association
followed by molecular orientation
Dispersion forces (London), which takes place between any type
of molecule as a result of the attraction between nuclei and electrons of
the same molecules
inductive or polarizing forces (Debye) occurring by the action of
polar molecules capable of creating an electric field to polarize the
molecules polar or low polarity.

20

CHAPTER 2

For the van de Waals forces is necessary to show an optimal


distance between the molecules (5 ... 10 A). At large distances (more
than 10 ) attractive forces are very weak and small distances (less than
4 ) attractive forces are compensated by the repulsive forces
generated by outer layers interptrunderea.
a. b.
Fig.2.5. a. Assembly exercises the forces between atoms
b. van der Waals forces Scheme
The forces of rejection are very high when the molecules are in
contact (at distances below 4 ) decreased as the distance between
molecules increases, as a result, the interaction (the resultant forces of
rejection and attraction) as a force of attraction, reaching a maximum
small distances between molecules corresponding to zero interaction
"d0" which tends to characterize the spatial structure of each substance
due to the minimum internal energy.
Size of van der Waals forces increases with the number of electrons
in the molecules, elements, molecular weight, respectively.
Force van der Waals attraction between molecules determine the real
gas, liquids ensure cohesion, the stability of crystalline solids molecular
network, causes the melting of molecular substances, fluids and
decrease condensation explains the solidification points etc..
The molecules in which hydrogen atoms are covalently bonded to
an electronegative element electronic shell is deformed so that
between adjacent molecules appear attractive forces.
Attractive forces between molecules can be established in which
hydrogen atom is covalently bound to an electronegative element
called hydrogen bonds are linked by bridges or hydrogen.
Hydrogen bridges occur between hydrogen atoms in a molecule
and electronegative atoms of neighboring molecules (fig.2.6 dotted
lines).
Fig.2.6. Hydrogen bridges
These links are static in nature and lead to the formation of
molecular associations. Decks are made primarily of hydrogen molecules
in strongly electronegative elements and small atomic volume.
Molecular associations through hydrogen bridges occur mainly in water,
alcohol, organic acids etc.. the associations formed between the filiform

CHAPTER 2

21

which may be linked by van der Waals forces. Molecular associations


thus formed modifies some properties of substances such as viscosity,
dissolution capacity, melting point, boiling point etc.
Bonds by hydrogen bridges of water explains some of the
characteristics: melting and boiling points very high compared with other
combinations of hydrogen with oxygen neighboring elements, the
maximum density at 40 C, high specific heat, etc..
Bonds by hydrogen bridges are stronger than van der Waals bonds by
forces weaker than electrovalente.
2.8. Carbon Structures
Elemental carbon in the natural state can be found in two forms:
diamond and graphite. Combinations of carbon occur in nature,
especially in the form of carbonate minerals that, CaCO3 - limestone,
marble, FeCO3 - ered etc., Biological carbonates (shells) in the form of
hydrocarbons.
Carbon atoms, because of electroneutru are property of the
covalent link between them by chains or chains of varying lengths
(acyclic structures) or cycles (cyclic structures), and the substances thus
formed are called hydrocarbons (or organic compounds) because
Hydrogen is the main type associated with the carbon atom.
Hydrocarbons containing the maximum possible number of hydrogen
atoms are called saturated hydrocarbons.
2.8.1. Carbonates
The most common form, such as mineral carbon, CO3 group is a
combination of metal and can be of two types:
normal or neutral carbonates M2CO3 structure;
carbonates or bicarbonates with acids struct MHCO3
Alkaline earth metal carbonates decompose heat up to
temperatures of 10000C and used to obtain lime and construction of
cement clinker (in combination with aluminum or silicon).
Calcium carbonate, depending on the type of crystallization: calcite
(crystallized in the rhombohedral system and aragonite (rhombic crystal
system) is one of the most common minerals in nature is a natural binder.
Calcium carbonate is poorly soluble but the solubility may increase
presence of carbon dioxide. The presence of calcium carbonate
hardness in water causes temporary water.
2.8.2. Simple hydrocarbons

22

CHAPTER 2

Because the valences of carbon atoms in space after call


directed corners of a tetrahedron (fig.2.7.a) and the possibility of turning
them into simple covalent molecules around, catenae not strictly linear
but simple form zig-zag ( fig.2.7.b, c, d).
Fig.2.7. The structure of simple acyclic hydrocarbons
If the chain carbon atoms are bound together by a single link (to
put together a valence) to form alkanes (saturated hydrocarbons),
where double bonds are formed at the triple alkenes and alkynes.
The series mentioned alkanes methane, propane and butane,
ethylene belongs to alkenes and Alkyne the most important product is
acetylene.
In cyclic hydrocarbons where the carbon atoms are linked by a single
link are called cycloalkanes and cicloalchine cicloalchene respectively
for two and three facets.
Most often the link five or six cycles of carbon atoms forming
ciclopentanii (fig.2.8.a) and ciclohexanii (fig.2.8.b).
Following the conveyance of the valence tetrahedral carbon
atoms, cyclic hydrocarbon structures are not flat but in two planes.
Fig.2.8. Cyclic hydrocarbons Scheme
The schematic structure of cyclohexane fig.2.8.c presented in 1.3
and 5 atoms are in a plan, and 2,4 and 6 atoms in another plane.
Simple cyclic hydrocarbons can put together two carbon atoms by
removing a hydrogen atom, forming condensed hydrocarbons. If the
condensation continues in all directions, eliminating all hydrogen atoms,
to reach the diamond crystal structure in which each carbon atom is
covalently bound to four other carbon atoms.
Fig.2.9. The structure of condensed hydrocarbons
Some cyclic hydrocarbons is made between carbon atoms linked
to higher energy so that it can bind only one hydrogen atom, but triple
joint connection between carbon atoms, given rise to cyclic aromatic
hydrocarbons.
The simplest aromatic hydrocarbon is benzene with three
conjugated double bonds and giving the name of this party - benzene
nucleus.

CHAPTER 2

23

The condensation of aromatic nuclei are formed with aromatic


hydrocarbons higher plane structure. If condensation is still fully in both
directions of the plan gives a plan called flat mesh network.
Overlapping may occur between reticular planes weak forces of
attraction Van der Waals-type structure leading to grafituluii (fig.2.10).
In graphite, crosslinking plans are not exactly superimposed
(hexagon over hexagon) but shifted by the length of a diagonal side of
the hexagon purposes. This structure explains the pronounced tendency
to split graphite (parallel open reticulation plans) and its use as a
lubricant.
Stable aromatic structures present state of hydrocarbons and
carbon crystallized at high temperatures.
Derived 2.8.3.Hidrocarburi
From simple hydrocarbons by replacing one or more hydrogen
atoms with other atoms or groups of atoms or by replacing carbon
atoms with atoms of another kind, derived substances are obtained,
which explains the large number of natural or organic substances
synthesis, more than 500,000. Derived substances have different
properties from being basic substances, in particular, easily react.
Atoms or groups of atoms that produce derived substances are
called functional groups and properties of the newly formed chemical
functions are called.
The most important groups of chemicals are those with oxygen
functions, namely:
alcohols - the presence of functional group in the molecule
oxidril
(-OH);
aldehydes - the presence of carbonyl functional group (= C = 0);
acids - containing carboxyl group (-COOH)
For example, ethane is obtained:
CH 3 CH 2 COOH CH = C = 0
CH3 CH3 CH3 CH3
From aminogel functional group (-NH2) derived substances called
amines are obtained.
Among derivatives of aromatic hydrocarbons, the most important
are those with oxidrilul and aminogelul (for example, benzene and
phenol and oxidrilul obtain the Bezen and aminogel - aniline).
Derived substances can be obtained with several functional
groups of the same or different way: the group oxidril two carbon atoms

CHAPTER 2

24

joining the simplest derivative is glycol, and derivatives of oxidril three


groups of three adjacent carbon atoms is obtained glycerin - the basic
substance of natural fats and cyclic hydrocarbons epoxizii - components
used to manufacture polyethylene.
Among the derivatives with different groups, particular importance
is the simultaneous presence in the molecule and carbonyl oxidrililor,
generating substances from sugar family (also called carbohydrates
because of their gross type - Cm (H2O) n and carboxyl groups and
aminogel that are found in amino acids.
Substances derived from different functional groups are obtained
with organic macromolecules present in both plant and animal tissues
but also in artificial materials "polymers" with a wide use in construction.
Derived molecules can associate by eliminating water molecules,
resulting in new features such as:
two molecules of alcohol-ether
C2H5 - OH + OH - C2H5 C2H5 - O - C2 H5 + H2O
from an acid molecule and an ester alcohol is obtained
CH3 - COOH + HOOC - CH3-COO CH3 - C2H5 + H2O
two molecules of acid anhydride is obtained
CH3-COOH + HOOC - CH 3 CH 3-CO - O - CO - CH3 + H2O
2.8.4. Organic Macromolecules
The large organic macromolecules containing over 1500 atoms
and molecular weight of 104 ... 106 and more than one order of
magnitude .
Macromolecular organic compounds molecules are formed
mainly by covalent bonds or electrovalente not fall into this category
agglomerations formed by Van der Waals forces or hydrogen bridges.
Macromolecules is formed, most often by polymerisation and
polycondensation reactions and sometimes by polyaddition.
Polymerization is the linking of several small molecule compounds
not resulting from secondary reactions, such as constituent atoms are
found in the same proportion and simple molecules and
macromolecules.
Initial molecules and macromolecules are called monomers are called
polymers obtained by polymerization were formed when the same
monomer and copolymers were formed when the monomers are
different.
Polycondensation is linking monomers with the elimination of
substances
with
small
molecules
(water,
ammonia,
etc.).

25

CHAPTER 2

Macromolecules and do not preserve the same ratio of constituent


atoms as monomers.
Polymerisation and polycondensation processes are carried out
under the action of heat, pressure, or radiation in the presence of
initiators. This gives the building materials such as organic even less
volatility and structural durability of physical and mechanical
characteristics.
Structurally, the organic macromolecules can be presented in
three ways: dimensional structure, branched structure (two dimensional)
and mesh (three dimensional).
Dimensional organic macromolecules have a thread-like structures, the
main thread is in a zig-zag (fig.2.11.a)
Fig.2.11. Dimensional structure of macromolecules
Substance composed of macromolecules have a structure felting
dimensional (with the wires close - fig.2.11.b) that change reversibly
under the action of external loads of low intensity, which is why these
structures were called elastomers. Under the action of external loads
dimensional macromolecules bound and placed parallel (fig.2.11.c),
achieving a targeted structure which vanishes at the outer end tasks.
Elastomers are characterized by high elasticity and solubility in
organic solvents to which the wires are liofili allowing drawing and film.
Lamellar structure tree has branched macromolecules consisting of
chains with many branches (fig.2.12) and are sparingly soluble in organic
solvents
Fig.2.12. Branched macromolecule structure
Macromolecules with mesh (fig.2.13) is formed by branched
macromolecules dimensional or links (called link crosslinking) valence or
bridges.
Fig.2.13. Mesh structure with the structure of macromolecules
Number of links leads to the formation of structures with different
properties as follows:
In a small number of links to get a loose mesh that acts as an
elastomer.

CHAPTER 2

26

With the increasing number of links, the structure becomes more


dense and the polymer becomes insoluble in organic solvents but swells
in the presence and under the action of external applications and the
plastic strain shows that such structures are called plastomers. Some
plastomers can easily handle moderate heat - plastomers thermoplastic
- without structural changes, or suffer structural changes in the heating
process (polymerization processes) forming thermosetting plastomerii.
If the number of connections is sufficiently high crosslinking
polymers are obtained with three-dimensional structure are rigid,
insoluble in solvents and do not inflate their presence, but decompose
on heating is characterized by good corrosion resistance but high brittle
(not withstand shocks mechanical).
Polymer Degradation and aging
During the processing and use of polymers and plastics containing
it they suffer from unfavorable changes in the characteristics. These
changes are due to demands being placed on the material during
processing (mechanical or thermal stresses), and actions while using
external agents (factors of climate, sunlight, physical and chemical
agents, etc..).
Modifications to polymers and plastics during processing and use is
called aging and degradation of plastics.
Aging is manifested mainly by altering the structural or physical
features such as:
Colour change or spots;
Opacifying;
loss of suppleness;
increasing fragility;
the appearance of cracks, holes, breaks local
The reduction of physical properties - mechanical;
Change the unfavorable properties of the products decreases the
amount of use by making them unusable in some cases.
Volume and type of polymer degradation are specific and
depend on: the structure of polymer blends components, manufacturing
methods, environment, etc. requests during use.
Officers determined the degradation reactions are:
physical (heat, light, climatic factors);
chemical (oxidation, hydrolysis, etc.).
Degradation reactions may be:
scinziunea chain reactions and Depoly;

CHAPTER 2

27

without scinziunea chain reaction.


Properties change during the aging process are due to the
following principle:
breaking the chemical bonds of the polymer;
breakage of chains;
new groups forming reactions;
formation of hydrogen bonds;
dispersal or the formation of regional guidelines (crystallizations).
Climatic factors that determine these processes are: solar
radiation, oxygen or ozone, humidity, precipitation, wind, atmospheric
moisture. The most important is the degradation under the sun which is
considered a degradation which is based on photochemical absorption
by the quantum link polymer of the ultraviolet energy.
The technical construction in general and in particular the
following polymers are used:
Thermoplastic Polymers
Polyacrylates derived from polymerization of acrylic acid,
methacrylic cloracrilici have the following properties: clarity and
transparency (light transmission coefficient ca. 92%), good resistance to
aging and chemical action, good dimensional stability and mechanical
strength. Occur in slabs, granules or beads. It is mainly used as adhesives.
Polyamides are products resulting from the polycondensation
between poliacizi polyamide. It may take the form of powders, granules,
sheets calendered, extruded, fiber. Polyamides can be tinted,
translucent products give good mechanical properties, especially
elongation at break. Melt between 150 and 2700C.
Polycarbonates are transparent thermoplastics clear color,
odorless, tasteless low water absorption, with good resistance to acids
and petroleum products, good resistance to weathering, even in
unfavorable weather conditions. They have a good dimensional stability
and low water absorption, good mechanical strength, especially in
shock. It can operate in a temperature range from-1000C to 1350 C. At a
temperature of 5000C is autoinflameaz.
Polyethylene basic formula - CH2 - CH2 - CH2 - come in two forms,
viscous liquid for lubrication and solid translucent plastic.
Depending on the polymerization system can be high pressure
polyethylene, medium and low.
Polyethylene is a thermoplastic material with greasy touch, flexible,
with flexibility to thin, tasteless, odorless, nontoxic decomposition

CHAPTER 2

28

temperature close to 3000C, 1150C soften around the temperature and


becomes brittle as the temperature 250C.
Polypropylene is a thermoplastic material colorless and odorless
with a better resistance to heat than polyethylene, and also with certain
physical characteristics - superior mechanical, such as tensile strength,
stiffness, reduced water absorption. A disadvantage of polypropylene
with polyethylene is reduced resistance to UV radiation. It comes in
granular form.
Polystyrene is based on styrene monomer with the formula C6H5 CH = CH2, molecular mass ranging from 70,000 to 800,000 and it looks like
a powder colorless, odorless, nontoxic, but for ease of processing
changes in natural or colored granules. Operating temperature is low
(65-950). In terms of polystyrene is used in many types
General purpose polystyrene, processed easily and is resistant to
shock, can not be used at high temperatures.
heat resistant polystyrene has a softening point at 950C is
obtained by the polymerization process as easy. It is transparent, slightly
stained and has a high resistance to solvents.
Polystyrene shock, also obtained by copolymerization, has a
tensile strength and elongation shock and double the general purpose
polystyrene.
Cellular Polystyrene obtained by expanding the general-purpose
polystyrene has a density between 15 and 300 kg/m3 (which determines
the scope of use in construction and a low coefficient of thermal
conductivity.
Vinyl polymers. Vinyl compounds based on radical CH2 = CH and
derived from ethylene. They are thermoplastic materials with a softening
point below 1000C, have a relatively good stability to the action of heat,
light and chemicals, are insipid, odorless and nontoxic.
The main representatives of the group are vinyl polymers:
Polyvinyl chloride (PVC) substance colorless, tasteless, nontoxic,
and depending on the system can be emulsion or suspension
polymerization. They are used only rarely, but when mixed with
ingredients (plasticizers, stabilizers, diluents, lubricants, fillers, pigments)
that improves the processing properties and behavior over time.
Commercial forms are presented PVC - your are training after
puberty, emulsions, solutions, adhesives, semi-hard and soft (tubes, pipes,
plates, profiles), hard and soft sheets and films, fibers, cellular products,
plates and blocks . PVC - is the remarkable resistance to acids, alkalis
and alcohols.

CHAPTER 2

29

vinyl Poliacetatul based on vinyl acetate monomer. Obtain a


material colorless, tasteless, transparent, with a density of 1200Kg/m3
stable at temperatures from-100C up to +600 C. It is supplied as an
aqueous emulsion used in painting.
polyvinyl fluoride polymer is a white or yellowish crystalline part
with a softening temperature between 70 - 1500C, non-flammable,
odorless, nontoxic, very resistant to chemicals.
Polyurethanes are polymers complex, in the form of granules which can
be injection and compression process and reflected in the composition
of varnishes, adhesives and cellular products are resistant to aging well,
the action of petroleum products and use temperatures up to 1300C.
The main groups of polyurethanes are:
Polyurethanes linear polyamides like structures have properties
but are close in color during processing and in the presence of air. Fuses
are easily produced, flexible, resistant to alkalis, alcohols, mineral oils.
Polyurethanes are obtained by copolymerization and crosslinking of this group are:
- Urethane oils with heat stability up to 2800C;
- Dust formation, together with wood flour allow the formation of
large parts with high electrical resistivity;
- Rigid and flexible polyurethane foams, the physical - made by a
superior mechanical foaming process.
- Urethane adhesives are high strength, elasticity, heat stability and
high resistance to solvents.
- Highly resistant urethane rubber chemicals
Polymers termorigizi
Aminoplastele are polymers characterized by group-NH3, are
generally insipid powders, odorless, colorless, thermosetting, stable to
light and heat, very good resistance to the action of alkalis, weak acids,
alcohols, acetone. Use the form pure polymers (resins) for processing by
pressing the form of laminated, glues and adhesives, cellular products.
Fenoplasticile are obtained by polycondensation of phenols with
aldehydes or ketones. The products are thermosetting natural coloration
from yellow to brown and odor resistance to heat, flammable almost
completely resistant to abrasion, high toughness, dimensional stability,
resistance to solvents and moisture. It is used for the stratificatelor (paper,
cardboard, fabrics, glass fibers), adhesives or dry form solutions stable at
hot and cold water and cellular products obtained by foaming used as
thermal insulation.

