The Basics of

Solvents and Thinners

L AFisher FTSC
Oil & Colour Chemists Association
OCCA Student Monograph No. 9

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OCCA
The Basics of
Solvents and Thinners
L AFisher FTSC
Oil & Colour Chemists Association
OCCA Student Monograph No. 9
Foreword
This Monograph is the first in a new series of Student Monographs published by the Oil & Colour
Chemists Association, and is part of a collaborative project with its South African Division.
The objective for these new Monographs is to provide a series of basic primers for newcomers to the
surface coatings industry and, specifically, for operatives and trainees in Southern Africa and the Indian
Sub-Continent. Companies, Trade Associations, Professional Bodies and the Authorities have identified
this sector as lacking educational resources and the Oil & Colour Chemists Association is pleased to
respond to this need.
The series has been published with the assistance of a grant by the Trustees of the Ellinger-Gardonyi
Fund, an educational trust, administered by the Oil & Colour Chemists Association and is supported
from resources provided by its South African Division from the funds generated by SURFEX Southern
Africa.
Published by the Oil & Colour Chemists Association,
1st Floor, 3 Eden Court, Eden Way, Leighton Buzzard, LU7 4FY, UK
OCCA 1997
ISBN 0 903809 39 7
Printed by The Burlington Press, Foxton, Cambridge CB2 6SW, United Kingdom
Typeset by My Word!, PO Box 4575, Rugby, CV21 9EH, United Kingdom
The Basics of
Solvents and Thinners
L AFisher FTSC
Introduction
Working in the so called third world countries is an education in itself. One of the things I came to realize
was that, due to lack of opportunity, there were many more people of high intelligence in the working
class than there are in the first world. The reason is due to the fact that in the developed nations
anybody with the brains and/or gumption can get an education. Hence by a natural selection system
there is a stratification. At the same time the type of education is also at variance; going from the farm
school with 30 pupils in 10 grades and one teacher, to the specialised schools with the capacity and
the staff to provide a broad curriculum. A further problem is that, as we develop, the basic qualifications
required also change 50 years ago a matric was a good starting point whereas industry can, and
does, now require a degree for the same job, thats progress. The result of this is that the first third
world gap is increasing.
In South Africa, as is also the case in Latin American and Asian countries, we have a strange mixture of
first and third world. This means that the education tends to be fairly rudimentary for the less privileged
and the Ox Wagon, Porsche gap has to be bridged. This means that industry must fill in the gaps
themselves. The result of this is that, because the demand is relatively low for such disciplines as paint
technology, the technical colleges cannot assist and the paint industry must provide its own education.
Unfortunately the courses available from the UK assume a basic school leaving certificate with maths,
physics and chemistry. To this can be added the language problems. Following on the results of the last
National Matric exams, the first post-apartheid ones in which students all wrote the same exam, one
official comment was to the effect that a greater emphasis on the Sciences will be required.
So, we have some very bright people out there with a basic education and they need only a little help.
We could throw them in the deep end, but it would be better to teach them to float first. The object of
these monographs is to help our students to bridge the gap. It is hoped that, by explaining the basic
concepts, in the least complicated manner, emphasising only the points they really need to know, they
will have a better understanding of what is going on and be less confused. We are not targeting the
higher modules of the course but only the beginners.
As someone once told me When you are up to your neck in crocodiles it can be difficult to remember
that the objective was to drain the swamp. At least let us attempt to extract some of the crocodiles
teeth.
About the author
Les Fisher has worked for over 40 years in a technical capacity in the paint, synthetic resin, GRP and
adhesive industries in the UK, USA, Latin America, SE Asia and South Africa.
Since retiring in July 1990 he has worked as a consultant in chemical technology specialising in the
identification and classification of chemical preparations with regard to their safe transport, general
handling, labelling, packaging, storage and use. He is currently also a tutor for the South African Paint
Manufacturers Paint Technology Course in the Durban area.