CHAPTER 2

30

Polyester and alkyd polymers resulting from the reaction between


an acid and alcohol. These polymers have a three-dimensional structure,
resulting in strengthening the action of a catalyst without releasing
volatile products. They have a high stability during storage, a rapid
hardening by polymerization forms at low temperatures, high
mechanical strength, heat resistance (temperature deformation at
3000C), chemical resistance.
Epoxy polymers are obtained by a process of polycondensation of
glycol and polyol. Are known as epoxy resin or epoxy. It is presented as a
viscous liquid and dust formation, liquid used for impregnation, adhesives
and laminated products as solid yellow to dark yellow, hard, but freabile.
Epoxy polymers show a high adhesion to metals and exceptional
chemical resistance.
Furan polymers based on furfuryl alcohol. In mixtures with
extraordinary resistance to the action fillings give strong bases and nonoxidative oxides, the products are infused at the final stage and insoluble
and used for roofing, cement refractory stratificatelor achievement,
wood.
Plastics based on natural proteins are polymerized products
featured below other plastics, have affinity for water and color can be
different tab.
This category includes:
Based on casein, thermosetting materials known artificial Galal.
Have a misconduct moisture, weak acids, alcohols, oils. It comes in the
form of tubes, plates, rods.
Based on Zein (corn gluten) in the form of white powder, soluble
in methanol and ethanol aqueous solutions, glycols, esters. Livraez of
film is resistant to water, fat and temperatures up to 1800C.
soy flour is made from soybean fibers through which the wire or
chemical resistant.

2.9. Structure silicates


Clark's high silicon Complexes with oxygen and the metal ions are
complex substances containing these combinations generally called
silicates, find themselves in one form or another in most building
materials.
Silicates may be natural, entering the composition of rocks and
used as construction materials or raw materials for construction materials

CHAPTER 2

31

and artificial silicates such as clinker silicate-based cements, ceramics,


etc..
Silicates are salts of the various silicic acids, whose chemical
composition can be represented by the formula type ySiO2 gross. zH2O
the y and z are variables. Y acids are called polisilicici 1.
Chemical combinations of silica, the most common are:
Silica (SiO2) with crystalline structure (quartz) core constituent of
the rocks and amorphous structure, present in volcanic ash or
sedimentary rocks (volcanic tuffs, pozzolana, diatomite.).
Silicic acids formed hydrated silica, slightly soluble or insoluble, unstable,
by polycondensation shifted from one form to another: ortosilicic acid
(SiO2. 3H2O) metasilicate (SiO2.H2O) disilicic (2SiO2.H2O) until finally the
complete elimination of water resulting polymer (SiO2) n.
Aluminosilicaii hydroxide formed from silicon polycondensed
(SiO2) n, where x groups were replaced with clusters of silicon oxide,
aluminum oxide (Si (nx) AlxO2n) and the x-valence due to the difference
between Si and The structure of the newly formed complex meanings
about the x unbalanced with opportunities to combine with various
cations, resulting feldspaii, which make up about 50% of the earth's
crust.
Main feldspar are:
Bleaching - sodium feldspar (6SiO2. Al2O3.Na2O)
ortoclazul - potassium feldspar (6SiO2 Al2O3 H2O)
anortitul - calcium feldspar (2SiO2. Al2O3. CaO)
Feldspaii can jell together in different proportions to form a series
of feldspar, is the most important series of feldspar calc-sodium and
sodium-potaso feldspaii.
Under the action of natural water a part of positive ions of metals
are removed by hydrolysis and feldspar in the crystalline network is
chemically bound water, the newly formed structures called the mice.
Carbonated water completely eliminated in mice positive metal
ions, which pass into clays, hydrated alumina-silicate with the general
chemical structure mSiO2. nAl2O3. pH2O.
Silicon compounds may have different structures from simple
molecules form a tetrahedron (SiO4) 4 - as revealed in X-ray diffraction
investigations, oxygen free valences (fig.1.24.a) can bind metal ions or a
silicon atom from a neighboring tetrahedral group, making complex
structures.
Fig.2.14. Simple structure of silicates

32

CHAPTER 2

After way of linking the tetrahedral groups are obtained the


following main structures:
Insulated Structures (island) may be formed from a single
tetrahedron or more connected by sharing oxygen atoms (fig.2.14. B, c),
loads of free positive ions being neutralized by metals.
Isolated structures can be found in: olivine (Ca and Mg silicates) that
occur in igneous rocks and used in the manufacture of refractory bricks
or extraction of magnesium and some brightly colored varieties are used
in ornamental work, mullite - composed of isolated silica tetrahedra
group setting (AlO6) 9 - 3Al2O3 2SiO2 chemical structure of the ceramics
appears giving them mechanical and chemical resistance.
Chain structures can be:
Simple chain structures (fig.2.15.a) is formed from the union by
bridging oxygen tetrahedron, the macromolecular chains infinite pooling
of atoms occurring ions (SO3) 2 -;
Double-chain structures (band) results from the union of two simple
chains by sharing of oxygen atoms (fig.2.15.b), the radical ion structure is
being repeated (Si4O11) 6
Fig.2.16. Band structure of silicates
Double-chain silicates with the structure because of the weak links
easily unravel simple chains as shown tremolite fibers and cristolitul
(hidrosilicai calcium and magnesium) components of the asbestos used
as reinforcement material, heat absorbing and insulating, sealing, etc. .
Planar structures (laminated) are made of the joint plan by sharing
the oxygen atoms, the band formed by six tetrahedral structures
constrained the form of rings, the radical ion structure which is repeated
(Si2O5) 2 -. This structure we meet at: small, used as dielectric material
and decorative plasters, talc (magnesium hidrosilicat (3MgO 4SiO 2H2O)
and components of clay - kaolin (2SiO2 Al2O3 2H2O) and
montmorillonitul (Al2O3 4SiO2.. H2O).
Kaolin is composed of independent packets (fig.2.16) consisting of
hexagonal rings of tetrahedra (SiO4) 4 - The top aluminum octahedra
which link type [AL2 (OH) 4] 5 -, placing layers one over the other
packages under orders a certain inclination, which determines the
stability of the different links (eg, kaolin, 1000 tilt between the packet 12
'is dehydrated between 4000 and 4500 C while dielitul the angle
between 96,050 packages' and part of the same category as kaolin, it
dehydrates between 5100 and 5750C). Tetrahedra and octahedra layers

33

CHAPTER 2

of kaolin layers form an independent package, unbound by the next


layer, which explains cleavage kaolinite blades. Kaolin clay is the main
component used in the ceramics industry (from the porcelain bricks).
Fig.2.16. Flat structure silicates
Montmorillonitul has the structure (fig.2.16.b) composed of two
layers of tetrahedra (SiO4) 4 - hex willing and related plan of
AlO4
octahedron (OH) 2
7 - between structural groups by absorbing a set
quantity variable water that gently remove from heat and ensure the
physical properties (plasticity, strength, etc.). montmorillonitice of clays
used in binders.
Spatial structures (dimensional) result from reciprocal linking,
unlimited three-dimensional tetrahedron with all vertices by sharing
oxygen atoms. Such structures occur in quartz and feldspar.
Quartz (crystalline silica) SinO2n formula is one of the most common
mineral in most rocks is meeting with technical utility, especially in the
optical industry, electrical and building materials in the manufacture of
glass, fine ceramics, etc..
Feldspaii (or alkali aluminosilicates alcalinopmntoi) have
spatial structure consisting of groups (SiO4) 4 - (AlO4) 5 - arranged in rings
of four tetrahedra. Tetraedrii Because of (SiO4) 4 - all have valences of
oxygen saturation and every tetrahedron of (Al O4) 5 - remains one free
valence, it is neutralized by positive ions of metals (Na, K, Ca), which sits
after giving some planes in the crystalline network feldspar cleavage
feature. Feldspaii used in ceramics and glass industry.
2.10. Water
Water plays an important role in many natural and technological
processes, often being essential or conclusive. In addition to its vital role
in the natural environment on earth, is water component in the
preparation of building materials, ceramics, concrete, mortar, etc.. ;
Influences durability of materials and construction elements mostly
unfavorable, or are certain construction tasks (reservoirs, dams, pipelines,
etc.)..
The waters have aggressive actions on materials which can lose
activity (cement, lime and plaster), the warp (wood), diminishes some
physical-mechanical and dielectric properties (paper, textiles, etc..).
Emphasizes the destructive action of water when porous materials are
associated with the crystallization of dissolved substances in water or

CHAPTER 2

34

freezing processes accompanied by increase in volume and introducing


efforts.
In such water is found in all states of aggregation: vapor in the
atmosphere, liquid surface water (hydrosphere, springs, rivers), solid
when the temperature drops below 00C (rime, hoar-frost, snow, sleet).
2.10.1. Water in nature
The atmosphere contains water vapor concentrations vary with
temperature and pressure, coming mostly from evaporation of oceans
and seas and to a lesser extent, glaciers and snow evaporation. Water
vapor in the atmosphere condenses to form clouds, fog, rain, hail or
snow, when it reached that temperature the saturation pressure in the
form of dew or hoar frost, when water condensation occurs on cold
surfaces. Atmospheric water forms "stormwater."
Higrosfera consists of oceans and seas to occupy 71% (3,62.108
km2) of total land area (km2 5,1.108) and is 10% occupied by glaciers.
Higrosfer water volume is estimated at around 1,37.109 2,9.107 km3 km3
and glaciers. If all the glaciers would melt, ocean levels would rise by
about 80 m.
Ocean water contains about 35 g salt per liter (27 g are NaCl).
Interior seas or higher salt concentrations (Mediterranean Sea) or lower
(Black Sea with about 17.7 g of salt per liter to 14 g NaCl). They were
identified ocean water some 70 items of which 20 have higher
concentrations.
Spring water and rivers. Meteoric water, once on earth can cross
the porous layers (sand, humus, etc..) To reach an impermeable layer
(usually clay) that forms the blade above the underground water
(ground water) or may remain on the surface moving under the action
gravity (streams, brooks, streams, rivers) which may reach the oceans or
lakes gather. Groundwater can be resurfaced in the spring, feeding the
streams.
The chemical composition of water varies with the nature of the
rocks that have been in contact. River water is increasingly polluted with
industrial waste, with adverse impacts on the environment and is one of
the major concerns of contemporary life.
An important part of spring water rich in mineral waters is the solid
or gaseous substances which are used as medicinal water.
Drinking water comes from, in general, spring and underground water in
rivers and lakes rarely (accumulation) but require purification before

CHAPTER 2

35

being consumed (purification can be chemical, mechanical and


biological).
Due to the large spread of water on the earth, it was necessary
preparation of chemical but a natural water purification, within certain
limits.
1.10.2. Chemistry, physical structural characteristics
Until the second half of the eighteenth century, water was
considered the body easy. In 1776 the chemical structure of water
Macquer observed hydrogen-air combustion. Composition by volume of
water has been established by Gay Lussac in 1805 and Humbold weight
and composition have established in 1820 Berzelius and Dulong.
Chemical formula of water is composed of an oxygen atom and
two hydrogen atoms covalently, achieving a symmetrical molecular
structure due to the oxygen atom valences orientation at an angle of
1040.
Molecular density of water is 18, derived from the density of vapor
at high temperatures and corresponds to the formula H2O.
Molecular weight of liquid water, determined by freezing or
ebulioscopic methods, is higher than would correspond to the simple
formula of water (H2O). This is because the liquid water are in addition to
single molecules of H2O and associations of water molecules.
Associations of molecules linked by bridges made by two hydrogen
(H2O) 2 or more (H2O) n simple molecules and explains the physical
anomalies of water.
There is no well defined associations, each water molecule tends
to surround himself with other molecules. Associations are formed in liquid
water two to six molecules of H2O, but this is only a short time.
Associations of water molecules unravel and recover steadily, in a way
that the total number, statistically associated molecules from a given
quantity of water to remain constant at a given temperature.
The sudden melting of the ice break 15% of the total number of
hydrogen bonds in its structure, to unravel 400C about 50% of links; 1000C
unravel all the hydrogen bonds, so that only water vapor molecules are
simple.
The crystalline water network (fig.1.18) as was determined by X-ray
diffraction, each water molecule is surrounded by four other molecules,
so the O atoms form a tetrahedron. Go on forever, this makes a
hexagonal structure. Valence angles in this structure increases from 1040
to 109.50 and HO covalenele elongate from 0.99 and OO distances

CHAPTER 2

36

are fixed at 2.76 . This structure explains the electrical dipolmomentul


higher H2O molecule in ice (2.5 D) than water vapor (1.84 D).
Ice presents seven polymorphic states depending on pressure and
temperature (from 00C loose lens system and the atmospheric pressure
to 2050 atm and tetragonal-220C, the cubic system at 2100 atm and 34.50 C.
Pure water at ordinary temperatures is an odorless liquid, colorless
and colored in blue thin layer in a thick layer.
Water freezes at 00C, turning into ice and boils at 1000C, forming vapor.
Heat of vaporization of water is (539.1 cal / g) and heat of melting ice is
(79.41 cal / g).
Heat of vaporization is transferred from vapor to condense and
heat of melting ice is given when the water freezes. This exchange of
heat, continuing the transformation of water masses is found on earth
makes the earth to maintain an average temperature between winter
and summer, almost equal.
Density of ice at 00C is 0.9168 kg/m3 and liquid water at the same
temperature is 0.999 kg/m3. Therefore, a volume of liquid water by
freezing its volume will increase by approximately 9.8% (fig.1.19) having a
particular importance and technical nature.
The specific weight of water varies with temperature as follows:
increase from 00C to +40 C, and then decreases. This has special
significance in nature. Surface water (lakes, rivers, etc..) Cooled to lower
temperatures, water is heavier on the bottom and allow the surface
water temperature rises and hence higher specific gravity lower. After all
water table has reached 40 C, the surface layer cools, reaching 00C
when the water freezes. Specific gravity of ice is lower than the water at
00C, the ice will remain on the surface. If the water layer is thick, the
bottom water remains liquid, so a higher temperature of 00C, so aquatic
creatures can survive the winter.
Melting and boiling temperatures of water were abnormal in
comparison with neighboring elements in the periodic hydrides. Water is
liquid at ordinary temperature, while neighboring hydrides elements
present in a gaseous state (Table 2. 3).
Tab.2.3.
HF S structure HO2 H4 CH4 NH3 HCl
Melting temperature 00 -830 -760 -1840 -1850 -115
Boiling 1000 -1640 -330 -112 -85 19.5

CHAPTER 2

37

Anomalies of physical properties of water (increasing volume at


freezing, melting and boiling temperatures, heat of vaporization, surface
tension etc.. H2O molecules is due to association by hydrogen bridges
(see 1.6).
2.10.3. Natural waters. Water hardness
Natural waters are solutions in water: gas (O2, CO2, NH3, H2S), salts
(carbohydrate, sulfates, chlorides, nitrates, etc..) Or organic substances
(humai, breakdown products of proteins) or containing mineral matter (
powders, banks, sand) or organic.
The composition of natural waters depending on the source: the
waters of dissolved gases in the atmosphere prevailing precipitation,
groundwater and surface waters dominated industrial salts are dissolved
and the solutions or suspensions of mineral or organic substances.
The presence of substances dissolved or suspended in natural
water use restrictions or cause difficulties in borderline cases and make
them unusable. Thus, soluble impurities have a corrosive effect on water
evaporation, crystallized or poorly soluble salts are deposited, resulting in
efforts that can destroy or change the structures of solids, change the
boiling and freezing temperatures, etc..
In natural waters can be found corresponding to approximately 30
combinations of elements, but for technical and construction industry in
general interested in the presence of calcium and magnesium salts,
which is the basic criterion for limiting the use.
Water hardness is defined by the percentage of calcium and
magnesium salts. Hardness due to the presence of calcium and
magnesium bicarbonates is called temporary hardness (dt) and
hardness determined sulphates, chlorides, nitrates and other salts of
calcium or magnesium hardness permanent form (dp). The amount of
temporary hardness and permanent hardness is total hardness (DT).
Temporary hardness (caused by bicarbonate) can remove from
boiling water, when passing the bicarbonate insoluble carbonates that
precipitate.
Permanent hardness (consisting of Ca and Mg salts other than
bicarbonates) can not be removed by boiling in water persists. If calcium
and magnesium salts are a small scale, are called soft water and high
water content is a tough call.
Conventionally, water hardness expressed in degrees of hardness
(d0). A degree of hardness corresponds to a CaO content of 10 mg per
liter of water.

CHAPTER 2

38

After the value of the degree of hardness, the waters are classified as
(tab.2.4).
Tab.2.4
Characteristic of water hardness
<50 Very Soft
Soft 50 ... 100
100 ... 200 Middle
Tough 200 ... 300
> 300 Very Hard
Hard water can not be used in boilers, the operation of pipelines
(salts deposit on pipe walls, and difficult to reduce the flow section) in
heat exchangers (deposited salts reduce thermal conductivity) in some
processes (preparation of concrete and mortars).
Water hardness which does not allow use in certain areas should
be subject to a complex: preparation processes - to reduce impurities treatment processes based on one of the following:
By mechanical removal of impurities is accomplished by
decanting (separation) in large tanks (settlers) by the separation of
suspended impurities is achieved under the action of its own weight.
Water, partially purified (clarified) is then filtered by passing through
layers of gravel and sand.
Coagulation is achieved by introducing colloidal impurities in
water of chemicals called coagulants, which carries agglomeration and
sedimentation of very fine dirt bands such large formats (see Chapter 3),
after which water is filtered through sand filters. Coagulanii most often
used are: aluminum sulphate, ferric sulphate, ferric chloride, etc..
Degassing seeks removal of gases, mainly aggressive (O2, CO2)
dissolved in water and heat is conducted in facilities called degassed.
Chemical softening seeks removal of ions that cause water
hardness (Ca 2 + and Mg 2 +) using the following methods:
Softening with lime and soda, the lime [Ca (OH) 2] and soda
(Na2CO3) lead to the formation of sparingly soluble carbonates which
precipitated
Ca (HCO3) 2 + Ca (OH) 2 + 2H2O
2CaCO3
MgCl2 + Na2CO3 +
2NaCl MgCO3
Softening trisodium phosphate is used when water is to achieve a
degree of hardness as a (d0 10), removal of impurities is achieved by
precipitation of calcium phosphate and magnesium.
3Ca (HCO3) 2 + 2Na2PO4 CA3 (PO4) 2 + 6Na) (HCO3)

CHAPTER 2

39

MgCl2 + 2Na 3 PO 4 Mg3 (PO4) 2 6 NaCl


I
on exchange softening using special filters containing porous
solids, insoluble are able to retain cations and anions in water. As ion
exchange using natural mineral hydrated sodium aluminosilicailor family
(zeolite) or organic substances - resins (allowed).
2.11. Air
The air is gaseous envelope of Earth, called the atmosphere and
coating has a thickness of up to 3000 km (where the air is rarefied and
ionized).
2.11.1. Composition
Air is a mixture of gases whose composition by volume is 78%
nitrogen, 21% oxygen, 1% other gases (carbon dioxide, water vapor, rare
gases and other gases from industrial activities). In the laboratory, air
composition is determined experimentally by oxidation of white
phosphorus in a limited amount of air:
P4 + 5O2 2P2O5 (white smoke)
Gas remained, which does not burn or sustain combustion is
nitrogen and has a volume of four times that of oxygen, resulting in that
a mole of air is a mixture of O2 and N2 in the molar ratio of 1:4.
2.11.2. Physical properties
Accurate determination showed that weighs 1293 g 1liter air at
normal temperature and pressure (273.15 K (0 C) and 1 atm). Normal air
pressure that presses on the earth's surface at sea level and at 00C is
daN/cm2 1033. This pressure balances a column of mercury 760 mm
high, or 1 torr.
Air density is taken as a point of comparison in determining the
density of other gases. Average molecular weight of air, determined
experimentally, is 28.9.
Air is a colorless, odorless, tasteless. It is expandable and
compressible. Solubility in water is very low. There is a good conductor of
heat and electricity. It can be liquefied by strong compressions, followed
by sudden adiabatic expansion when the temperature drops to - 1930C
(considered liquefying air temperature). Air liquefaction is carried out by
special machines called cars Linde or Claude. Air is a clear liquid with
bluish reflexes and flows like water. Keep in Dewar vessels (double-walled

40

CHAPTER 2

glass vessels, silver, of which the air out). One thing worth mentioning is
that substances placed in liquid air changes its properties:
flowers, meats, fruits become brittle;
rubber loses its elasticity and is also brittle;
mercury solidifies and becomes malleable;
produce lead to striking, metallic sound (specific).
Liquid air is used to obtain very low temperatures and also to study
the behavior of substances or materials at such temperatures. Of liquid
air by fractional distillation, separated oxygen, nitrogen, rare gases.
2.11.3. Chemical
In terms of chemical properties have air gas components. Due to
the presence of oxygen, air support combustion. But burning is less
intense than in oxygen because nitrogen reduces oxygen action. Air is
essential for life. man can live weeks without food, several days without
water, but can not survive without air or 6 minutes. Man eating,
breathing, 12 kg of air in 24 hours.
In addition to the maintenance of life and as a source of CO2 for
plants, the air is of particular importance in the industry. In ferrous and
nonferrous metallurgy, all oxidation processes ore roasting and occur
only in the presence of air. The research laboratories are used to obtain
very low temperatures. Mixed with coal dust, in certain circumstances,
be used as explosives in underground works.
The sheath air of our planet depends on:
preserving the earth's heat;
the role perfectly natural filter for certain solar radiation;
protection from the meteor shower;
achieve optimum water flow;
the possibility of transmitting sound, Radio etc..;
conducting flight operations;
providing the conditions essential to life.
2.12. Macrostructure materials
Materials may have a unitary structure in a volume sufficient to
achieve a majority element of construction but have a composite
macrostructure, made from fixing a matrix of components that are
present in different forms (fig.2.17).
Fig. 2.18. Macrostructure materials

CHAPTER 2

41

Fiber, yarn, sticks (fig.2.18.a.) - Two bodies approximately equal


sizes and much lower than the third, with an elastic behavior - made of
metal, glass, organic structure, etc..
Particles (granules) (fig.2.18.b.) - irregularly shaped bodies in
pieces, with sizes ranging between 0.2 mm and 150 mm, sand, gravel,
granulated slag, etc..
Powders (fig.2.18.c.) - very small particles or react chemically inert cement, plaster, filler, etc..
Cuts (fig.2.18.d.) - bodies of regular geometric shape (cubic or
prismatic Typical) - bricks for masonry buildings, paving, etc..
Laminated (fig.2.18.e.) - pieces with constant section and length
dimensions very large compared to the section made of metal, wood,
plastics etc..
Plates (fig.2.18.f.) - Two bodies approximately equal sizes and
much higher than the third and rigid - tiles, floor tiles, plywood etc..
Sheets (fig.2.18.g.) - very small plate thickness, elastic and can run
without compromising the structure - cardboard, tin thin plastic sheets,
etc..
The union of these structures resulting congestion or construction
elements with single aspect such as:
- Agglomeration of particles resulting from mortar, concrete;
- Binding cuts in masonry, floors;
- From sheet waterproofing etc is done.
Fibers, hairs, dust particles and sintering non pile forming materials
(bulk).

CHAPTER 3

3. STATES OF MATTER
Matter can be presented in 4 states: plasma (99.98% of the
matter in the universe), gas, liquid and solid. For the study of
construction materials it is in our interest only the states in which matter
is found on earths conditions temperature and pressure meaning
the states: gas, liquid and solid.
In a material found in well determined physical conditions
(temperature and pressure) there are 2 tendencies that act in opposite
directions and lead to the realization of its own state:
The first tendency is due to the forces of interparticular
bondage (Van der Walls forces, hydrogen bonds etc.) under the
action of which the particles tend to dispose themselves orderly,
realizing a state of equilibrium poor in energy;
The second tendency is due to the thermal agitation of
particles which never disappears, its size depending on temperature
and leads to the destruction of the orderly structure.
Depending on the share of these tendencies, in a material one
of the 3 aggregation states can be realized
The solid state in which the tendency to order
predominates, the thermal agitation of particles manifesting
under the form of small amplitude oscillations around a position
of equilibrium (considered fixed in space) and for this reason
solids have own volume and shape.
The liquid state in which the constituent particles, under
the influence of the thermal agitation, execute a movement of
oscillation and one of translation, without producing major
modifications on the distance between particles (which are
found at a medium distance.
The gas state defined by
attraction forces, under the action
constituent particles have a chaotic
from this one result the status with
volume.

very small interparticular


of thermal agitation, the
translation movement and
indeterminate shape and

3.1. Solid state


The particles find themselves in front of each other at the

CHAPTER 3

distance do (resulted from the ordinate tendency) specific to each


material for a given temperature.
3.1.1. Crystallized solid state
Solid matter which has the tendency to ordinate their
component particles (ions, atoms, molecules) in order (regular
geometric pattern) characterized through minimal internal
energy, form the crystallized solid state.
In crystallized solids the order of the component particles is
present in all the materials volume.
The ordinate arrangements, in space, of places which can
be occupied by the particles of crystalline state, determine a
spatial network, called crystalline network.
The places were the particles are dispose in the crystalline
network are called knots of the crystalline network.
A unit from the network by whose translation, on the three
directions (edges) a crystalline network is obtained, it's called
elementary cell.

Fig 3.1 Elementary cell


The directions of the edges of elementary cell are called
crystallographic axes. The relative sizes of the elementary cells edges
form the constants of the crystalline network.
As main geometrical elements in the crystallized solids
classification, the relative sizes of the edges a, b, c and the angles , ,
from elementary cell, will be considered.
All crystallized solids can form seven types of elementary cells
called crystallization systems; each of the crystallization systems can
be presented in many class of symmetry (in all 32) fig.3.2.
The 7 lattice systems

CHAPTER 3

triclinic (parallelepiped)

simple

centered

simple

basebodyfacecentered centered centered

simple

bodycentered

monoclinic (right prism


with parallelogram base;
here seen from above)

orthorhombic (cuboid)

tetragonal (square
cuboid)

rhombohedral
(trigonal trapezohedron)

hexagonal (centered
regular hexagon)

cubic

simple

body-centered face-centered

CHAPTER 3
(isometric; cube)

Fig.3.2. Crystallization systems


The crystals are solid with polyhedral form, delimited by
sides which are intercepted in the edges and the edges meet
the corners (knots).
The arrangement of the particles of the crystalline networks
knots leads to the
realization of symmetry elements series which define the symmetry
degree of the crystal.
The symmetry elements are:
The symmetry center the imaginary point in report which all the
sides, the edges and the knots are symmetrical two by two.
The symmetry axis the imaginary line in report which at the
elementary cells rotation, the particles occupy the same position of
two, three, four and six times (the symmetry axis will be binary, ternary,
quaternary or senary).
The symmetry plan the imaginary plan that splits the
elementary cell in two identical parts where are found one by another
as the mirror imagine.
With how much a crystal has more symmetry elements the
symmetry degree is bigger the structure will be more compact, with
stronger bonds. Thus, the cubical and hexagonal systems are having
the most symmetry elements and forms compact solids, and are
characteristic to most of the metals.
Nature of the particles from the knots and the bonding types
between the particles determine the crystalline networks:
a)
Ionic networkss formed from ions of contrary signs,
monatomic or complex ions, alternative placed in the networks knots
and between which is achieved connections of electrostatic nature.
The sodium chloride (common salt) forms a crystalline ionic network,
with monoatomic ions of Na+ and Cl-; the calcium carbonate and the
calcium sulphate form a crystalline network with Ca2+ ions and CO32- and
SO42- complex ions. Due to the weak connection forces (electrovalent)
the solids with ionic networks are characterized by hardness, medium
melting temperatures and mechanical strengths, brittle fractures etc.
b) Molecular networks realized with molecules in the network
nodule which connect trough week Van der Walls forces in the case of
polar molecules and electrostatic forces in the case of the polar
molecules with big dipole moment as well as trough hydrogen
connections(as ice). The majority of the organic substances crystallize

CHAPTER 3

trough such networks. Crystalline substances with molecular networks


characterize trough low toughness, low melting point and so on.
c) Metallic networks with the particles under ionic shape and
metallic connections, which leads to a more compact
system(crystallization in a cubic and hexagonal system with the highest
symmetry degree). Metals characterize trough specific glisten, high
thermal and electrical conductivity, superior mechanical resistance,
high deformational properties until breaking and so on.
Crystallized solids characterize trough the energy of the
crystalline network, which represent the energy needed for separating
the constituents of the crystalline network at a distance where they
cannot interact between them and it is equal with the energy liberated
at the forming of the crystal using the constituent particles in the
hypothesis that these would be found in the status of ideal gas, at the
temperature of the crystal. From the energy of the network depends
the elasticity, toughness, mechanical resistance, melting point and the
dissolution of the substances. Also, the stability of a crystal is direct
proportional with the energy of the crystalline network.
In nature the crystallized solids dont form an ideal shape (ideal
networks), in which case it would be necessary a huge amount of
energy for disrupting the balance of the interior forces, in order to enter
a chemical reaction; the natural crystals (real crystals) present different
imperfections forming real networks.
The imperfections can appear during the forming of the
crystalline network or deteriorate due to the action of the exterior
forces along the formed crystallites.
Structure imperfections arisen during the forming of the crystalline
network are owned to (fig 3.3):
- Vacancy of some particles from the networks knots, when
among particles remain un-equilibrated;
- Substitution of some networks knots by other particles with
other dimensions that they produce deformation as big as the foreign
particles have bigger dimensions.
- Presence of the same nature particles or foreign particles
between the networks knots followed by the networks deformation of.

CHAPTER 3

Fig.3.3. Network defects


Exterior solicitations producees deformations like the following
types:
- Distortions (fig. 3.4.b) that are produced by wedge shape
actions
- Translation (fig. 3.4.c.) under a sliding form of some pockets ,
one over the other that are accompanied by deformation in the
network, being a form of a scissoring forces;
- Macles (fig. 3.4.d) produced by partial roles of the network over
the macle plane (A-B) under the force of compression.

a.

c.

b.

d.

Fig.3.4. Displacements in crystalline networks


The less the substance is stable at the chemical actions, the more
a network is deformed, because of the dislocations and structure flaws.
At a high rate of flaws and dislocations, a crystalline structure behaves

CHAPTER 3

such as an amorphous solid and the phenomenon is called


amorphization.
The amorphization is used in practice to increase the chemical
reactivity of some materials. Actually, the process consists in grinding
the material which produces a series of dislocations. For example, the
kaolin which in natural state has a crystalline structure, doesnt dissolve
in concentrated hydrochloric acid, but if is subjected to grinding, it
amorphizeises and become soluble in hydrochloric acid (after one
thousand hours of grinding it dissolves in proportion of 58% in diluted
hydrochloric acid, at room temperature).
Grinding some materials together leads to technological
advantages such as reducing the temperature and the reaction time.
Crystallized solids present physical and mechanical anisotropy
(the special features are different at the direction testing variation). This
specific feature permitted to make studies regarding the crystals
network special features, flaws, dislocations and to achieve crystals
recognition from the structure of a mineral or a rock.
The study of crystals with the help of Rntgen rays or in
monochromatic or polarized light is based on the changes of the
characteristics of monochromatic rays crystalline network (reflections,
refractions, double refractions with null results - extension or double
maximum light etc.). It has been determined the distance between the
network plans and between knots, this allowed to be made the first
appreciations above the dimensions of ionic and atomic rays, it have
been put in evidence the structure and dislocations defects, inclusions
etc.
Isomorphism, polymorphism, allotropy
The substances which can crystallize together, in the
same system of crystallization, forming an isomorphic series, are
called isomorphic substances.
Two substances could form an isomorphic series if they have
ionic or atomic approached rays and similar chemical structures
(composed of the same number of ions and atoms) and approached
network parameters. In the case when the ionic rays are different with
less then 10% there are forming complete isomorphic series (chloral and
bromide of potassium, where the ions of Cl and B are replacing each
other in unlimited proportions) and when the ionic rays are different
with more then 10% it could form a isomorphic series limited (the
calcium and magnesium carbonates form the double carbonate
called dolomite, which the Ca2+ and Mg2+ ions substitution can be
realized in a maximum 8% proportion.
Feldspats can form special isomorphic series; so the calco sodium feldspats are stable at any temperature while the albit - orthosis

CHAPTER 3

is stable only at high temperatures and the anortit - orthosis isomorphic


series is stable at any temperature.
The composed substances which can be presented in
many crystallized systems, depending of the finding
temperature, have the property called polymorphism.
The quartz (SiO2) presents the polymorphism characteristic with
the metastable states, important for the study of construction materials.
There exist 3 critic points (temperatures) when are produced reversible
transformations of the quartz. The first transformation takes places at
573 C when alpha-quartz passes in Beta-quartz; the second
transformation is suffered by the quartz at 870 C when it passes in Beta
tridimitium and the third at the temperature of 1470 C when the quartz
is transformed in B crisobalit, because at the temperature of 1713 C its
melting becoming a liquid stage (amorphous).

OC

1713

573

tridimit

870

cristob
alit
sticla de c
uart

1470

topitura

cristobalit

tridimit
cuart
cuart
timp

racire-incalzire lenta
racire rapida

Fig.3.5. Polymophic ransformations of the quartz


The tridinit and cristobalit are stable in some limits of temperature,
but they can show polymorph states, at quick cooling, with different
characteristics ( the tridinit melts at 1670 C etc).
The polymorphic transformations of the cuartz are accompanied
by modifications of volume that can be defects in some obtaining
processes of constructions materials at the burning of briks it may
happen destroys- or the thermal variation behavior of some materials
can be determined - refraction materials, concrete etc.
The substances formed by a single kind of atoms
(elements) which can be presented in more forms of
crystallizations, depending of the temperature they have, have
the property of allotropy.