Part 1 Elementary Solvent Chemistry 1
Organic Chemistry 1
Elements, Compounds and Mixtures 1
Atoms and Molecules 1
Bonding of Atoms 1
Chemical Annotation 1
Valency 2
Carbon Compounds 2
Homologous Series 2
Isomerism 3
Branched Chain Isomers 3
Aromatic Hydrocarbons 4
Other Solvent Groups 5
Physical Properties 8
Conclusions 9
Part 2 Thinners and Solvents 10
Solvents and Dispersions 10
Class of Solvents 11
Diluents 11
General Considerations 12
Ozone - what is it? 13
Contents
1
Organic chemistry
The chemistry to be dealt with here is referred to
as organic chemistry. This is a very complex
science and all living organisms are covered by it
as well as a host of others. The basis of all
chemicals in this class is that they contain the
element Carbon in combination with others. In
order to keep things uncomplicated the first
chemical compounds dealt with will only involve
three elements: carbon, hydrogen and oxygen and,
as will be shown, it is in the permutations and
combinations of these that gives the differences
that make up most of the chemicals called solvents
and which are of concern to us at present.
Elements, compounds and mixtures
The first requirement is an understanding of what
is meant by an element and a compound.
An element is a single substance which cannot
broken down any further by normal chemistry, it
would require drastic action in a nuclear reactor to
change it. A compound is a chemical combination
of two or more elements as opposed to a simple
mixture. The properties of a compound are
distinct for that compound and differ from those
of the elements from which it is derived. A
compound cannot be converted back to its
original components by physical means.
A mixture would combine the properties of the
substances from which it was prepared and it will
be possible to separate the components by a
physical process ie dissolving one out, boiling one
away or even hand sorting. For example carbon is
a black solid, air is a simple gaseous mixture
essentially composed of around 1 part oxygen
and 4 parts nitrogen. If carbon is burnt in air a
chemical reaction will take place, the oxygen
present combining with the carbon to form carbon
dioxide, also a gas. The result will be another
mixture but this time it will be a mixture of carbon
dioxide and nitrogen the carbon dioxide being a
compound and the nitrogen an element. If
required the carbon dioxide can be dissolved in
water and so removed from the mixture.
Atoms and molecules
An understanding of the difference between atoms
and molecules is now required.
An atom is the smallest particle of any single
element as found in nature which can be identified
as forming part of any substance and taking part
in a chemical reaction. When several atoms join
together chemically, either with like atoms or
those of other elements, to form another stable
substance or compound, this is called a molecule.
In this way although an element may exist as a
molecule ie two or more atoms joined together, a
compound must, by definition, comprise two or
more atoms and so is always a molecule. These
are the stable forms which we encounter under
normal conditions.
Bonding of atoms
The first element to consider is carbon.
Carbon acts as a single atom and it has the chem-
ical symbol C. Hydrogen, as found in nature comes
in pairs. It has the symbol H but, because of this
pairing, will usually be written as H
2
when shown as
taking part in chemical reaction equations. Similarly
with oxygen, this is never found in the natural form
as an atom but as a molecule consisting of two
atoms. Its symbol is O and in chemical equations
will generally be represented as O
2
.
Chemical annotation
Water is often referred to as H
2
O, that is the
molecule is made up from two atoms of hydrogen
chemical symbol H and one atom of oxygen
chemical symbol O.
To familiarise you with the way we write chemical
equations the reaction of hydrogen and oxygen
would be shown as
2H
2
+ O
2
+ 2H
2
O
This equation indicates that two molecules of
hydrogen react with one molecule of oxygen to
form two molecules of water.
In reality this reaction does not take place
immediately and the two elements can be mixed.
But, once a spark or a flame is placed in the
mixture, the reaction will take place immediately
in fact it will do so with explosive violence!
So take warning! This is an opportunity to caution
everyone to take care when mixing chemical
Part I Elementary Solvent Chemistry
2
substances. Always ascertain what might happen
and by first consulting someone with experience.
To further understand what is happening the
molecule of water, H
2
O, can also be shown as:
H O H
that is two hydrogen atoms are connected to
one oxygen atom. This is what is known as the
chemical structural formula.
Valency
Note that an oxygen atom has two points at which
other atoms can be attached while hydrogen has
only one. These points are called valency bonds
and we say that oxygen has a valency of two while
hydrogen has a valency of one.
Carbon compounds
Let us now consider carbon. This has a valency of
four that is it can join up with four other valency
bonds from other elements to form compounds.
Carbon dioxide consists of one atom of carbon
and two atoms of oxygen, this formula is written
CO
2
and shown structurally,
O=C=O
again each bar in this example represents a
valency bond.
Similarly methane is made up of one atom of
carbon and four atoms of hydrogen ie CH
4
or,
when shown structurally:
note the valency bonds.