CHAPTER 3

temperatura (C)

Iron presents the property of allotropy, with high implications in

lichid

1538
1390

ferita cub centrat 2,93 m.10 -10 nemagnetica dizolva max.0,1%C


ferita

906
768

ferita
ferita
timp

cub cu fete
-10
nemagnetica dizolva max.1,7%C
centrate 3,66 m.10
2,90 m.10 -10 paramagnetica
cub centrat 2,88 m.10 -10 feromagnetica dizolva max.0,03%C

Forma de
cristalizare

Parametri
de retea

Principalele
caracteristici

Fig.3.6 Starile alotropice ale feritei


practice. So, the ferrite (0,03 % C impure iron) presents the fallowing
allotropic states : up to 906C it presents in the ferrite state , it
crystallizes in the cubic system forming a structure in shape of a
centered cub (in the center of each cube, which constitute the
elementary cell, it can be found an iron ion); ferrite has magnetic
properties till the temperature of 7680C; Between 768 9060C the ferrite
presents the state (it crystallizes in centered cube system with other
parameters), has paramagnetic properties. Between 9060C and 13900C
the ferrite is in ferrite state (it crystallizes in the centered face cubic
system on each side of the cube it can be found an iron ion. It
presents nonmagnetic properties but it is dissolving the higher carbon
percent (max. 1%); between 13900C and 15280C, the ferrite crystalises
again in the cubic centered system, achieving ferrite state, with
nonmagnetic properties and over 15280C it goes in the liquid state.
Fig.3.6. Irons allotropic states
The different allotropic states of the ferrite it offers to this distinct
characteristics because of the different ionic radius (2,88 for ferrite
and 2,93 for ferrite) and to the different coordinate number (8 for

ferrite and 12 for ferrite). The

ferrite state has magnetic

CHAPTER 3

10

properties, ferrite can be alloyed with the carbon, which penetrates


through diffusion the free centers of the cubes etc.
The materials formed by a very big number of real crystals (the
crystal dimensions are small compared with the material dimensions)
have a polycrystalline structure, to which the anisotropic
characteristics dont manifest in the mass of the material and it obtains
isotropic characteristics (the rocks, the metal case etc.).
Amorphous solides
The solids which dont have an orderly arrangement, in
their entirely mass, to the constitute particles make the
amorphous state, which, through resemblance with the usual
glass, it is named glass state or vitreous state.
Even though at the amorphous solids, the particles are not
arranged in an orderly way, the rontgenographics studies make
obvious the orderly arrangement (the appearance of some week
interference areas).
The amorphous solids are richer in energy than the crystallized
solids and because of that; they are less stable, with the tendency of
crystallization - devitrefication. Because the solid particles movement
for the orderly arrangement is very slow, devitrefication proceeds in a
big period of time, years. In this way, it can be explained why some
transparent materials (glass) become opaque or they are destroyed
because of the pulverization (basaltic rocks) because the pressure of
the volume is increasing in the microcrystal formed by devitrefication.
In comparison with crystallized solids, the amorphous solid
have isotropy from the physico mechanical properties point of view,
an increased fragility and durity, as well. The amorphous solids instability
imposes some special tests to be proceeded aiming to working
conditions choosing and characterization.
3.2 Liquid state
The liquid states constitutive parts can be made of molecules
or, in case of metals or some salts, from ions.
The particles from a liquid enough high to give them an
oscillation and translation move and to range the particles to an
equilibrium distance d0, bigger than at solids, that explains at
macroscopic level the proper shapes lack, flow under different loads
(gravity, pressure etc.).
Very long time it was considered that liquids have a disordered
structure, but rntgenometric studies have established that this state is
a determined order (which increases with temperatures decrease).
Orderly settlement of liquids particles are kept only for small distances,
in two or three layers of particles and therefore was called local order,

11

CHAPTER 3

which means that if we refer to a given particle, all neighboring


particles are ordered arranged, but as we move away from this, the
arrangement of other particles is becoming less ordered so the
settlement is quickly disappearing.
Liquid state is a complex state; there is no unitary theory to fully
characterize this structure.
The main characteristic properties of liquids are:
Limited volume and indefinite shape;
Isotropy;
Flow and incompressibility.
Liquids properties depend on temperature, coming close to the
gas at high temperature and solids at low temperatures.
3.4. Superficial surface
A liquid substance is separated from the surrounding
atmosphere (where its vapors exist) through a superficial surface, which
determines some the liquid states characteristics.
The analysis of the resultant force of interparticular attraction of
particles located inside the liquids mass and the particles from the
liquids surface (fig.3.7) shows the following: on the particle from inside
the liquid, the resultant interaction forces is close to zero and very little
influence the free movement of particles, the particles are at the limit
of separation between liquid and surrounding atmosphere, acting as
interaction forces and the particles of liquid gaseous environment
which, however, are very small, characteristic of this state, so the net
force will act towards the interior of the liquid.

Fig.3.7. The resultant action on the particles of liquid


interparticulare
It's called a superficial surface the layer of particles from a
liquids surface which is in direct contact with its vapor and
extends in depth at a distance equal to the radius of the sphere
of action of the particle.
The existence of the superficial surface has the following
consequences:

12

CHAPTER 3

the superficial surfaces particles act as resulting from the


interaction surface to the interior of the liquid, exerting pressure on the
inner layers of particles - molecular pressure;
because of the cohesion forces, relatively large, between
liquid particles in comparison with the forces of interaction with
particles in the atmosphere, molecular pressure is very high, which
explains in principle the practice incompressibility fluids to achieve a
noticeable compression, a liquid be subjected to pressures
comparable to or even higher molecular pressure, given the forces of
rejection, while reducing the distance between particles.
3.5. Liquids viscosity
Under static (constant loads) in the fluids occur only pressure
loads (under their action of liquids can flow).
In dynamic conditions, the fluid in addition to the pressure
loads, internal friction and viscous friction occur as well, as a disturbing
of the equilibrium interaction loads between the particles and witch
are occurring as tangential loads that opposites the displacement of a
liquid layer to another.
If between two parallel plane plates there is a liquid having a
thin film form and over one of the is acting with a load enough big to
put the plate in motion, the following can be observe:
Plate velocity depends on the thickness of liquid film, which is
all the greater as the film thickness is less;
For different surfaces of the plates, for the same load
displacement speeds are decreasing with surfaces increasing;
The changing of loads intensity (for the same film thickness
and surface) forces increased with increasing speeds;
The displacements speed depends on the nature of the
liquid (when other parameters are constant).
It follows that to the moving liquids tangential loads are
appearing on the motions direction and witch depend on the size,
speeds variation depending on the distance between the motion
liquid layers in - speed gradient (reopanta) and the liquids nature.
As there is proportionality between tangential stress and
velocity gradient there are normal - viscous liquids (Newtonian) and
abnormal-viscous (Unnewtonian).
For viscous fluids normally Newton established the following law:

dv
dx

(3.1)
where:
= tangential stress that appears to move by a force of a
portion of a liquid than other portion;

dv

dx

velocity gradient (reopanta)

13

CHAPTER 3

= dynamic viscosity coefficient or viscosity depending on


the liquids nature N.s / m2
In the case of normal-viscous liquids (Newtonian) there is not a
proportionality between tangential stress reopant and the dynamic
viscosity coefficient; connection between them is as follows:
n
dv

dx
(3.2)
where: a nonlinear function of

n = constant that depends on the liquids nature.


Following modes of behavior are distinguished from nonnewtonian liquids flow:
speed gradient liquid which is a nonlinear function of the
tangential tension but independent of time;
systems in which the relationship between velocity and
pressure gradient tangential depends on time and other influences;
systems that have both characteristics of solids and liquids
(fluid viscoelastic).
To study the construction materials of interest, in particular,
liquids which category one two gradient dependence of the
tangential velocity and pressure can be of type:

a.
b.
c.
Fig.3.8. Voltage dependence tagenial - speed gradient liquid
and plastic flow cvasiplastic
Liquids with a threshold voltage (fig.3.8) cvasiplastice plastic
and which is characterized in that the stream must exceed a threshold
voltage (. In this category are oil paints, clay pasta, fresh concrete,
etc..
Fluids characterized by fig.3.8.a curve (plastic flow), are called
Bingham fluids, thus assumed that the fluids flow at rest have a certain
rigidity following a three-dimensional structures, able to withstand the
efforts of unit lower than threshold voltage. Once destroyed this
structure, fluid flow, behaving like a Newtonian fluid (as it explains that
dyes remain on the support webs).

14

CHAPTER 3

Pseudo-flowing liquids, at any value of the tangential tension


and the viscosity decreases with increasing velocity gradient (fig.3.8.b).
That category includes suspensions and pastes some of the cement
manufacturing process.
Liquids dilated, and the pseudo blood flow to whatever
tangential, but the viscosity increases with increasing voltage
tageniale (fig.3.8.c). In this category are highly concentrated
suspensions.
The viscosity of liquids depends on the temperature and
pressure, increasing with decreasing temperature and pressure
increase after the exponential law of the form:

0 ea

0 ebp
where:
= Viscosity of liquid at normal atmospheric temperature and
pressure
= temperature;
p = pressure
a and b = experimental constant
Variation of viscosity with temperature explains why, for
optimum lubrication of machine parts are used, as seasons, lubricants
with different viscosities.
In practice, the viscosity can be expressed in the form of
kinematic viscosity, defined as the ratio of dynamic viscosity and
density of the liquid for a given temperature:

N.s.m / kg

For some materials, such as paints, varnishes, petroleum


products etc. relative viscosity is used, is defined as the ratio of two
times the volume of fluid leakage, one of which (usually water)
drainage time known - Engler viscosity measuring unit degrees Engler,
0E - or defined by time leakage, in seconds, of a certain volume of
liquid through a standardized unit - Saybald viscosity.
Size reverse flow is called viscosity ( = 1/). Some substances free-flowing - are able to reduce the viscosity of liquids, having wide
applications in the service of liquids in pipelines and in processing.
3.6. The gas state
In the gas state, particles can be characterized by a large
freedom of movement, which leads to elastic collisions between
particles (at normal temperature and pressure 10 collisions per
second take place) followed by a new layout. As a consequence of
this behavior of particles, the characteristics of gases are determined
by temperature, pressure (which influences the movement) and the
concentration of particles in the unit of volume.

CHAPTER 3

15

The gas state, is the state in which matter is found,


characterized by the property that it does not have own volume
and shape, occupying all the available space.
From the specific properties of the gases, the most important,
which interest the study of construction materials, are:
The gas pressure, which represents the measure of the
action of the particles of the gas over the surfaces which
delimitate the space in which they are found.
The pressure is a direct function of the number of particles in the
delimitated space the law of Avogadro and of the temperature of
the gas the law of Gay Lussac.
The gas diffusion is the characteristic of gases to
occupy the whole space they have at disposition, through the
particles of another gas, until the realization of the same
concentration in the whole available space, without the
intervention of external forces.
The ionization of gases is the process of forming ions
(simple or complex) under the action of some exterior factors
(ultraviolet radiations, electric discharges, nuclear or cosmic
radiations).
The ionization explains the changing of the electric
conductibility followed by corrosion.
The humidity of gases represents the way in which the
particles of water or water agglomerations (drops) contribute
to the formation of the voids volumes.
A special importance for the study of building materials
constitutes the humidity of the air, which influences the forming process
of the building materials, and their behavior in time.
The quantity of atmospheric vapors represents the humidity of
air and the scientific domain that studies these phenomenons is called
hygrometry.
The absolute humidity or the density of water vapors
represents the quantity of water existing in the unit of volume.
For practical necessities its currently used the relative humidity.
The relative humidity represents the ratio between the
pressure p of the vapors that exist in the air at a certain
moment and the pressure ps of the saturated vapors at the
same temperature as the air.

16

CHAPTER 3

p
ps

sau U

p
100%
ps

(3.3)

The humidity of air can be experimentally determined with a


series of instruments hygrometers which are composed on different
principles such as: the changing of air pressure depending on the
humidity, the changes of a volume of air at humidity variations, the
changing of the lenght of a line(the hair hygrometer).
The Joule-Thompson effect represents the property of gases
of decreasing their temperature when they relax they go from
very high pressures, through narrow orifice, to the atmospheric
pressure.
The phenomenon can be explained by the energy
consumption necessary to sever the coupling between the particles of
the gases under high pressure (100...200 atm.); at these pressures the
particles are very near to each other thus there is the possibility of
creating Van der Waalas particles couplings.
This capability is used to obtain low temperatures necessary for
testing construction materials or in the refrigeration technique.
3.7. Transformation of aggregation states
A substance may be found in different aggregation states,
depending on temperature, pressure, specific volume, that represent
the main state parameters, characterizing the internal energy.
The temperature is the main physical dimension which
characterizes the thermal state (the heating degree) of a body
in thermodynamic equilibrium.
The measure unit for temperature in the I.S. is the Kelvin K; in
practice the Celsius degree C is used.
The pressure is the numerical state parameter equal to the
force generated by the particles of a gas on the surface that
delimitates the volume occupied by it.
The measure units currently used for pressure are:

The Pascal Pa = N/m2

Physical atmosphere atm. =1.013105 Pa

The Torr (mm Hg column) 1 torr = 1.33105 Pa

The Barr = 105 Pa

CHAPTER 3

17

The specific volume is the numerical state parameter equal


to the ratio between a portion of the volume the gas has
available and its mass.
The measure unit of the specific volume is m3/kg.
Le Chatelier (1885) has formulated the constraining
principle showing that by the exertion of a constraint on a system
in equilibrium, the later is moving in such way that the constraint
is minimal.
By forcing a system we understand the modification of one of
the parameters which determines the equilibrium, in case of states
transformations, temperature, pressure and the specific volume.
At the increasing of the temperature of a substance, the kinetic
energy increase increases by amplitude the particles moves and
the equilibrium goes to the state characterized by more possibilities of
particles movement; the solid state goes into the liquid state, which
gives more freedom to move (vibration and translation with bigger
amplitude then those at solid bodies) and the liquids goes into the gas
state, which gives more freedom to move. As the temperature
decreases, the kinetic energy decreases too, which determine the
inverse transformations, gas- liquid- solid.
Pressure, as a parameter of statement, determines the
concentration of particles in a volume with influence on the liberty to
move. We can say that the principle is, that on a higher pressure, will
be stable the pressure which has a smaller specific volume, so it has a
bigger pressure.
The transition of a substance from one statement to
another its called state change or physic state change.
3.8. Reciprocal transformation between solid and liquid state
The transformations solid liquid and liquid solid are
producing as a following of the temperature modification; the pressure,
as a statement parameter of those transformations, it cant manifest
because this condition is characterized by a constant volume. The
pressure determines, on another hand, the temperature to which the
transformation produces to.
The transformations solid liquid its called melt down and
the transformation liquid-solid its called solidification. The
solidification of substances, which, in normal conditions of
temperature they can be find in liquid statement, called
freezing.

18

CHAPTER 3

The transformations solid- liquid and liquid-solid, they arent


producing all of them after the same law, but different at crystallized
solids, amorphous solids and at extreme speed of variation of
temperatures. (fig.3.9)

Fig.3.9. Solid - liquid and liquid solid transformation


The heat increases the kinetic energy of solid particles is to
increase the distance between them and therefore reduces the
possibility of return to equilibrium position the force of attraction
between the particles become smaller and reorganized its local solid
body structure.
The melting temperature of the attractive forces are so small
that particles can not take the old position of equilibrium, so the
structure is destroyed and the substance passes into the liquid.
a) melting and solidification of crystalline solids
Under normal conditions, the melting of crystalline
substances occurring in a well-defined temperature called the
melting temperature (t - Figure 3.5), which remains constant
during melting.
The melting temperature depends on the pressure at which
they melt.
Melting and solidification are the reverse phenomenons
occurred at the same temperature if the pressure is the same.
The melting temperature (solidification) solid and liquid
states are in equilibrium.
b) Melting and solidification of amorphous solids
Amorphous solids pass from solid to liquid in a temperature
range (fig.3.9) through a process of softening.

CHAPTER 3

19

Amorphous state is closer to the liquid phase, melt can be


considered as a change in viscosity - solid which has a high viscosity
decreases with increasing temperature.
A special case presents the solidification temperature
decreases rapidly when the liquid phase can be kept below the
temperature of solidification (fig.3.9) as unstable state that is rapidly
destroying the shaking, etc. in the presence of a crystal. When the
temperature rises very quickly to solidification temperature.
If subcooling condition is not destroyed or cooling rate is very
high (fig.3.9) liquid viscosity increases very quickly, the particles lose
their mobility and solidification occurs with formation of amorphous
structure (named for that reason and liquid subcooling).
Melting and solidification are accompanied by changes in
volume. Typically, the melting is accompanied by an increase in
volume and hardening occurs with the decrease in volume,
phenomena can be explained as a result of different distances
interparticular two states of aggregation.
But there are exceptions to this rule, water, iron, etc. which is an
increase volume at solidification, where water can be explained by
hydrogen bonds that lead to agglomeration.
Increasing the volume of water solidification (freezing) to about
10% (fig.3.10) a defect of construction materials, which can destroy,
but it is essential for life in lakes and rivers (ice floats on the water easier
than Having the role of thermal insulation in deep water, which do not

freeze).
Fig.3.10. Changes in the freezing water volume
Experimentally, it was revealed that: substances which increase
the volume of melting, melting temperature increases with increasing
pressure, the substance which reduces the volume of melting, melting
temperature decreases with increasing pressure.
3.9. The mechanism of crystallization from melts
It was shown that the method of solidification and cooling rate
depends on the chemical nature of the melt - a rapid cooling

20

CHAPTER 3

solidification of substances takes place in amorphous form, some


substance solidifies as amorphous regardless of the mode of cooling.
If a liquid is solidified by a moderate cooling without subcooling
phenomena near the solidification temperature, molecular
associations of the liquid increases, become stable and form crystals or
crystallization centers (fig.3.11), to represent the plan of the

phenomenon.
Fig.3.11. Crystallization from solutions
scattered throughout the melt mass. When the temperature of
solidification, the particles are disposed around the crystallites, not
randomly, but in future crystal axes, making the tree formations called
dentrite (fig.3.11). Melt the metal cools, the crystallization tendency is
so pronounced that at the melt surface, dentritele is observed with the
naked eye. Over time, the solidification temperature of the particles
from the melt takes place between the branches dentritelor - ordered
filling gaps - and thus take the form of solid crystal in all directions.
Following the process of melt crystallization throughout the
mass, the first phase crystallites are spread across the table and they
melt and are formed around dentritelor dentritele be isolated crystals
grow continuously until they meet. Since the meeting between the
crystal is made at random crystal growth stops after random buttons, so
that the crystalline solid formed from the melt, crystals are not regular in
shape - ideal - but the crystal grain of irregular shape. Ordered
structure but each grain is characteristic of crystalline state. In this way,
explains the characteristics of crystalline structures of isotropic grain
(rock, metal, etc.).
3.10 The liquid transformations to gas and the gas
transformations to liquid
The liquid transformations to gas and the gas transformations to
liquid produces to the variation of all parameters of state(temperature,

CHAPTER 3

21

presure and the volume of unit mass) which is conditioned reciprocally


(mutual).
a) The liquid transformations to gas
The process of pass of substances from liquid state to gas
state in a limited volume is appointed the vaporization.
The process of pass of a liquid into vapors only through the
free surface of the liquid and in a unlimited volume (free air) is
appointed evaporation.
In particular conditions of temperature and pressure it is
possible to arrive to the situation in which the number of evaporated
particles is equal with the number of particles which come back into
liquid (is condensed).In this situation the vapors and the liquid are in
dynamic equilibrium.
The vapors which dont seem to be in dynamic equilibrium
with the liquid from which they comes are called saturated
vapors.
The pressure for which, to a determined certain
temperature is achieved the dynamic equilibrium is called the
pressure of saturated vapors (Pvs).
The vapors which have the pressure smaller then the vapors
pressure are called non-saturated vapors.
In the case of vaporization it is possible to arrive at the
realization of saturated vapors which isnt possible in the case of
evaporation.
If a liquid is warm-up, the absorbed air by the liquid, in the form
of agglomerations (bubbles) and the volume becomes bigger in which
take place the evaporation of the liquid, in the way of saturated
vapors. When the volume of the bubbles is enough big, pass troughs
the liquids viscosity and go up to the free surface, so the boiling
process is realized.
Boiling is the evaporation process witch take place in all
the liquids mass, at a constant temperature, called boiling
temperature.
The boiling process begins only when the pressure of the
saturated vapors inside the bubbles becomes equal with the exterior
pressure (from the free surface of the liquid).
With the increase of exterior pressure, the temperature of
boiling is also increasing.

CHAPTER 3

22

If a liquid is heated in an enclosed space the pressure over it is


equal with the sum between airs pressure and saturated vapors, so the
liquid can not rich the boiling. This characteristic of vaporizing at high
pressure it's used to realize autoclaves, closed spaces where water
can be heated over 100 degrees, realizing atmosphere with vapors
with high temperature and pressure and the chemical process of
making the cement more strong are very accelerated, with implication
for production process.
b. Gas - liquid transformation
The passing of a liquid from has shape to liquid shape, is
called condensation, if the normal shape of the substance is
liquid and liquidification if the substance from normal shape to
gas.
Condensation may be realized as a fact of a lower
temperature, the contact with cold surfaces - the principle of cold wall
of Wald.
Distillation is the partial vaporization of a liquid followed by
the vapors condensation and the collect of the formed liquid
mass.
By boiling, the liquid turns into vapor that condenses in contact
with a cold wall. Because the boiling temperature depends on the
liquids nature, a separation of different liquids from a mixture fractional distillation - or a purification of a liquid can achieved.
Liquidification can be achieved by decreasing the
temperature, increasing the pressure, reducing the volume of gas,
parameters are mutually conditional.
A gaseous substance is called the gas, if it is at a higher
temperature than the critical temperature and is called vapors, if the
temperature is lower than the critical.
Liquidification can be achieved through several methods:
isothermal compression of gas at a temperature below the
critical one - the process is used for easily liquefiable gases (with high
critical temperature) such as carbon dioxide and ammonia;
simultaneous cooling and compression - use ice for cooling or
other liquefied gas;
cooling in steps (Kamerling Omers method) which liquefies
the gas in steps, such as oxygen, nitrogen, hydrogen.
3.5. The low temperatures obtaining
The low temperatures below -150C, corresponding to natural
water freezing temperature) are used in construction materials testing

23

CHAPTER 3

in destructive actions resulting from the increased volume of water


during freezing.
The process commonly used to reduce temperature in an
enclosed and thermal insulated space, is based on the vaporization of
a liquid at a pressure which corresponds to a low saturation
temperature; by vaporization is consumed a quantity of heat which is
taken from a enclosed space. As refrigerant agent ammonia Freon
(derivative of methane and ethane) can be used.
3.6. Dew point temperature
Dew point temperature is the temperature at which moist
air must be cooled at constant pressure, for water vapor
becomes saturated.
The phenomenon is very important for comfort in the buildings
or construction elements moisture protection. If the dew point
temperature is inside of a construction element or on the interior face
of the element, the vapors from the built space will condense and
collect in / on the construction elements in the drops form.
Sublimation
Vaporization of solids is called sublimation.
In some solids substances at a temperatures increase vapors
are appearing before the solid to be liquidificated; if the saturated
vapors pressure equalizes the atmosphere pressure, at ambient
temperature, the gas-solid transformation occurs. Iodine, benzoic acid,
etc. are substances which sublimates.

CHAPTER 4

4. SUBSTANCES SYSTEMS
In nature, so in the construction materials, substances (with the
same structure and chemical composition) can not be found singular,
only very rarely, usually in a system form and in contact with other
substances.
In the separation limit of two substances, their homogeneity
changes, peripheral layers of particles (molecules, atoms, ions) are
subject to different actions than those the inner particles are subjected
and consequently the structure of substances with greater cohesion
forces molecular pressure occurs and in the same time will attract
particles of substances having smaller cohesion forces and thus in the
contact area, the concentration of the substance becomes bigger than
the rest of its volume.
These disturbances lead to the interface phenomenon (contact
area of two substances).
4.1. Interface phenomenons
Interface phenomenons depend on the internal cohesion forces
and their intensity will depend on:
the chemical structure of substances with they are coming into
contact, because it determines the size of the internal cohesion forces;
the substances states of matter, because for the same
substance the cohesion forces size depends on the state of matter
(decrease from solid state to the gaseous state)
temperature and pressure, because the energetic state and the
internal cohesion are modified.
particles concentration, as internal cohesion depends on the
number of constituents.
4.1.1. Adsorption, absorption, sorption and desorption
Adsorption is the phenomenon witch leads to form of a layer
particles (molecules, atoms, ions) from a substance with less internal
cohesion forces (liquid or gas) on the surface of a substance with greater
cohesion forces (in liquid or solid).

CHAPTER 4

The phenomenon of physical constituents attraction of a


substance at the contact with another substance, as a result of cohesion
forces disequilibrium is called adsorption or physiosorption.
Substance with greater cohesion forces, which cause adsorption is
called the adsorbent and the substance whose particles are attracted is
called the adsorbate.
In the adsorbed particles layers the concentration is maxim at the
contact with the adsorbent and decreases rapidly as the particles are at
a greater distance from the contact area.
If the forces witch create adsorption are weak, usually Van der
Waals type, the process is reversible with state parameters (pressure,
temperature) modification and when they are interatomic bonds type,
the process is irreversible.
The process of chemical bonds forming at the adsorbate adsorbent contact is called chemisorption and is an irreversible process.
Chemisorption differs from physiosorption by:
- Is achieved through interatomic bonds (usually electrovalent)
- Is selective, so an adsorbent do not adsorb any adsorbate
- Particles chemisorbed are not mobile on the absorbents surface,
are fixed in certain well-defined positions
Phisyosorption is a reversible process and may occur on state
parameters (temperature, pressure) modification, by modifying the
adsorbates structure or under some external loads (electrical energy,
mechanical, etc.).
The adsobates removing process from the adsorbents surface is
called desorption.
Solids, due to the presence of open pores, can attract the
substances witch have weaker cohesion forces within the volume as
well, realizing the absorption phenomenon.
Absorption is the penetration and distribution process of a
substance in the whole volume of another substance.

CHAPTER 4
Sorption is the sum between adsorption and absorption.

Adsorbed substances change close to the contact surface with


the adsorbent some characteristics such as: viscosity (increases),
evaporation temperature (increases), etc.
4.1.2 The Superficial Tension
Like a consequence to the action of the resultant of the forces
adsorbent-adsorbate, the superficial blanket of the adsorbent will strive
to reduce his surface. Since, to the directions included in interface, the
forces of cohesion between molecules mutual balances (between
molecules it is produced the same substances) the superficial blanket will
act like a plasticity membrane.
The force which acts tangential to the interface of 2 substances,
on a line of 1 m length, it is called superficial tension. In the case when
the both substances are in contact are liquids, this force is called
interfacial tension.
The value of the superficial tension (interfacial) has meaning only if
thee are determined the substances in contact and their temperature.
4.1.3. Lyophilia and lyophobia
A consequence of the superficial tension is behavior of the
substances that come in contact, as:
A liquid molecule from the solid liquid and liquid gas separation
limit is supposed on the following attraction forces (fig.4.1.): sg (solid
gas), sl (solid liquid), lg (lichid gas) and the resultant is .
g

sl

lg

sl

Fig.4.1. Liquid to solid adhesion


If a drop of liquid it is found on the surface of a solid, the system
being in gas, in the point contact of all 3 states of aggregation it will

CHAPTER 4

manifest the superficial tensions corresponding to the interfaces: solidgas, solid-liquid and respectively liquid-gas.

lg

sg

lg
sg

sl

sl

Fig.4.2. Liophilia and liophobia


The equation equilibrium of forces (stresses) in this point will be:
sl - sg lgcos =

(4.1)

The resultant () of superficial tensions, in the treble point of


contact is called of adhesion to solid force.
The angle is called angle of wetting and represents the variable
parameter in the equilibrium equation 4.1. Thus, the conditions for to
be minim are:
- 00, if sg>sl
- 1800, if sg<sl
In case which 0 has the same meaning with sg, the liquid will
spread in monomolecular stratum on the solid surface; the liquid will wet
the solid.
The lyophilia defines the solids affinity with respect to the liquid
(the liquid wets the solid) and is achieved when the angle of wetting
takes values less then 900.
In case which 0 has the same sense with sl, the drop of the
liquid will restrict on the surface of the solid, between liquid and solid
interposing an gas layer; the liquid will not wet the solid.

CHAPTER 4

The lyophobia defines the absence of the liquid affinity with


respect to the liquid (liquid will not wet the solid) and is achieved when
the angle of wetting takes values more then 900.
If the liquid substance is water, the described phenomenas takes
the name of hydrophlia and respectively hydrophobilia.
4.1.4. The capillarity
Another consequence of the disturbance of the surface
tension at the contact between different substances (such as structure
and state of matter) is the capillary.
The trend of lifting or lowering of a liquid into a solid capilar is
called capilar ascension.
A capilar is formed into a solid by the merger of pores when has
not a linear axis and constant section, or may be a capillary vessel when
it has a linear axis, and a small and constant section.
If the solids surface tension is bigger than the liquids, in the capilar
the liquid tends to ascend (water in solid) (fig.4.3a.) If the liquids surface
tension is higher, it tends to descend (mercury in a capilar vessel)
(fig.4.3.b.).

b
Fig.4.3. Capillary movement

The ascending or descending height (also called capillary height)


of the liquid in a capilar will depend on the physical characteristics of the
liquid and the capilars geometric elements. For a capillary vessel,

CHAPTER 4

capillary height can be calculated from the equilibrium between


adhesion to solid force () and hydrostatic pressure of the liquid.

d2
.g.h
4

4
h .
g .d

(4.2)

where:
d = diameter of the capillary tube
= liquids density
g = gravity acceleration
Note that the capillary height for the same liquid and solid will be
grater as the diameter is smaller. In a capilar, the capillary height will be
lower than in a capillary vessel due to the diameters variationan
nonlinear path, so in a sandy soil capillary height will be higher than in
gravel. To prevent ground water to rise in constructions walls, building
elements which cut capillaries are provided (fig.4.4).

Zidarie
Sistem de intrerupere
a capilaritatii

Teren
umed

Fundatie din beton

Fig.4.4. Capillarity interruption in construction elements


4.1.5. Liquids miscibility
If two liquids ca not be mixed to form a homogeneous structure
(constituent particles can not diffuse to each other) their interface, due
to interfacial tension, acts as a waterproof membrane.
The liquids miscibility is their property to form homogeneous
mixtures by mutual diffusion of the components.
Liquids miscibility is reduced by interfacial tensions increasing.

CHAPTER 4

The liquids that can not form homogeneous mixtures are called
immiscible.
4.1.6. Influence of absorption on the substances characteristics
At the gas - liquid separation surface and immiscible liquids by
adsorption the surface tension is modified. In the adsorbed layer the
surface tension has a intermediary value between the surface tension of
the two substances that come in contact, closer to the lower surface
tension.
Liquids surface tension, with application in practice can be
modified using the surface-active substances.
Surface-active substances, generally organic substances having a
polar structure, accumulate on the liquids surface of orienting
themselves according to the surfaces (hydrophilic or hydrophobic)
nature forming "molecular brushes".
The formed monomolecular layer modifies the attraction force
between liquids molecules that leads to surface tensions modification
to the characters (hydrophobic or hydrophilic) modification.
Adsorption on solid surface modifies a number of their properties.
Practically all the solid materials in the air can be considered that they
have on their surface an adsorbed film from the gases and water vapor
in the atmosphere, it producing the following changes:
Gradual increase in volume, beginning from the contact
surface, which can cause cracks in the solid;
Decrease of the tensile strength, due to open microcracks from
the solids surface, where the adsorbed molecules protrude, widening
and deepening them with a wedge effect (fig.4.5); it was established
that the tensile strength of glass bar heated (in vacuum at 3500C when
the gas desorption is produced from the glasses surface) is two times
higher than a similar sample, but kept in the air; this explains why the
thinner wires strength is greater than those with higher cross section.

Desorbtie
Adsorbtie

Fig.4.5. Wedge effect of the liquid adsorbed layer on solid

CHAPTER 4

the decrease of the friction between solids the film having a


lubricant role; in the case of an adsorbed layer (fig.4.6) the friction
between the solids is more reduced, (the friction coefficient is below
unity, and if the adsorbed layer is removed by heating coefficient of
friction increases significantly above unity.

P
F

Fig.4.6. Adsorbed liquid lubricant role

4.1.7. Application of interface phenomenons


One of the most common in engineering applications of interface
phenomenons is the modification of the character lyophob or lyophil
materials.
water

oil

oil

water

a.

b.
Fig.4.7. Liophobisation and liophilisation processes

Liophobisation (hirophobization) represents the decrease of the


substances affinity to the liquids (water) by surface-active substances
using. On the liophilic surface of the solid the surface-active substance
adsorbs with the polar terminals on the solid and with the non-polar
terminals to exterior (fig.4.7.a) giving to the assembly a hydrophobic
character.

CHAPTER 4

The building materials liofobization applies to: clays stabilization,


obtaining of the waterproof cement and water-protection materials.
Lyophilization (hydrophilisation) aims to change the liophobic
character of a substance using surface-active substances having
elongated molecules witch are orienting on the liophile substance
surface (fig4.7.b.). Is applied, in particular, for emulsions obtaining
(mixtures of immiscible liquids such as oil in water, bitumen in water etc.).
Flotation is used to improve the content of utile substances from
ore. Ores are natural materials containing utile metal combinations with
the sterile. The active part of a ore has hydrophobic character and the
sterile has a hydrophilic character. Ore is finely milled so that surface
tension to be greater than the particles weight; the obtained powder is
spreaded on the waters surface, achieving a separation, the utile part
of the ore will float on the waters surface and the sterile particles decant
due to the increased weight by waters adsorption and the separation
will be prosecuted.
Washing. Organic substances removing of from a solids surface is
very difficult because they are hydrophobic. By adding soap or
detergents, they modify the dirty surfaces character from hydrophobic
to hydrophilic; the dirt is fractured, is emulsified and can be removed.
Chromatography is the separation of complex mixtures into the
component substances.
4.1.8. Specific surface
The surface phenomenons depend on the size of the contact
surfaces between them and how the solids have their own volume and
shape, depend on the solids surface in contact areas.
The specific surface of a material represents the ratio between the
area that separates it from the environment and its volume.
Surface area depends on the materials of fragmentation degree.
If we consider a cube with 1cm sides, and a 1cm3 volume, fragmentation
by sides geometrical progression reducing, the following progression of
the number of cubes and specific surface is obtained.

Cubs side
1cm
1mm

Nr. of
cubs
1
103

Table 4.1.
Specific surface
cm2/cm3
6
6
60
6x10

10

CHAPTER 4
100
10
1
100m
10m
1m

106
109
1012
1015
1018
1021

600
6000
60000
600000
6000000
60000000

6x102
6x103
6x104
6x105
6x106
6x107

If the particles shape is spherical (the sphere has the lowest surface
volume ratio from al the geometrical bodies) the specific surface is
reduced to 80%.
The specific surface size can be accomplished by several methods
such as:
Materials milling (in tubular ball mills) when the particles can
reach the size in order of microns (for cement) and if one takes into
account the surfaces rough of the particle the specific surface increases
significantly.
Increasing of the surface roughness, especially by the moderate
action of corrosive agents. Due to the solids surfaces unhomogeneity,
the corrosion occurs ununiform, the surface turning into a field filled with
microscopic grooves.
Precipitation methods. The products resulted from chemical
reactions, precipitate on inert solid support from chemically point of
view.
4.2. Disperse systems
It was shown that the materials consist of mixtures of substances
which can be distinguished between them by the chemical structure or
state of mater. The substances mixtures are forming the substances
systems which are characterized by:
The components of the system, defined by the individual
substances chemically differentiated.
Systems phases are consisting of homogeneous and distinct parts,
physically separated from each other through well-defined surfaces.

11

CHAPTER 4

So the components of a system define its parts which can be


customized by chemical structural aspect and phase system, the parts,
which can be customized by physical aspect. For example:
Mixture of water and its vapors (during boiling) forms a system
with one component (water) and two phases (liquid and gas);
Mixture of two gases or two miscible liquids realizes a system with
two components and one phase (gas or liquid);
Mixture of a liquid and a gas (carbonated water) form a system
with two components and two phases.
Single-phase systems where the components can not be observed
(individual) in a physical manner (in natural light) are called
homogeneous systems.
Systems with two or more phases that can be physically
individualized through their separation surfaces formed heterogeneous
surfaces.
The predominant (continuous) part from a system forms the
dispersion medium or the dispersant phase and the discontinuous phase
is called dispersed phase or dispersoid.
The substances systems can be differentiated by the systems
phases or the dispersoids size (table 4.2).
Dispersed systems can be stable or unstable (the maintaining or
not of the dispersed phase) as a consequence of interface
phenomenons that allow or not the dispersed phase agglomeration and
its removal by sedimentation or diffusion, phenomenons depending on
the dispersoids specific surface.
Table 4.2.
Dispersoids
size
cm

Systems type

Systems
name

< 10-7

homogeneous

Solutions

10-7 ... 10-5

heterogeneous

Colloids

Observations
The dispersoid has small
molecules of the atoms or
ions, can not be observed
by optical microscope
The dispersoid can be
observed by high definition
optical microscope but not
by free eye

12

CHAPTER 4

> 10-5

The dispersoid can be

heterogeneous Suspensions observed by optical

microscope and by free eye

A dispersed system is more stable as the dispersoids specific


surface, will be higher due to the surface phenomenons intensity and at
the same time, in function of the difference between the densities of
phases that facilitate the separation by sedimentation.
4.2.1. Solutions
The solutions are the most common systems found in nature and
are the basis of construction materials influencing their sustainability.
Homogeneous systems in which the dispersoid is composed of
small molecules, atoms or ions (not exceeding 10-7 cm in size) are called
solutions.
The solution is called the dispersion medium and the solvent or
solvent component solution is called dispersed, or dissolved solute, the
delivery of solutions (solute dispersing in solvent) is called dissolution.
Phases of the designation system solutions (used for scoring states
of amatter symbols: G - gas, L - liquid, S - solid (Table 4.3).
Dissolution occurs differently depending on the nature of
interatomic bonds and the state of aggregation of the components that
make up the system and therefore the diffusion of the solute in solvent.
Table 4.3
Solvent
solut
symbol
Components state of matter

name

gas

gas

G-G

Gas
mixtures

liquid

gas
liquid
solid

G-L
L-L
S-L

liquid
solutions

solid

gas

G-S

alloys
solid
solution

G-G and G-L solutions are achieved due to the gas ability to
diffuse gas through the solvents constituents;

13

CHAPTER 4

The L-L and S-L solutions dizolvation occurs in two stages: in the
first stage the solutes bonds are destroyed realizing solvent solute
bonds witch are diffusing in the solvent in the next stage.
G-S and S-S solutions are realized in liquid state of the solvent
and, if necessary, of the solute, according to L-L mechanism.
S-S solutions basic constituent for metals and isomorphic crystalline
substances, are achieved by replacing the solvent from the crystalline
lattice with solute particles substitutional solutions or by positioning of
the solute particles in the interstices of the solvents crystalline lattice interstitial solutions (fig.4.8).

a.

b.

c.