Other similar compounds are:
and so on with:
Pentane C
5
H
12
Hexane C
6
H
14
Heptane C
7
H
16
Octane C
8
H
18
Nonane C
9
H
20
Decane C
10
H
22
Unodecane C
11
H
24
Each substance having one carbon atom and two
hydrogen atoms more than the one before it.
Counting up the valency bonds on all these
structural formulas, will show that they are all
used up or satisfied.
Note that various specific arrangements keep
appearing and repeating and it is these
arrangements which are used to typify the various
compounds into special categories.
All of the above compounds have the same basic
formula
C
(n)
H
(2n+2)
that is the number of hydrogen atoms is equal to
twice the number of carbon atoms + two. They
consist of only carbon and hydrogen.
Homologous series
This is known as a homologus series and, in this
case, these are the aliphatic hydrocarbons or
alkanes (note the names all end up with -ane).
You will generally meet up with these as natural
petroleum products or as derivatives from the
petroleum refining industry.
The first members of this series are gases and
then from pentane on they are liquid. Propane and
butane are marketed as Liquefied Petroleum
Gases (LPG) as they are easily compressed into a
liquid and sold in the familiar gas bottles.
As the molecules gets bigger the compounds
become liquids. They then begin to be more
viscous eventually becoming pastes. As the size
increases further the compounds are waxy solids
and these get harder as the chain length increases.
The liquid members of this series we meet up with
as solvents, the pastes and the solid members as
greases and waxes.
H H C
H
H
C
H
H
C
H
H
C
H
H
Butane C
4
H
10
H H C
H
H
C
H
H
C
H
H
Propane C
3
H
8
H H C
H
H
C
H
H
Ethane C
2
H
6
H C
H
H
H
3
It is also possible to react these compounds with
others and the part which is created is then called
a radical. When shown as a radical the last
hydrogen atom is omitted and the result is:
Methyl radical CH
3

Ethyl radical C
2
H
4

Propyl radical C
3
H
7

In the following formulae these radicals can be

substituted whenever an R is shown. R
1
, R
2
, and
so on, indicate different radicals.
Isomerism
The next consideration is that of the phenomena
of isomerisation.
Isomers are compounds which have the same
combination of atoms but have them arranged
differently. Consider Butane.
C
4
H
10
The formula we have given above is, in fact, that
of normal Butane and when shown structurally
would be as follows. (We use symbols for the
carbon and the hydrogen atoms this time for
simplicity and clarity).
Note that all the carbons are in a straight line.
It is, however, possible for the carbons to have a
branched form and would be as below.
Note that this substance has exactly the same
combination of atoms as the first, (n-butane), but,
although it is very similar to the first, it can react
in a different way and has slightly different
properties.
So much for the simple members of the group but
it should be appreciated that, as the number of
atoms in the compound increases and the chain
length gets longer and longer, all sorts of
combination will be possible in much the same
way as it happens with a tinker toy or Lego set.
Branched chain isomers
The members of the series other than the straight
ones are referred to as branched chain isomers.
As an indication of the manner in which the structure
can change as the size of the molecule increases,
consider a member of the series, Hexane, and see
how the number of isomers increases.
All the substances which have a straight backbone
are called normal and given the n- prefix; the
branched ones are given names to indicate the
structure by numbering the carbon atoms in the
main backbone, naming it as it would appear in
the series and then naming the attached groups
and indicating to which carbon they are attached.
Examples are as follows:
Isomers of Hexane
If the last one was turned sideways it could then
be called 2.2-Methyl Ethyl Propane.
2,2-Dimethyl
Butane
2,3-Dimethyl
Butane
2-Methyl
Pentane
n-Hexane
iso-Butane
n-Butane
4
This way of naming these compounds is useful to
chemists by indicating how they will react with other
substances and what the end product will look like.
At this stage the principal concern is with their
physical properties and so, when solvents are
referred to as being iso- or secondary or tertiary
it can be understood that these are different sub-
stances. They have the same basic chemical com-
position as the normal but are structurally different
and with some differences in their properties.
Commercially many solvents are supplied as
mixtures of isomers as there is no useful purpose
served in separating them.
As a point of interest, in the aliphatic series of
hydrocarbons, the number of possible isomers for
each is as follows:
C8 18
C9 35
C10 75
C11 159
C12 355
C13 802
C14 1858
C15 4347
C20 366 319
C25 36 797 588
C30 4 111 846 763
C40 62 491 178 805 831
Aromatic Hydrocarbons
The next homologous series for consideration
also contains only carbon and hydrogen but,
instead of being arranged in open chains, the
atoms form a closed loop to which other groups
of atoms can be attached. They are known as the
Aromatic Hydrocarbons.
These are distinguished by having, as a basic
entity, a ring structure with six carbon atoms.
The first one in the series is Benzene C
6
H
6
and
this has the following structure
Again the valency bonds can all be accounted for.
For the sake of simplicity this is often shown in
forms such as those below.
The next member of this series is Methyl Benzene
or, as you may also have heard it called, by its
more familiar name, Toluene with the formula
C
6
H
5
CH
3
or structurally:
Putting the methyl radical into simpler form -CH
3
permits the showing of Toluene in a simpler way.
Once more we find a homologous series
developing.
The next member is Dimethyl Benzene, or as it is
usually called Xylene.
Again the problem of isomerisation arises the
above structure represents ortho-xylene (o-xylene)
and there are two other possibilities, meta-xylene
(m-xylene) and para-xylene (p-xylene).
Benzene
Radical
Methyl
Radical
Methyl
Radical
CH
3
Benzene
Radical
Methyl
Radical
or
Benzene
C
6
H
6
5
Following on with the logic the next chemical in
the series will be
The above can be repeated with the ethyl radical -
C
2
H
5
in one or more of the positions shown and
then with the higher members C
3
H
7
, C
4
H
9
and
so on.
It should now be appreciated that permutations
and combinations of the radicals are possible
giving Ethyl Methyl Benzene, di-Ethyl Methyl
Benzene and so on. As different radicals can be
tacked onto any of the three points, this should
give an appreciation of how many possible
combinations there can be.
These substances are called Higher Aromatics.
As the size of the molecule increases so will the
viscosity and so it is only some of the lower
members that we meet up with as solvents.
Other solvent groups
Until now the chemicals which have been
dealt with have contained only hydrogen and
carbon, these are referred to as hydrocarbons.
The next compounds for consideration also
contain another element, namely oxygen. These
are often referred to as the oxygenated
solvents.
The oxygen can be bonded into the structure in
several different ways and, depending upon this
basic grouping, we classify each group. Again
there will be variations following the homologous
series we have mentioned earlier, this should
become apparent later on when considering the
members of each group.
The different bonds, double and single, should be
easily recognised and it should be remembered
that where there is an R this refers to one of the
hydrocarbon radicals. To recap. R
1
, R
2
indicates
that different radicals are involved. These could
be Methyl , Ethyl , Propyl , Butyl ,
Pentyl and so on.
Just for a bit of confusion the Ethyl is
sometimes called the Acetyl radical and
Pentyl the Amyl radical. These names are
of historical significance rather than technical.
Alcohols
The simplest member of the Alcohol family is
Methyl Alcohol and it has a structure as shown
below.
Go back and look at the structure of Methane. The
similarity should be apparent at once, all that has
happened is that we now have an atom of oxygen
introduced into the chain or, to put it another way
we have added an OH group onto a Methyl
(CH
3
) radical.
Chemical name Short name Formula
Methyl alcohol Methanol CH
3
OH
Ethyl alcohol Ethanol C
2
H
5
OH
Propyl alcohol Propanol C
3
H
7
OH
Butyl alcohol Butanol C
4
H
9
OH
Pentyl alcohol* Pentanol C
5
H
11
OH
Hexyl alcohol Hexanol C
6
H
13
OH
Octyl alcohol Octanol C
8
H
17
OH
* also known as Amyl alcohol
H
|
H C OH
|
H
Functional Name Actual example
Group
ROH Alcohol CH
3
OH
Methyl alcohol
O O
|| ||
RCOR Ester CH
3
COCH
2
CH
3
Ethyl acetate
O O
|| ||
RCR Ketone CH
3
CCH
2
CH
3
Ethyl methyl ketone
ROR Ether CH
3
OCH
2
CH
3
Methyl ethyl ether
ROROH Glycol ether CH
3
OC
2
H
4
OH
Ethylene glycol
methyl ether
Tri-Methyl Benzene
CH
3
CH
3
CH
3
ortho-
xylene
meta-
xylene
para-
xylene
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
6
Examining the Aliphatic series again we find a
range of similar compounds but this time they all
have an OH Group replacing an H or tacking
itself on to a radical.