Fig.4.8. Solid Solutions


The substitutional solutions can be formed if the constituent ions
have equal or close ionic radius when ca be replaced in the lattice in
any proportion (fig.4.8.a).
In interstitial solutions when constituent ions are different in size so
that particles can be placed in solvent particles interstition, the
distribution may be uniform (fig.4.8.b.) or disordered (fig.4.8.c.) but at a
certain temperature can uniform the distribution forming the surfaces.
The solutions forming also depends on the nature of interatomic
bonds because is necessary that the solvent - solute interaction to
compensate the solutes particle interaction and can be achieved
when:
the components chemical bonds and the solvent - solution
bonds are similar in nature; substances with ionic bonds are dissolved in
substances having the same bonds or polar covalent bonds (water) and
are not dissolved in substances having unpolar bonds (organic solvents).
the components bonding energies are comparable or lower
than the solvent - solution bonding energies; molecular lattice solids are
dissolved in organic solvents because connection from the crystalline

14

CHAPTER 4

solvent

solvent

+ hidratare +- - + +
+
+
+ -+
a
+ -+
z
i
l
hidro
- +
- - +- +
+ polarizare - +
+
- +
+
- +
disociere electrolitic +
+- + - +- +
a) solut cu reea ionic
b) solut cu reea molecular
a.
b.
Fig. 3.7. Schema dizolvrii solidelor n lichidecu moleculepolare
+
+ e
r
a
t
a
r
- + hid
+ -+
++
-+
+ +- +
za i
l
o
r
d
i
h
+
-++
-

solut

solut

lattice are van der Waals type or hydrogen bonds and the solvent
solute connection forces are van der Waals type.
For the study of building materials is particularly interested in the
mechanism of dissolving of solids in liquid solvents, especially water.
Dissolving will depend on the soliss (the solute) and waters
(solvent) bonds nature and occurs in two stages (fig.4.9).

Fig.4.9. Hydration - hydrolysis process


In the first stage of the polar water molecules are attracted to the
constituents to form solid films with different densities, maximum at
surface contact, a step called hydration.
In the second stage, called hydrolysis solvent particles leads to
breakage of structural units of the solute (ions in the crystalline lattice fig.4.9.a, molecules in molecular lattice - fig.4.9.b.), which are diffusing in
the solvent (water) as hydrated particles. In molecular bonded structures
of the solid links and a third stage occurs when the hydrated molecules,
formed in the second stage, hydrolysis is realized.
Through hydrolysis in water new bonds are realized that have as
effect the appearance of ions in solution, a phenomenon which is called
electrolyte or ionic dissociation and the influencing substances are
called electrolytes.
Hydration process - hydrolysis has great significance in
strengthening the mechanisms of mineral binders (gypsum, lime,
cement).
4. 2.1.1. Concentration and solubility solutions
The main solution characteristic is the concentration.

15

CHAPTER 4

The solutions concentration represents the size of expressing the


ratio between solute and solvent.
After concentration, they differ:
concentrate solutions - the solute amount is large relative to the
solvent amount;
diluted solutions - the solute amount is small compared with the
solvent.
After the expression of the solutions parts to a concentration may
be:
Percentage concentration of mass - is the ratio of solute mass and
100g of solution.

%Cm

s
S
100

(4.3)

Where:
s - mass of solute (g)
S - solvent mass (grams)
Concentration percentage of volume - is the ratio of solute mass
and 100ml of solution.

%Cv

s
V
100

(4.4)

Where:
s - mass of solute (g)
V - volume of solution (ml)
Mass of solution in grams contained in one milliliter of solution is
called titre and is denoted T.
Volume percentage concentration represents the ratio between
the solute and 100 units of volume of solution.

%Cv

v
V
100

(4.5)

Where:
v - solute mass (ml)
V - volume of solution (ml)
Molar concentration (molarity) - is expressed by the number of
moles of solution dissolved in one liter of solution.

16

CHAPTER 4

%Cm

m
V
1000

(4. 6)

Where:
m - the number of moles of solution
V - volume of solution (ml)
Molal concentration (molality) - is expressed by the number of
moles of solution dissolved in 1000 g of solvent.

%m

m
Vs
1000

(4. 7)

Where:
m - number of moles of solution
Vs - volume of solvent (ml)
Normal concentration (normality) - is expressed by the number of
gram equivalents (val) solution dissolved in one liter of solution.

%m

m
Vs
1000

(4.8)

Where:
V1-number of validated solution
S solutions volume (ml)
In practice there are cases in which substances can form
homogeneous mixtures, mix in any proportion between them, but more
often mixing can be achieved within certain limits, that can have a
maximum concentration - the saturation limit.

Maximum concentration that can reach a solution is called the


saturation concentration and the achieved solution in this way is called
saturated solution.
Saturation concentration will be determined by the nature of the
solution constituents, temperature and pressure.
Solute concentration in a saturated solution is called the solubility
of the solute (substance).

CHAPTER 4

17

Depending on the maximum solubility in water (S - grams of


saturated water solution at 100g, 1 atm and 200C) substances can be:
slightly soluble substances (S> 10g,> 1%)
poorly soluble substances (S = 10g ... 0.01 g, 1% ... 0.1%)
insoluble (S <0.01 g)
Solubility varies with temperature and pressure (the gas increases
with pressure and decreases with increasing temperature).
If a solution is saturated state the parameters of the solution can
be removed until the solution reaches the solubility of the new
conditions.
Remove solution from a saturated solution to change the
parameters of state, is produced by degassing solutions G-L, L-L and
separation from solutions by precipitation from solutions SL.
It is sometimes possible to delay the elimination of the solute in
solution to produce, so it reaches a concentration above saturation.
State of the solution in which the concentration is higher than the
solubility condition is called oversaturated state.
When a solution is supersaturated state due to a chemical
reaction with the solvent and solute when the new structure is lower than
solubility the precipitation occurs which explains the hardening process
of mineral binders such as plaster.
Saturated state is unstable in case of energy intake or the
presence of a crystal, the solution precipitates and crystallizes.
4.2.1.2. Binding properties of the solutions
Solutions presents a number of different properties of the solvent
and depend on the number of particles present in the system and
independent of particle properties.
Feature-binding is a property of a system determined by the
number of particles in the system, but independent of their particle
properties.
Binding properties of the solutions are:
Lowering the vapor pressure;
Raising the boiling point;
Lowering the point of solidification (freezing);
Osmotic pressure.

CHAPTER 4

18

F.M.'s Law Raoult (1867) states that the relative decline of the
vapor pressure of a dilute solution is directly proportional to the mole
fraction of solute in solution is independent of temperature and nature of
the solute.
According to Raoult's law vapor pressure of a solution will always
be lower than that of pure solvent - the solvent molar fraction are several
solution to pure solvent solution where the fraction is 0.
The consequences of reducing the vapor pressure are boiling
temperature raising and lowering the solidification temperature
(freezing) with liquid solutions of pure solvent.
Lowering the freezing temperature of water solutions have
application in the implementation of building construction in cold
weather (pouring concrete and mortar processing) or de-icing roads.
Osmosis is the process of passing through a semi-permeable
membrane has a solvent in the same solvent solution or a diluted solution
more concentrated one.
Semi-permeable membrane is a film with very small pores that
allow passage of solvent molecules retaining the solute molecules.
Osmosis phenomenon occurs because of a solution to reduce the
concentration diffusion.
If in an enclosed space (such as a glass bell) is located two bowls:
one with a solvent and a solution of the same solvent (Fig. 4.10) the
following process occurs: the two vessels in the area will be closed vapor
was the two liquids (solvents and solution) with different vapor pressure in
this space and how there can be only one vapor pressure means that
the two vapor pressures must be equal. How p0 solvent vapor pressure
must be constant change of the solution vapor pressure p1. This process
is possible only if the solution is diluted, which is a condensation of the
vapor evaporating the solvent and therefore its continuous. The process
ends when all the solvent evaporated. Trend follows the dilution of the
solution.

19

CHAPTER 4

Fig.4.10. Modification of the solvents percent from a solution


Osmotic pressure is the pressure equivalent to a solution of water
pressure that impedes the flow of solvents and solvent in the solution
when the solution is separated by a semi-permeable membrane.
Osmotic pressure can be put out in a cell osmotic (fig.4.11) consists
of a container in which the solution is diluted or solvent (3), man will find
funnel the concentrated solution (1) closed at bottom with a semipermeable membrane (2).

Fig.4.11 Osmotic cell


The phenomenon of osmosis will lead to the increase in the more
concentrated solution because the corresponding diffusion solvent and
will raise the liquid from the funnel until the liquid column pressure
becomes large enough to restrained diffusion of solvent molecules
through semi-permeable membrane. Liquid column height h of the horn
is the osmotic pressure.

20

CHAPTER 4

Osmosis explains some biological processes at the plant and


animal cell, enhancing hydraulic binders, binders reinforced corrosion
etc.
4.2.2. Colloidal systems
Microeterogeneos disperse systems where the dispersoid have
sizes ranging from 10-7 10-5 are called colloidal systems or colloids.
In colloids dispersed systems occupy an intermediate place
between dispersele homogeneous (solutions) and coarse dispersele
neomiogene microeterogene systems being considered in aerosols are
particles larger than small molecules but smaller than the wavelength of
light in the visible spectrum (can not observed under the optical
microscope).
Por colloidal systems are formed between all phases except for
GG to form a homogeneous system (Table 4.4)
Table 4.4.
Dispersion
Dispersoid Symbol
medium
The components state of matter
liquid
L-G
gas
solid
S-G

liquid

solid

gaz

G-L

liquid

L-L

solid
gaz
liquid
solid

S-L
G-S
L-S
S-S

Name
aerosols
Fine
foams
Coloidall
emulsions
sols
xerogels
gels
alloys

Large specific surface particle aerosols and interface facilitates


development of such phenomena can be liofili colloids (hydrophilic)
particles which are wetted by the dispersed phase and dispersion
medium liofobi (hydrophobic) in the dispersed phase particles are not
wetted by the dispersion medium.

CHAPTER 4

21

For the study of building materials primarily interested colloids SL


structures with solid aerosols - ground and LS - gel. Achieving these
structures begins with soil formation.
Soli liofili
The messages affinity liofili environment due to the dispersion of
aerosols particles are dispersed autodifuzeaz, each particle aerosols
are made of a shell environment will be restrained from dispersion due to
agglomeration elasticity structure. Through this mechanism is hindered
particle agglomeration aerosols are partly offset by the density
difference between phases of the system.
Soli liofobi
If liofobi colloids, due to lack of affinity between phases, to
achieve dispersion and stability of the system it must first change the
feature of surface aerosols in liofil luiofob and surface-active substances
that are used.
Adsorb surface-active substances on the surface of aerosols to
form a hydrophilic film loaded with electric charge (A) (fig.4.). Around
these structures will be attracted contraioni complex ion (B) (ions of
opposite ions in the first layer - A) of the dispersion medium forming an
electric double layer system, called the micelles formed. When the
electric charge of the first layer has a negative ion or anion system is
called negative and positive ions when their task is called positive or
cationic system.
Messengers hydrophobic stability is ensured by forming micelles
that are rejected due to a static electrical charges of the same sign.
Getting colloidal systems
Methods for obtaining colloidal systems vary by the type and
nature of colloid phase components.
1. Methods of dispersing the dispersed phase is finely fragmented
and scattered up to a size colloids dispersed phase, this will be done by:
mechanical dispersion - colloidal grinding mills;
Dispersal of electricity - electrical discharges between two
electrodes;
ultrasonic dispersion - the use of high frequency sounds.
2. Condensation methods by which the agglomeration of small
particles (molecules) from a colloidal solution to size using:

22

CHAPTER 4

Chemical methods - the double-exchange reactions, hydrolysis,


reduction - oxidation;
Changing the solvent - the solvent is changed by adding slowly
and stirring;
Condensation of vapors of substances.
Phase separation in colloidal systems
Phase separation of the applicant may be required in some
processes of construction materials and processing can be achieved by:
evaporation of the liquid phase;
Salting is the introduction of electrolytes in liofili messages that
produce desorption phase dispersed aerosols particles that remain
without cover eleastic, come together in large formations (a process
called coagulation) and settle;
centrifuge - intalaii use of high speed centrifuge, while the
centrifugal force when the stage is crowded with high density at the
periphery of the centrifuge.
Electrophoresis and apply liofobi messengers is to apply a static
electric field that guides contraionii, on the one hand and retul Miceli on
the other hand, for corespuztori electrodes.
4.2.3. Gels
A colloidal structure in which the dispersion medium is solid and
dispersoid is liquid is called gel.
Gels are obtained by gradually reducing the liquid phase of soil
structure (by evaporation, absorption to the substrate) until aerosols
particles come into contact forming a three-dimensional network that
remains dispersed in the liquid phase (fig.4.12). Gels can be achieved by
reducing the energy of a system of high concentration soil type.

micele
Faz lichid dispersat

Fig.4.12. Structure gels

23

CHAPTER 4

The transformation of sol - gel called gelling and should not be


confused with clotting, whereas no phase separation occurs in the
micelles.
Gelling occurs through changes in its colloidal system: the
disappearance or reduction of liquid phase characteristics (increased
viscosity, flow loss) and appearance properties of solids (mechanical
strength (elasticity, hardness).
The main feature is the mechanical elasticity of the gels depends
on the form of aerosols, gels are more elastic as aerosols has a more
elongated and the percentage of liquid phase is higher.

gel

sol
Fig.4.13. Gelling

If between gel particles dispersed phase connects interparticulare,


sol-gel transformation process is reversible, if the contact points of
particles dispersed in the structure of chemical bonds is achieved gels
gelling process is irreversible.
Sol-gel transformations applied to the use of building materials can
be achieved by:
Add the liquid (dispersion medium original) - transformation of
lime paste obtained by adding water and milk of lime;
Energy intake (mechanical stirring, heating moderate) - vibrating
concrete in casting, heating bitumen in asphalt concrete achievement
etc.
Use of chemicals (usually electrolytes) that adsorb onto solid
particles increasing their electrokinetic potential leads to particle

CHAPTER 4

24

dispersion, substances used for this purpose are called gum inhibitors,
and the process is called peptizare.
Tyxotropy gels are owned (tyxotropic) the applicant passes the
energy intake.
While kept in dry gels lose by evaporation or chemical processes
much of the liquid phase is replaced by a gaseous phase realizing the
drying process.
Gels in which the liquid phase was replaced by a gaseous phase
are called xerogels.
Drying gels is accompanied by:
large volume contraction due to rearrangement strucuturii, if
contraction is hindered (for accession on aggregate cement stone in
concrete) structure may crack;
Reduced elasticity, the increase of stiffness due to the
completion of additional physical connections and sometimes the
chemical bond.
Stiffening process irreversible in time, gelurior, as a result of
structural changes is called physical and chemical aging gels.
In contact with the liquid phase (if water wetting) gels absorb the
liquid and increase its volume, a process called dipping. Drying gels after
soaking leads to a further reduction in the volume of lower intensity than
before realizing mbibrii. Variations in volume during drying - are all
soaking strongest gels are more elastic and fresh.
Explains the phenomena of colloidal systems strengthening
hydraulic binders, bitumen processing processes, structure and use of
sealants, the behavior of clays etc.
4.2.4. Heterogeneous systems
Macroeterogen dispersed heterogeneous systems are systems, less
stable, the size of aerosols is larger than 10-5cm.

CHAPTER 4

25

Heterogeneous systems can be achieved by all states of


aggregation combinations except combination GG.
Heterogeneous systems environments have few stable liquid
aerosols due to the size (surface phenomena can not compensate for
the weight of particles) and density differences between components.
Suspensions in liquid media

CHAPTER 5

5. CHEMICAL KINETICS CONCEPTS FOR


BUILDING MATERIALS FIELD
The processes by which certain substances produce changes
of other substances with different characteristics are called
chemical reactions.
Substances that react together are the forming reactants;
substances that result from a chemical reaction are called products of
the reaction; the vessel, device or facility in which chemical reactions
occur is called reactor.
After the reactants characteristics, chemical reactions may be:
Reactions in homogeneous systems, the reactants are gaseous,
solutions or miscible liquid (reactants mixture forms a single phase).
Reactions in heterogeneous systems, the reactants are in different
states of matter, all of them are in solid state or immiscible liquids.
5.1. Thermodynamic concepts
All the modifications suffered by the substances are according to
the principles of thermodynamics.
Thermodynamics is the part of physics, which studies the variation
and interconversion of different forms of energy that accompany the
physical and chemical processes.
In 1842, the German physicist Julius Robert Mayer, studying the
mechanical work and heat, concluded that the heat is a form of energy
and sets the first law of thermodynamics.
The first law of thermodynamics is stated as follows: In any
transformation, the internal energy modification depends only on the
initial and final state of the system and is independent of the systems
intermediate states.
The second law of thermodynamics was discovered by S. Carnot
in 1824 when conducting studies on the efficiency of thermal machines,
determining that the known energy forms at that time (mechanical,
electrical, chemical, radiant) can be entirely converted into heat, but

CHAPTER 5

the heat can not be converted into mechanical, electrical or chemical


work.
The principle of thermodynamics II, after Thomson Plack sets that in
a reversible cyclic process is impossible to transfer heat from a heat tank
and its entirely conversion into mechanical work, without, at the same
time, to transfer a certain amount of heat from a warm to a cold body.
R. Clauseius, German physicist formulated the IInd principle of
thermodynamics as follows: the heat does not spontaneously pass from a
cold to a worm body.
Chemical thermodynamics studies the chemical systems
chemical stability conditions and the laws by which they evolve to
achieve a maximum state stability or minimum energy, chemical
equilibrium state.
Thermodynamic study of a chemical transformation leads to the
knowledge of released or absorbed energy by a system, the
development and maximal conversion sense, taking into account only
the initial and final state of the system without taking into account the
reactions mechanism, so without obtaining information on the speed
that the transformation occurs.
Mechanisms and development speed of chemical reactions are
studied by chemical kinetics.
A chemical reaction can be studied both thermodynamic and
kinetic.
System means a portion of the substance isolated from the rest of
the substances by conventional separation surfaces.
Thermodynamics studies the substances systems only in chemical
sense, which means the substances that consist of molecules, atoms,
ions.
Systems can be isolated (do not exchange energy or matter with
the environment), closed (only energy exchanges with the environment)
and open (both matter and energy exchanges with the environment).
In terms of constituents, the systems may be:
- Homogeneous - their macroscopic properties are identical in the
entirely mass;
- Heterogeneous - presents jumping variations of their macroscopic
properties.
The areas where the constituents properties jumps are presented
are separating surfaces and the areas delimited by these surfaces form
the systems phases.