Obviously there are many Alcohols and the picture
is complicated by the fact that there are many
possible Isomers. In fact we have many more
Isomers than just those arising from the branched
chain iso-compounds because, in addition to the
branching of the main backbone, the -OH group
itself can be attached at different positions so
giving further different compounds. This is
demonstrated by looking at the Butyl Alcohol range
where we have secondary, and tertiary Isomers.
Butyl Alcohols
CH
3
CH
2
CH
2
CH
2
OH Normal Butyl alcohol
CH
3
\
CH
2
CH
2
OH Isobutyl alcohol

CH
3
CH
3
CH
2
CHCH
3
Secondary Butyl alcohol
|
OH
CH
3
\
CH
3
COH Tertiary Butyl alcohol

CH
3
Chemists, being great lovers of shorthand, will
refer to these as n-Butyl Alcohol, IBA, sec-Butyl
Alcohol and tert-Butyl Alcohol and at the same
time use Butanol instead of Butyl Alcohol.
In the case of the other Alcohols, their is also a
variety of Isomers and each set will have similar
properties, but this will not usually have much
consequence in their use as solvents.
Esters
The next group of concern is the Esters. Again
there is oxygen along with carbon and hydrogen.
The active group is
O
||
CO
and is between two other radicals
O
||
R1COR2
Whilst in general terms the two radicals can be
any of the hydrocarbon radicals we have
mentioned earlier, consideration here will be with
one series where one of these Rs is always a
Methyl group.
O O
|| ||
RCOCH
3
CH
3
CH
2
COCH
3
Acetate Ethyl acetate
These are called Acetates and they are the most
common esters employed as solvents.
Once again, there is an homologous series
following the Alcohols as given earlier.
Chemical name Formula
Ethyl acetate CH
3
CO
2
C
2
H
5
Propyl acetate CH
3
CO
2
C
3
H
7
Butyl acetate CH
3
CO
2
C
4
H
9
Pentyl acetate* CH
3
CO
2
C
5
H
11
Hexyl acetate CH
3
CO
2
C
6
H
13
* also known as Amyl acetate
These form a very useful range of solvents and
are effective on a wide range of resins.
There are other Esters and you may hear of them
as Lactates, Phthalates, Maleates, Propionates.
Although these also have solvent powers they are
not used in the thinners type of application as
they do not evaporate easily.
Ketones
The general formula for Ketones is
O
||
R1CR2
There are two radicals attached to the =C=O
group.
Ketones are good solvents and will dissolve
almost all resin systems. Some of the Ketones
you may come across in the paint industry are:
O
||
Acetone (dimethyl ketone) CH
3
CCH
3
O
||
Methyl ethyl ketone CH
3
CCH
2
CH
3
O
||
Methyl isobutyl ketone CH
3
CCHCH
3
|
CH
3
7
Other Ketones of interest
Another Ketones which is frequently used because
of excellent solvent properties, combined with
slow evaporation rate, is cyclohexanone.
H
2
H
2
C C
\
H
2
C C=O
\
C C
H
2
H
2
Note that this is not Aromatic, there are no double
bonds in the ring, it is one of the cyclic
compounds which are in effect molecules
wrapped around so that the ends join up.
Just for good measure there is one hybrid solvent
worthy of mention at this stage and that is di-
acetone alcohol.
O CH
3
|| |
CH
3
CCHOH
|
CH
3
It should be easy to identify the Ketone group and
the Alcohol group in this molecule.
Ethers
The general structure of Ethers is
R
1
O R
2
typical members of this group are
Diemethyl Ether CH
2
OCH
2
Methyl Ethyl Ether CH
2
OC
2
H
5
Diethyl Ethyl C
2
H
5
OC
2
H
5
It should be be possible to work out others which
can be expected.
Dimethyl Ether (DME) has found use as aerosol
propellant as it is a gas at normal temperatures
but compresses into a liquid very easily while at
the same time it is an excellent solvent so
maintaining the paint liquid in the can.
Diethyl Ether (ethyl ether) is the one which is often
simply called ether. This, along with Methyl Ethyl
Ether, has found use as an anesthetic.
Being very volatile they do not find acceptance
directly as solvents in the paint industry other than
as mentioned.
Because of their excellent solvent powers Ethers
are very important industrial chemicals particularly
in the extraction of organic substances from
vegetable matter.
The Ether group is also found in the structure of
certain materials called surfactants which are
used in the manufacture of emulsion paints.
There are, however, some higher members of the
group which have very useful solvent properties
and evaporation rates and so makes them very
acceptable as paint solvents. These chemicals are
a mixture of an Alcohol and an Ether and are
known as the glycol ethers.
Glycol Ethers and Esters
To illustrate these consider the simplest member:
CH
3
O C
2
H
4
OH
This substance is known as 2-methoxy-ethanol or
to give it another name ethylene glycol
(mono)methyl ether (note the mono is sometimes
omitted). It can also be referred to by its initials
EGMME or by a multitude of trade names; the
most famous of which is Methyl Cellosolve.
Note however that Cellosove is the registered
trade mark of the Union Carbide Co. and, by
rights, only their products should be referred to
by that name. However, it is quite common to
hear the word used as if it was the generic name.
As a guide, other trade names include
Dowanol Dow Chemicals
Ektasolve Eastman Kodak
Oxitol Shell Chemicals
Sensolve BP (NCP)
The naming and the structure should be obvious
now, a radical attached by an ether link, (O),
to another radical to which an Alcohol group is
attached.
Why a glycol? A glycol is in fact another form of
alcohol but one with more than one hydroxyl (OH)
A Word of Warning
Some very low boiling aliphatic hydrocarbons
are often referred to as Petroleum Ethers. As
this is both incorrect and misleading the use of
this term should be discouraged. These solvent
fractions are also often called Benzine (note
the spelling). This is also incorrect as well as
misleading due to its similarity to Benzene and
its use must also be discouraged.
8
group and here, in the case of ethoxy methanol, it
can be said that the parent glycol is ethylene
glycol with the formula:
OH C
2
H
4
OH
where one of the OH groups and has been
replaced with an ether link to a methyl group.
Methyl alcohol + Ethylene glycol
CH
3
OH OH C
2
H
4
OH
gives
Ethylene glycol methyl ether
(Methoxy ethanol)
CH
3
O C
2
H
4
OH + H
2
O
This group of solvents becomes more interesting
as it progresses, the next variation is the di-glycol
series.
Again a simplest member illustrates this:
CH
3
O C
2
H
4
O C
2
H
4
OH
Diethylene Glycol Methyl Ether
or Methoxy-Ethoxy Ethanol
Note that it starts out as an ether then has
another ether bridge and ends up with an alcohol
group, another example of, tinker toy or Lego
chemistry. This compound also has a multitude of
names including DGME and, again you will often
hear it referred to as methyl carbitol.
Note however, that Carbitol is a trade mark of
the Union Carbide Co. but the other producers
have their own names such as methyl dioxitol
(Shell).
As a matter of interest, due to the fact that they
may have long term health problems, the use of
ethyl and methyl versions of this group has been
drastically reduced. Some companies have
eliminated them from their range. Even the Buty
versions are suspect and attempts to replace
them with the Propyl version are being made.
Glycol Ether Esters
As was the case earlier when it was shown that an
Alcohol could be converted to an Ester, a similar
reaction with these solvents is possible and a
series of Esters is possible, the simplest
examples is:
CH
3
O C
2
H
4
COO CH
3
Ethylene Glycol Methylether Acetate
Being Esters they have different solvent powers.
The naming of these solvents is fairly complex
and especially when isomers are concerned. It is
common for ethylene glocol methyl ether to be
named ethylene glycol monomethyl ether so as to
ensure there is no confusion with the dimethyl.
Just ensure that you are aware of which one it is.
The present tendency especially in Europe is to
use the 2methoxy ethanol style wherever
possible.
Physical properties
In paint formulation it is the physical properties of
solvents which are important and not so much the
chemical properties. The chemical grouping is
important because, if a given resin is soluble in
one particular type of solvent or combination of
solvents, then generally any solvents in the
particular group will show the same
characteristics. Thus if a resin is soluble in
acetone it will almost certainly be soluble in other
ketones. As a general rule it is also the case that
the lower members of any homologous series will
give a lower viscosity, on a volume to volume
basis, than that given by the higher members. In
other words the cutting power (ability to reduce
viscosity) will be greater for the lower members.
At the same time the evaporation rate, (the rate at
which the solvent leaves the films) will change with
the size of the solvent molecules (number of
carbons in the backbone) in any homologous
series. Such properties as Boiling Point, and Flash
Point will also follow a similar pattern but
remember that this is generally confined again to
the homologous series.
Specific gravity
It is the custom, in many companies, to use
weight in their formulations rather than volume.