CHAPTER 5

The process means the shift from an initial state of the system in a
final.
Thermodynamic processes can be classified by many criteria, but
in terms of chemical interest:
- After the processs sense, are: reversible processes, the system
can be restored to its original state from the final state on the same sense
that the direct process occurs and irreversible processes, the system can
not be restored to its initial state on the direct processs sense;
- After the occurring conditions: isochoric processes (v = const., dv
= 0), isobar (p = const., dp = 0), isothermal (T = const, dT = 0), adiabatic
when there is no heat exchange, Q = 0).
When in the Ist principle of thermodynamics the pressure and the
temperature are chosen as independent variables, frequently
encountered conditions in practice, the heats variation at constant
pressure is called enthalpy or caloric content in transformations case.
If the system fails heat, enthalpys variation will be negative and
the process will be called exothermic.
If the system receives heat, enthalpys variation is positive and the
process is called endothermic.
In a chemical reaction we encounter:
- Reaction enthalpy (reaction heat) - the amount of absorbed or
released heat during a chemical reaction
- Formation enthalpy of (heat of formation)
- Enthalpy of reaction for the formation of a substances mole
- Enthalpy of combustion (combustion heat) - the amount of
released heat in complete combustion of a substances mole
If the amount of released heat (Q) by unit mass (kg) or volume
3
(m ) of substance is estimated, the calorific power (q) is defined.
Q = q. m (J / kg) Q = q respectively. V (J/m3)
Thermochemical laws are:
Lavoisier - Laplace law - the amount of necessary heat for a
substances decomposition into its components is equal to the amount
of consumed heat in forming the substance from the same elements.
Hess's Law - the amount of absorbed or released heat in a
chemical change is the same regardless of how transformation occurs
directly or in stages.
Equilibrium normal states in nature tend to minimum internal
energy with temperature decrease during the transformations. This
tendency of the system to move toward the minimum energy state is

CHAPTER 5

expressed through in thermodynamics entropy, a concept introduced by


the German physicist R. Claudius in 1850.
Entropy is a measure of a systems state of and how it is more
ordered the entropy is lower. Physical meaning of entropy is the amount
of necessary heat to bring the system from minimum energy state to the
desired energy state at a particular temperature.
In an isolated system, in a spontaneous processs case, entropy
increases to a maximum value. This tendency is not universally valid
because it corresponds to a "thermal death".
The entropy of a substance in the amorphous state is greater than
in crystalline state.
Variation of entropy in a chemical reaction is given by the
difference between the entropy of resulted substances and the entropy
of substances which react.
5.2. Reactions in homogeneous systems
In a homogeneous chemical reactions occur between ions and
between molecules. For two particles to react with each other they must
come into contact (to face); this first condition for a chemical reaction is
not sufficient; indeed, the two components of air, O2 and N2 molecules
collide for many times and dont react; if they chemically react, would
form nitrogen oxides and thus the life would not be possible on Earth.
To produce a chemical reaction, in addition to the condition that
the reactants particles to come into contact, they must be in a richer
energy state (active state); the energy excess of the particles, necessary
to produce the chemical reaction is called the activation energy witch
can be transmitted to the reactants through various forms such as:
- Heating, thermochemical reactions;
- With electricity, electrochemical reactions;
- In the presence of light, photochemical reactions;
- Bombardment of nuclear particles, nuclear reactions;
- The intake of chemical substances, called catalysts, catalytic
reactions etc.
Physical sense of activation energy is as follows (fig.5.1.): suppose
that the reactants particle energy is Er and the products energy of
reaction at the end of chemical reaction is Ep; the energy difference Er
Ep = E represents the thermal effect of reaction. For the reactions
occurring, the reactants particles must be brought to an energy Ea
called energy barrier higher than the reactants energy Er; the difference
Ea - Er is the activation energy of the reaction.

CHAPTER 5
energy

Er

energy

energy Ea

Ea

Er
Ep
time
a) exothermal reaction

Ea

Ep
Er

Ep
time
b) ) exothermal reaction

time
c) endothermal reaction

Fig.5.1. Physical sense of activation energy


When Er > Ep (fig.5.1.a) the difference Ea-Er Ea Ep, the reaction
occurs with heat release - exothermic reaction.
The reactions where Er Ep (fig.5.1.c), with the difference Ea-Er
Ea-Ep, for the processs occurring, a supplementary energy contribution
is necessary - endothermic reactions.
Chemical processes are carried out according to some universal
available laws, characteristic and the most important are: the speed of
reaction and the reaction order.
5.2.1. Speed of reaction
Speed of reaction defines chemical reactions in time occurring
and depends on: the chemical nature of reactants, concentration of
reactants and reaction products, temperature and pressure at which
reaction occurs, the presence of catalysts.
Speed of reaction can be appreciated by the reactants
concentration (which decreases in time) or the reaction products
concentration (which increases in time).
The mathematical expression of the reaction rate which assesses
the chemical nature and concentration is:
v

dc
dt

(5.1.)

Sign - for reactants concentrations decreasing


Sign + for reaction products concentrations increasing.
Assuming that it takes into account only the concentration, other
factors remain constant, its influence on the reaction rate is the law of
mass action, as determined by Guldberg and Waage in 1867:

CHAPTER 5

The speed of a chemical reaction is directly proportional to


the concentration of reacting substances (the law of mass action)
In a general reaction of the form aA + bB + cC + ... mM + nN + oO
... , the speed of reaction (reduction or increase of reaction product
reactant M) can be expressed as follows:
v

dCA dCM

k.C Aa .CBb .CCc ... kAa .Bb ...


dt
dt

(5.2)

where:
k = speed constant (depending on temperature, pressure, presence of
catalysts, etc.).
CA, CB, CC ... and A, B, C...represents the molar concentration of
reactants, A, B, C...
a, b, c ... coefficients
Temperature affects the reaction speed as the kinetic energy of
the reactants increases with temperature; is experimentally
demonstrated that increasing the reactants temperature with 100C the
resulted in a doubling or tripling the reactions speed. This is used in
practice to reduce the construction materials forming time.
The pressure at which chemical reaction occurs is also a mitigating
factor of great importance to the reaction rate, whereas the
compactness of the system and thus influence the probability of collision
of particles and is determined when the reactants are gaseous
reactants.
The presence of catalysts (substances that occur in a chemical
process without going into the reaction products composition)
accelerates the chemical reaction. The mechanism of these chemical
reactions can be explained by the formation of intermediates products
(catalysts and reactants) and that are quickly passing in reaction
products and catalyst regeneration, following the formula:
A + B + K AK + B AB + K
(5.3)
5.2.2. Order of reaction
Order of reaction is expressed by the sum of the reactants
concentration exponents involved in the reaction speed reflecting
the number of particles witch by simultaneous interaction,
determines a chemical reaction.

CHAPTER 5

Depending on the order of reaction size, there are chemical


reactions with 1,2,3 order or higher. It was shown that chemical reactions
occur as a result of activated particle collision. For the first order
reactions the clashes may be missing, the reactions take place under the
activation energy contribution; in second order reactions, the collision is
necessary and collisions probability is high, so that the reactions are
carried out relatively easily, in the third order reactions and higher, of
collision probability of three particles or more is very small, practically null,
these reactions occur in steps characterized by 1 or 2 order reaction.
The reactions of various orders and their reaction speeds have the
form:
- First order reactions - the decomposition processes where a reactant
gives multiple reaction products:
- A reaction products
v1= k1 CA = k1
- CaCO3 CaO + CO2

v1= k1 . CaCO3

- Second order reactions are the most common and consist of the
forming from two reactants of reaction products:
A + B reaction products

v2 = k2.CA. CB = k2 A1 B1

H 2 +Cl 2 2 HCl

v 2 = k 2 . H2 1 .Cl2 1

- Third order reactions are chemical processes of three types of


molecules:
2A + B reac tion products

v3 = k 3 . C A. CB . CC =
= k 3 . A1.B1 . C1

2H 2 + O 2 H 2 O

v 3 = k 3 . H 2 2 .O2 1

5.2.3. Types of chemical reactions


The most common chemical reactions are:
a) Synthesis reactions of the form A + B = C, such as oxidation,
combinations of halogens, addition and polymerization reactions;
b) Decomposition reactions:
- Simple form: A = B + C, such monomolecular substances decomposition
in a heating process, called thermal dissociations (CaCO3 CaO +
CO2);

CHAPTER 5

- The double decomposition having the form: A + B C + D reactions


including hydrolysis, saponification, substitution polycondensation;
c) Neutralization reactions occur when strong acids reacting with
strong bases (NaOH + HCl NaCl + H2O);
d) Hydrolysis, the reverse of the neutralization reaction in which
the water can decompounds a salt in the forming base and acid. Only
salts formed from a weak acid and a base strong or a strong acid and
weak base can be hydrolyzed at a normal temperature, the reactions
stopping in an intermediate equilibrium state (Na2CO3 + H2O NaOH +
NaHCO3; FeCl3 + 3H2O Fe(OH)3 + 3HCl). The salts formed from strong
acids and strong bases hydrolyze only at high temperatures in the
presence of water vapors.
e) Substitution reactions such as replacing the anion of a salt with
another anion derived from a strong acid or replacement of a cation
with another cation derived from a harder base (Na2CO3 + 2HCl
2NaCl + H2CO3; NH4Cl + NaOH NaCl + NH4(OH).
5.2.4. Chemical equilibrium
Chemical reactions are not carried out in all cases in a single sense
(from reactants to reaction products) but at some point between the
reaction products to form reactants interactions occur, so a reversible
reaction A + B C + D is realized.
Reversible reactions are occurring in both senses until a
chemical equilibrium is achieved.

Reaction speeds can be expressed as follows:


a
b
for reactants:
v1 = k1 . A .B

for reaction products:


v2 = k2 . C .D
k1 and k2 are speed constant
Analyzing the reaction speeds result that v1 will decrease in time
and v2 will increase v1 and v2 varying in opposite directions at a moment
v1 = v2, which leads to:
-

k1 . Aa .Bb = k2 . Cc .Dd
k
Cc .D
k 1 a b
k2 A .B

(5.4)

k = equilibrium constant, equation (5.2) is the mathematical


expression of mass action law.

CHAPTER 5

Equilibrium in a chemical reaction can be a drawback in some


industrial processes that ensure that the reaction to go to the end. The
metallurgical furnace reduction technologies based on metal oxides
with carbon monoxide. Carbon monoxide is obtained from burning coke
in a stream of air at a temperature of 9000C carbon in the coke can not
be directly oxidized, the reaction is carried out by extracting oxygen
from carbon dioxide resulting from burning. At one point establishing a
chemical equilibrium between carbon monoxide and carbon dioxide,
with therefore reducing slow reactions and thus slowing the process
technology. Achieving high burning stoves, furnaces, had no influence
on the chemistry, but only the use of additives, a catalyst, solved the
problem.
Moving chemistry in homogeneous systems is carried out
according to Le Chatelier's principle, distractions as concentration,
temperature and pressure.
Influence of concentration on chemistry is included in the mass
action law. Movement of chemical equilibrium in this case can be
achieved by decreasing concentrations as the reactants are formed,
removal of reaction products can be volatile as a result of heating the
products resulting are volatile, heavy precipitation when soluble
products, etc..
Temperature
affects
the
chemical
balance
reactions
accompanied by heat absorption or release, which are exothermic and
endothermic in a sense the other way. Echiibrul moving in one direction
or another to the heating or cooling.
Pressure only causes displacement reactions chemistry between
the gases, which are followed by changes in volume. Thus, under
increasing pressure favors processes with decreasing volume and
reduced pressure favors reactions that occur in the volume increases.
5.3. Reactions in heterogeneous environments
In heterogeneous systems, in which phases are different
aggregation states and not dissolve into one another, or are in the same
state of aggregation, but still, the chemical reactions are preceded by
interface phenomena (adsorption, chemisorption) accompanied by
activation of particles Therefore the difference in surface tension.

10

CHAPTER 5

The chemical reactions in heterogeneous systems due to


interface phenomenons, the reaction products intercalate
between the phases as a thin layers shape.
Nature of surface separation between phases, consisting of
reaction products, determines the subsequent reactions, so (fig.5.2)
a) layer consists of reagents (C) is soluble in one phase, reacting
flows until all the reactant that is a lesser amount (fig.5.2.a, the reactant B
is the lesser amount);
b) reaction product (C) is insoluble but permeable to a reactant or
less permeable to one of the reactants, the reaction continues until all
the reactant reactant less permeable or a lesser amount (fig.5.2.b), the
layer insoluble (C) in the two phases A and B is more permeable to
reactant A (which is significantly higher). This case explains the oxidation
of iron in the air, the product of the reaction Fe2O3 (rust) is insoluble in iron
and air permeable to oxygen in the air so that the reaction continues
until all the iron, oxygen from the air in excess;
c) reaction product (C) is insoluble and impermeable to both
reactants, the reaction stops at the formation of a thin film, tight and
waterproof (fig.5.2.c). A typical case for this type of reaction is the
coating of metal oxides (such as the aluminum Al2O3) films which form
tight, waterproof, very thin, is a protective layer.
The heterogeneous chemical reactions occurring are influenced
addition to the nature of the reaction products layer and aggregation
state in which the reactants are as follows:

a)
b)

c)

A
C

produi de reacie

Fig. 5.2. Heterogeneous chemical reactions


occurring

CHAPTER 5

11

5.3.1. Reactions in systems consisting of a gas and a liquid phase


As a result of gas diffusion, the system consists of a gas and a liquid
phase, the reactions were usually a fairly high rate of reaction if the
reaction products are formed from a waterproof film.
Strengthening the paint, with the formation of an impermeable
film, mechanically and chemically, the appearance and aesthetic role,
is due to oxidation of drying oils. Paint must be applied in thin layers
because the oxidation starts from the surface (the contact between the
reactants), the viscosity change is observed after 24 hours, normally
formed film is impermeable to oxygen. If the coating is thick,
impermeable film surface chemical reactions and prevent the paint
starts to run from the base.
In keeping slaked lime (Ca(OH)2), the loss of water, it becomes
permeable to CO2, the carbonate lime (Ca (OH)2 + CO2 CaCO3 +
H2O); the reaction does not cover the whole mass of limestone for CO 2 is
little air and reacts with Ca (OH)2 immediately after coming into contact,
CaCO3 crystallizes very quickly and form a layer that diffuses the slightly
more compact for Ca(OH)2 paste is offset CO2 crust is formed
increasingly more compact and less permeable to CO2. Lime paste
retained its characteristics and structure a long time.
5.3.2. Reactions in systems of two immiscible liquid phases
Such reactions occur when the liquid reactants are immiscible with
different densities, which lead to phase separation and appearance of
buttons, but this is small compared to the mass of reactants. The
chemical reaction could be achieved if the reaction products would be
soluble and have a density intermediate between that of reactants,
forming an insulating blanket and the reaction intermediate stops. To
remove this drawback reactants are heated to boiling or moderate heat
and shake mechanically.
Among the chemical reactions between immiscible fluids have included:
making soap by boiling fat and moderate shaking in a solution of sodium
hydroxide, the manufacture of explosives of aromatic nitro compounds
rendering them (as trinitrotoluene, or TNT is obtained).
5.3.3. Reactions in systems consisting of a gaseous or liquid phase
and solid phase
Such reactions occur in many processes in building materials or
construction operation (in particular the corrosion processes).

CHAPTER 5

12

In solid-gas system occur in building materials a series of reactions,


of which would be typical:
a) Reduction of metal oxides with carbon monoxide: MeO + CO
Me + CO2; Me2O3 + CO 2Me + CO2.
b) Corrosion of materials in the atmosphere (Chapters will develop
specialist);
c) The combustion of powdered coal. Burning coal is carried on
racks on the outskirts of their pieces to the inside; leading to melting
resulting from the combustion products, which includes some useful
material (lost 30-40% of dry fuel). Grinding coal and coal and air mixture
injected into the furnace, burning to make a rapid and complete,
releasing energy and forming reaction products in the form of powder,
amorphous structure, which can be used as construction materials;
d) The action of air humidity and CO2 on lime, lime water off the
atmosphere (CaO + H2O Ca(OH)2) and act with lime CO2 with the
formation of calcium carbonate powder with an amorphous structure
without practical value. For this reason, quicklime is limited term storage.
Chemical reactions in liquid-solid systems meet the corrosion of
materials and particularly the concrete and mortars with mineral binders.
Natural waters with different characteristics (hardness, acidic, weak
solutions, etc.) react with cement components (silica, alumina, calcium
ferrite and calcium hydroxide) resulting reaction products with different
structures of the reactants (slightly soluble, with low mechanical strength
with increase in volume).
5.3.4. Chemical reactions in systems consisting of different solid
phases
Chemical reactions between solid phases have been studied
much later than other types of reactors, have been improved when
research methods (using heating curves, crystallographic study of the
composition of the reactants and reaction products, separation of
reaction products, etc.).
At normal temperature the reaction rate is very low, practically
zero, only raising the temperature leads to measurable response rates,
when solid particles in the interlayer diffusion of the reaction products
and reactants is high.
Chemical reactions between solid phases depend on a number of
structural factors, environmental (temperature), diffusion rate, etc., But all
resulting in several intermediate steps (fig.5.3).