The reason for this lies in the fact that the specific
gravity of solvents varies. That is, a litre of one
solvent will not weigh the same as a litre of
another. At the same time volume is temperature
dependant, that is to say that on heating a liquid it
will expand, this in turn means that the volume of
a given weight will increase with temperature. It
therefore, follows that, if volume is to be used as
a measure, then the temperature will need to be
controlled for all substances used. In the
laboratory the weight method has generally
become the preferred procedure. In the factory
9
volumes are often used, especially for solvents,
some operators using a standard conversion,
others relying upon the final adjustment to make
up differences. In general, paints, while being sold
by volume, are packed by weight for operating
convenience and accuracy. Whether the volume or
weight method is used is not of such great
importance as that of understanding the
implication and taking the correct precautions.
The paint formulator must therefore bear the
concept in mind when substituting solvents and
allow for differences in specific gravity. Also
remember that the non-volatile content of a paint
in generally expressed in terms of weight and so
is influenced by the specific gravity of the solvent.
Boiling point
With regard to boiling point; pure chemicals have
a fixed boiling point but mixtures will have a
range. The mixture will usually start to boil at or
around the boiling paint of the lowest one in the
mix and the final (dry point) will be around that of
the highest component. For any mixture of
solvents these two figures will not change to any
great extent and so the information is somewhat
limited. The exact composition of mixtures can
only be compared properly by considering the
distillation range. This is given as the percentage
of liquid which distils over at defined
temperatures. By comparing the ranges of two
mixtures the composition of two mixtures can be
compared.
Evaporation rate
This effect also applies to evaporation rate. The
evaporation rate is a fixed figure which only really
tells us the slowest member. For this data to be
useful it should be read in conjunction with the
distillation range.
The evaporation rate may also be affected by the
solvent affinity of some resins. Different resins
have different release rates for certain solvents. In
this case a solvent entrapment or slowing down of
speed of set of the coating can be the result. Do
not be surprised if a coating does not follow the
path expected from the evaporation rate. At the
same time do not be surprised if a coating which
appeared to dry will becomes brittle after a few
days, this can be the result of solvent affinity and
so what we have is a temporary plasticiser.
Flash point
With regard to flash point this will generally
depend upon that of the lowest member of the
mixture. But a word of warning, the flash point of
some mixtures can be lower than the expected
one. An example where this can happen is with
butanol and xylol. If this is near the cut off point
used in legislation, it is better to carry out a final
check on the finished paint.
Conclusions
Solvents are in general the tools of the trade for
paint formulators. They are hammers,
screwdrivers and spanners. They do not remain in
the finished coating but instead provide a way of
getting the coating into the required place in the
required way. Just as there are different sizes and
types of hammers, screwdrivers and spanners so
there are different types of solvent groups. Having
decided just what type of spanner is needed to
adjust a particular fastener we next need to know
what size it is. Using the wrong one could damage
the fastener and so weaken the whole structure.
So it is with solvents, being near enough is not
always good enough and, as the skilled engineer
must know how to judge and pick the correct tool
and apply it properly, so must the paint formulator
know his solvents. Aliphatics, Aromatics, Esters,
Ketones and are the hammers, screwdrivers and
spanners of the paint chemist. Knowing how to
use them properly is the most important skill of
the paint formulator.
Note that when the job is finished the tools are
taken away in the same way as the solvents. Any
10
Liquid paints consist essentially of two parts, the
solids which will be left after it has dried and the
volatile portion which evaporates during and after
application and thereafter plays no further part in
the action. During this initial phase, as the solvent
evaporates, the applied paint increases in
viscosity. If this takes place too quickly it will be
difficult to apply and will not flow out to give the
desired finish, if this takes place too slowly sags
and runs will be the result. For these reasons the
volatile component has to be carefully chosen.
This volatile part is referred to as the thinner or
solvent and, if the paint has to be applied by
brush or roller, it will generally be slower
evaporating than the one needed for spray
application. This thinner/solvent is only required
for application purposes, is completely disposed
of and hence to some extent fills the same role as
the container. In other words it gets the paint from
the manufacturer and onto the job where it is then
thrown away. What is therefore required is the
most cost effective method of getting the proper
thickness of paint onto the job but, as these
liquids are Volatile Organic Components
(VOCs), they also have environmental side
effects which must be kept in mind.