13

CHAPTER 5

a)

b)

c)

reaction products

reactants

Fig. 5.3. The chemical reactions occuring in a system


consisting of two solid phases
Two solid phases in contact and the temperature is high enough, it
forms a layer of reaction products "C" (fig.5.3.a). With increasing
temperature of the reactants diffuses through a layer formed by the
reaction products. At this stage of the reaction, particles are arranged
disorderly reaction products (fig.5.3.b). Only further warming and raising
the temperature allows the orderly arrangement of reaction products
(fig.5.3.c) as a result of particle mobility.
To obtain a crystalline solid particles of the reaction products is
therefore necessary to carry out heating to a certain minimum
temperature and heating time. If you are seeking an intermediate
structure (richer in energy) for heating reactants limited duration.
C

C2S

Fig. 5.4. CaO SiO2 reaction in a


solid medium
When obtaining heating cement raw materials form CaO (C), SiO 2
(S) chemically active and react with the formation of solid 2CaO.SiO 2, in
this case CaO diffuses through the formed reaction product realizing the
reaction (fig.5.4).

CHAPTER 5

14

Increase speed of reaction heterogeneous system consisting of


solid phases can be achieved under the following conditions:
a) By increasing the surface area - which is usually done by
grinding, it is done and strain and dislocation of the crystalline structure,
which increases the ability of the reaction;
b) Making an intimate contact between particles of reactants by
mixing finely ground or milled together, leading to increased contact
surface.
c) heating the mixture at high temperatures, but below the melt
temperature of issue, thus making the kinetic energy of particles
increased with the establishment of links interparticular reactants and
thus increase the reaction rate. Heating the reaction mixture is followed
by thermal dissociation and structural changes with implications for the
size of specific surface (increases) and solid stability. In solids where
heating causes polymorphic transformations - the intermediate stages
are more active than the initial and final states (Hedvall's principle) and
therefore easier to react chemically, is the case of silica cement which
becomes active in that state tridinit formed at temperatures above
8700c;
d) Speed of response is increased if the preparation is done at low
temperatures reagents - explanation is that temperatures jose, crystalline
defects in the network area is increasing and is chemically active. In
preparing mixtures of reactants at high temperatures lead to lower
particle mobility of structural defects.
5.4. Materials corrosion
Corrosion is the result of harmful chemical action it determined by
natural factors or human activities. In terms of technical progress and
industrial development, corrosion has become a scourge of the modern
world. Damage due to corrosion are significant both economically - it is
estimated that one third of world steel production is lost due to corrosion,
but also by reversing the technical operating conditions and
construction of related facilities. Corrosive effects of the fixes are costly
and very difficult.
Accompanying corrosion processes are very complex and
therefore difficult to classify. Most often they take into account the
destructive mechanism of action and conduct of two types:
- Chemical corrosion due to chemical reactions
- Electrochemical corrosion - in the presence of an electric current
in an electrolyte solution

CHAPTER 5

15

After the appearance of damage, corrosion can be classified into:


- Continues corrosion - the entire area was covered by the
aggressive action
- Local corrosion - when damage occurs only on certain portions
of the surface attacked
For evaluation of corrosion processes using different methods
adapted to the type of corrosion, so we have:
- Direct methods: weighing, measuring thickness, etc. aggressive
agent consumption.
- Indirect methods: electrochemical measurements, electrical,
optical, etc..
Quantitative assessment of the corrosion process can be
accomplished by determining the corrosion rate by:
- Gravimetric index (kg), expressed as weight variation g/m2.h
which defines a sample from corrosion; kg is positive when the reaction
products remain on the surface is negative assaulted kg when reaction
products are removed from the area attacked
- Penetration index (Ip), which characterizes the only corrosion
continues and is reducing the average sample thickness is expressed in
mm / year.
5.4.1. Metal Corrosion
Corrosive effect on metals is facilitated by them, is in the form of
multi-machining alloys, resulting in a higher energy state plus the ability to
form an electrolytic cell under environmental conditions.
The metal may occur two types of corrosion:
- Chemical corrosion - is due to dry gas and liquids without electrical
conductivity;
- Electrochemical corrosion occurs in solutions of electrolytes and the
presence of moisture, a process accompanied by passing an electric
current through metal, generated by the trace of corrosion.
5.4.2. Types of corrosion
Corrosion of metals can occur macroscopic or microscopic. The
macroscopic corrosion may be general or pointed; intercrystalline
corrosion can be microscopic or selective.
General corrosion belongs to continuous corrosion continuing
process of "rust" the pieces of steel in the open air and is less dangerous
because it is easily observed and can intervene effectively.

CHAPTER 5

16

Pointed corrosion occurs only on very small surfaces thoroughly


and continues until the metal is pierced
This type of corrosion is most often occur in closed volume of
construction elements - tanks, piping, etc.. and is dangerous because
there is observed only when the construction element is perforated.
Intercrystalline corrosion is due to the fact that between the
crystals at the contact surface, tensions, the particles are activated and
therefore more susceptible to corrosive agents than Microcrystalline.
Separation layer is attacked as weakening the link between crystal
intercrystalline.
This type of corrosion occurs in steel and aluminum, which is very
dangerous, not apparent, leading to breakage of the metal elements
under load, without their appearance be changed
Selective corrosion of alloys is characteristic mixture consisting of
at least two types of crystals. The aggressive action is corroding agent
Microcrystalline voltage of dissolving only the largest (the most negative
electrode potential) and the alloy is transformed into a microporous
material. Due to increasing porosity, the metal resistance element
gradually decreases until it breaks under load, this type of corrosion is
dangerous because it can not be seen by simple examination.
The pointed "pitting" corrosion is determined by the existence of
pores in the layer of protection, which continues to deeply penetrate
metal element. This type of corrosion is found especially in pipes through
which water in some areas when conditions appear favorable for the
formation of a trace and galvanic corrosion products are removed by
mechanical action of moving fluid.
This type of corrosion is dangerous because it is observed only
when the item (usually a pipe) to drill and was removed from service.
Contact corrosion occurs at the joining of two or more metals, alloys or
different parts processed differently (joint with rivets or welding). This form
of corrosion is extremely dangerous with a high propagation speed.
5.4.3. Chemical Corrosion
Chemical corrosion of metals in heterogeneous system occurs on
the surface of metal parts. This form of corrosion occurs in particular
cases.
On the metal surface a 110 thick oxide film is formed. If the
oxide volume is slightly higher than the metal they formed (Vox / VM > 1),
the film is compact and dense surface protects the metal from further
oxidation and occurs in aluminum, copper, chromium, nickel, when the

CHAPTER 5

17

volume oxide is greater than the volume of metal consumed in its


formation (Vox / VM 1), the film is deformed and detached from the
metal surface - the case of iron oxidation. If the volume is lower than the
metal they formed (Vox / VM) <1, the film formed cracks, becomes
porous, allowing the continuation of the corrosion process - the case of
magnesium.
Oxide film character are assessed by the coefficient of expansion
which is the ratio between the volume of oxide formed (Vox) and
corroded metal volume (VM).
Chemical corrosion process is influenced by several factors, which
can be grouped as follows:
- External factors, among which the most important are: the speed
of aggressive agents, the environment interacting with the metal
composition, temperature, etc.
- Internal factors which take into account the nature, structure and
composition of the metal, surface condition, mechanical, etc. degree of
tension.
5.4.4. Electrochemical Corrosion
Characteristic of electrochemical corrosion of metals, metal bond
is a consequence of which the crystalline network is composed of ions
and free electrons. In the presence of an electrolyte solution, the metal
interface with the environment is formed galvanic elements (cells) to
generate an electrical current.
Galvanic cells thus formed lead to two types of electrode
reactions, opposite and equal speeds. It is done as follows:
- An anodic reaction (oxidation) by metal ions leaving the crystal
network, passing in a corrosive environment (dissolved) in the form of
hydrated ions and the metal surface leaving an equivalent amount of
electrons.
- Metals tendency to yield cations in the crystalline lattice in the
electrolyte solution is called dissolving tension.
Whilst there is a cathodic reaction (reduction) by free electrons
involved in reducing an oxidant (depolarize) the electrolyte (hydrogen
ions, dissolved oxygen, metal ions, etc.).
Electrochemical corrosion is therefore a mixed oxidation-reduction
process, which consists of anodic oxidation of metal and simultaneous
cathodic reduction process, which consumes electrons generated by
the anodic reaction.

CHAPTER 5

18

Electrochemical corrosion processes can be divided into the


following types:
- Releasing hydrogen process called depolarization of hydrogen
corrosion (eg, Zn+2NaOH NaOH + H2)
- Processes with oxygen depolarization 2Fe+2 H2O + O2 2Fe(OH)2
- Processes to dissolve metals, together with another metal separation,
reduction of a higher valence cation at a lower discount or another
oxidant
Sn + CuSO4 = SnSO4 + CU
Fe + Fe2 (SO4)3 3FeSO4
3Cu + 8 HNO3 3Cu (NO3)2 + 2NO + 4H2O

In metal buildings, acts as an electrolyte is introduced air unit,


which condenses on the metal surface, storm water and natural waters
containing dissociated electrolyte.
When two metals with different dissolving tensions are in contact
and in the presence of an electrolyte solution, dissolving the metal with
higher voltage corrode.
If a piece of metal covered with another metal, you may
encounter the following situations (macroscopic electrodes):
When the metal coating has higher dissolving tension, the base
metal does not corrode as long as its surface is metal coating, for zinccoated steel sheet, which does not corrode even the incomplete
coverage.
When the metal coating has lower dissolving tension, the cover
must be perfect, otherwise it will corrode the metal cover (winding
voltage is higher).
If mixing alloys, which are composed of at least two kinds of
crystals, which were always different winding voltages on the surface of
metal microelectrodes conducting trace formed cells.
Electrochemical corrosion can occur when the same metal, as a
result of different processing processes have different winding voltages,
where processing is leading to the film version of the structure, such as
riveting (the piece is rolled, forged rivet), welding ( Welded parts are
normally rolled and welding is a fusion).
It can be concluded that the bare metal parts, any unevenness
physical, structural or mass of metal or chemical environment may
create conditions for an electrochemical process, with a resultant metal
corrosion.

19

CHAPTER 5

5.4.5. Methods of metals corrosion protection


Development of corrosion protection methods requires knowledge
of the corrosion mechanism and the influences of various factors on
corrosion rate. There are many criteria for the classification of corrosion
protection methods, but most used is the factor which must be acted on
and how to apply protection
Table 5.1.
Rational choice
material
Metallic. raw
. Heat-treated or
mechanical
. ally
Metal. inorganic
. organic
Application of protective coatings. metal deposition
. inorganic films (oxides, phosphates, chromates, silicates,
emails)
. organic coatings (paints and varnishes)
Conditioning corrosive environment. vent
. oxygen deficiency in bottom
. use of corrosion inhibitors
Using electrochemical methods
protection. anodic protection
. cathodic protection
Constructive elements of rational choice. protection of metal contacts
. welding protection
. protection zone tense
. protect joints and cracks
. eliminating areas of stagnant fluids
The choice of protection method is to be applied taking into
account the maximum efficiency, on techno-economic study, to
consider the concrete conditions of operation of the construction

CHAPTER 5

20

element and how the additional expenditure is reflected in the


protection of construction cost.
The rational choice of material
The first measure is to combat corrosion rational choice of building
materials, taking into account actual operating conditions of the
assembly building.
Protective Coatings
By their nature, can coatings: metallic, inorganic and organic
a) Metallic coatings - are obtained by different methods:
electroplating, metallization, diffusion, immersion in melted metal
Galvanization is the submission of a layer or more layers of metal. It
is accomplished by electrolysis of aqueous solutions containing metal ion
coverage. The layer thus deposited is very pure and uniform thickness.
Most often, galvanic coatings are zinc, nickel, chromium plating, copper
plating, etc..
Metallization is the spray application of protective metal melt
surface to be protected. Metallization is used to cover the tanks.
Diffusion is done by treating the metal surface with another metal
protection at elevated temperatures, when forming a protective layer
consisting of a solid solution of the two metals. The realization of this kind
is known chromium plating (chrome coating is).
Immersion in melted metal, used mainly to protect the steel is
covered with a metal with lower melting point than steel, is used most
often zinc, lead, tin
Plating is done by pressing or rolling, hot, two different metals.
b) Inorganic coatings to be obtained by chemical treatment of
metal to obtain a corrosion resistant film. Such coatings are produced by
oxidation, phosphate, etc. enameling.
The oxidation is formed on the metal surface of a metal oxide, with
a protective role, that is obtained by phosphating a protective
phosphate.
Enamel surface means depositing metal layers of vitrified, opaque.
Emails should have a coefficient of thermal expansion close to the metal
shielded to not fall off or crack.
c) Organic layers - skin forming an insulator between the metal
and corrosive environment, protective layers must be adhesive,
continuous and impervious. Most used are organic protective varnishes
and paints.
Conditioning of the aggressive environment

CHAPTER 5

21

Treating the environment, in order to reduce aggression, is the


change in pH, removal of aggressive gases, the use of inhibitors and
pasivatorilor etc.
The use of corrosion inhibitors is a modern way of protection of
metal alloys. Corrosion inhibitors are used as organic or inorganic
substances, which present in very small proportions aggressive
environment, reduce or even halt the corrosion of metal. Organic
inhibitors are: aldehydes, ketones, amides, etc.. And as inorganic
inhibitors - hydroxides, cromaii, carbonates etc..
Pasivitors metal act on changing its potential to corrosive solution
that comes in contact. Chromates and electrolytes are pasiviting the
iron.
Electrochemical Protection
Protection is to reduce the electrochemical corrosion rate of steel
construction by their polarization. Electrochemical cathodic protection
and anode can be.
Cathodic protection can be applied in two versions: with anode
and current patrons outside.
Protection with anode protectors (of sacrifice) is the link to the
protected element of plates or bars of metal above electronegative
character of the protected metal. In this assembly will act as a
protective metal anode (more electronegative and will corrode, making
protected metal cathode element does not corrode. As a protective
metal commonly used in zinc, aluminum, magnesium. Thus, currently
protects cables groundwater.
Cathodic protection by external current element is the binding of
metal to the negative terminal of a DC source (with a role of cathode)
and anode is used as a buried piece of steel, aluminum, zinc, graphite,
etc. In this way it protects buried construction elements (pipes, tanks,
etc.).
Anodic protection is achieved by binding of metal elements to the
positive pole of a DC source. The process is applicable to only those
metals that are easily pasitiveaz.
The rational choice of the type of construction and mining
machinery mode
Character building and operating mode affects the corrosion rate
and location. Measures can be taken in this case are:
Protective measures required due to the heterogeneity of structure

CHAPTER 5

22

Metal metal joining systems require different processing (riveting,


welding) and different tensions, which, as shown, helps accelerate the
corrosion rate.
If mechanical reasons, the contact of two metallic structures can
not be avoided, corrosion can be reduced by some constructive
changes in nature, such as:
- Isolation of the contact areas electrically conductive materials
(fittings, plastic, rubber, resins, etc..)
- Higher electronegativity metal deposits that come into contact
metal (Al or Zn).
Corrosion protection for the action of liquid retained on the surface
metaliului
Damage during construction, metal surfaces and their joints while
creating narrow gaps on the metal surface, phonographic, slits and
cracks that develop an intense local corrosion, facilitated by the
presence of an electrolyte. In this case, it is advisable to take protection
measures by painting or galvanizing.
Concave areas corrode metal structures due to moisture condensation
and partially enclosed areas - Shell) allows accumulation of water
creating areas of active corrosion.
5.4.6. Corrosion of oxide material (inorganic)
Oxide materials (rocks, minerals, cement, glass, etc..) Have a
complex structure - heterogeneous, so complex and aggressive
environments react differently depending on the structure (porosity,
degree of crystallization, etc..) Chemical composition (mineralogical,
temperature and operating time, etc..).
Corrosive environment, where the oxide material, acting through
specific chemical reactions (currently the heterogeneous system).
Findings of the corrosion mechanism in this type of material is achieved
through processes determined the effects of the resulting reaction
products.
The corrosion processes of dissolution and leaching components
are readily soluble or reaction products that can be removed by
leaching (washing).
In acting this way:
Soft water, which dissolve some soluble components of building
materials (such as Ca (OH) 2 cement stone) or hydrolyze
hydroaluminates, hydrosilicates and calcium (calcium oxide out) making
the process of decalcification that leads to lower mechanical resistance

CHAPTER 5

23

of the corroded material. - Carbon dioxide from the air, in the presence
of atmospheric moisture makes the poorly soluble calcium carbonate
calcium carbonate readily soluble, easily washed natural waters
- Sulfur dioxide present in the atmosphere as a result of
technological processes (burning coal in power plants) along with
atmospheric humidity changes CaCO3 of different materials (natural
stone - limestone construction, etc..) In soluble calcium sulfate as easily
washed (the levigheaz).
Corrosion processes with the formation of reaction products
Soft or low mechanical strength
The chemical reactions occur between the corrosive substances in
the environment and some components of building materials, resulting
reaction products with low mechanical strength, which weaken the
material etched. Thus:
Alkali oxides (Na and K) are combined with some of the structures
of silicon making them poorly soluble substances stable substances with
low resistance (typically type gel).
Organic acids, fats, etc.. attacking some of the material by
saponification oxide (forming calcium soaps) forming substances without
mechanical strength.
Corrosion processes with the formation of reaction products with
high volume (corrosion by expansion)
Environment corrosive chemical reaction in heterogeneous system,
resulting in reaction products with a high volume, especially after
crystallization, with setting a high percentage of water of crystallization.
The chemical reaction takes place in the structure of solid material,
which opposes free-formed development of new chemical structures
and therefore impede the freedom of education., The efforts appear
corroded material can overcome interparticulare links resulting in
material damage.
Such acts of sulphates and chlorides with the formation of cement
stone structure that crystallized with 31 molecules of water.
Corrosion can occur simultaneously oxide substances through the
three operating modes, making it very difficult to analyze and prevent.
5.4.7. Corrosion of polymeric materials
For polymeric materials, corrosion is identified with the dissolution in
different solvents and aging. Sometimes, the dissolution process is
accompanied by chemical reactions.
Dissolution of polymer materials is preceded by inflation, leading to
an increase in volume up to 10 times. Between macromolecules and

CHAPTER 5

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solvent molecules penetrate interparticulare destroy links between them.


Inflation is followed by actual solvirea macromolecules. Cross-linking
polymers in the presence of certain solvents, blowing only present stage
with the formation of gels.
Polymers are only solve with the same polarity solvents (polar
polymers are soluble in polar solvents and the polar in polar solvents).
The polymers obtained by polycondensation polymers are more soluble
than by polymerization.
Aging of polymers has been treated in chapter 2.