What is the difference between a solvent and a
thinner? A solvent, as we know it in the paint
industry is, almost without exception, a thinner. A
thinner, on the other hand, is not always a true
solvent. In others words if you mix a thick liquid
with a thin liquid then the thin liquid can be
described as the thinner. In simple terms it will
reduce the viscosity. In the case of emulsion
paints the thinner is water but it is in no way a
solvent for the system as a whole! When a liquid
can be mixed with another, but is not a solvent, it
is referred to as a diluent. This is only a physical
mixture of two liquids.
In some cases, when further additions of the
thinner are made a situation could arise when the
mix begins to curdle and throw out. An example of
this would be an automotive lacquer which will
only take a limited quantity of white spirit before
curdling.
This problem can become obvious when it comes
to washing the equipment. In the case of the
emulsion paint the equipment can be washed with
water because the paint will accept unlimited
addition of water. This is because it is in a
dispersion and not in a solution!
Washing equipment used to apply industrial paints
calls for a careful choice of a suitable agent the
thinner might do the job easily but it is not
necessarily so. There are cases where the thinner
is not the best cleaner. After all the thinner was
formulated with application properties in mind. A
gun/equipment cleaner may be a more
economical and better proposition; especially
when formulated for the job.
Solutions and dispersions
Generally liquid coatings are of two types, solution
based or dispersion based. Solvent based
coatings will be based upon a solution of
polymeric or polymerisable material(s) whilst, in
the case of the dispersion, the solid or semi-solid
particles are suspended in another liquid. As
mentioned above the objective in both cases is to
make the paint sufficiently fluid so that it can be
applied easily.
By definition a solution is a homogeneous mixture
of two or more substances. The dissolving
medium is called the solvent, and the dissolved
material is called the solute. In most common
solutions, the solvent is a liquid, and the solute
may be a solid, gas, or liquid. Syrups are
solutions of sugar, a solid, dissolved in water.
Soda water is a solution of carbon dioxide, a gas,
in water, and Vinegar is a solution of acetic acid, a
liquid, in water. A solution is not necessarily liquid,
it can be solid certain plastics are examples of
this and so are some coloured glass objects for
example sunglasses.
In other words the resultant mixture will appear as
one and will result in a clear (coloured maybe, but
transparent) product. This is referred to as a
single phase system.
In the case of solution materials the bigger the
polymer, the bigger the individual molecules and
consequently very viscous solutions are the result.
This means that the amount of polymer in the
solution can be low with the result that the film of
the paint/lacquer, after the solvent has
evaporated, will be very thin. To give an adequate
Part 2 Thinners and Solvents
11
coating under these circumstances will usually
mean that several coats will need to be applied.
In the case of the dispersion resins (the most
common and best known are usually referred to
as emulsions) relatively big molecules or particles
are involved. If these were to be used in solution
form, they would give high viscosity materials of
no practical value. By suspending small particles
of these resins in a water phase we can produce a
liquid material which will permit a high solids film.
In this case the resin particles usually need to
have a small quantity of solvent added to them to
make them stick or coalesce together. This
solvent, which evaporates after the water has left
the film, is referred to as a coalescent.
As a point of interest, note that the term emulsion
resins comes from the method of manufacture
they are not true emulsions but are actually
latices (latexes). By general definition a latex is a
dispersion of a solid in a liquid while an emulsion is
the dispersion of a liquid in a liquid. In the emulsion
polymerisation process the monomer(s) from
which the polymer is made are emulsified first and
then converted into the final product.
The speed at which a solvent leaves a system is
something which must be given careful
consideration. Resins and polymers have a
variable tendency to hold on to solvents and some
can be retained by the film for some time. When
solvent is retained it acts as a temporary
plasticiser and so the film can appear to be quite
flexible but after a period the film may become
brittle and lose its flexibility. Always check for this.
This effect is often noticeable in the form of the
smell it gives off if kept in an enclosed space. It
also accounts for the solvent smell which come
from certain water-based paints and which can be
noticed after the room has been left closed for
some time quite a problem for hotels who want
a quick turnaround of their rooms during
maintenance.
This affinity for solvents varies with the resin
system and the solvent, in other words some
classes of solvent are retained more easily by
some systems than by others. Care must also be
given to the problem of case hardened coatings.
Often the surface of the paint can dry more
quickly than the underlying layers thus trapping
solvent. The use of anti-skinning aids in
convertable systems often proves necessary but
the use of small quantities of high boiling point
(slow evaporating) solvents may also prove
necessary.
Classes of solvents
A true solvent is one which will satisfy the criteria
in all proportions. There is sometimes a limit to the
amount of substance which can go into a solution.
If salt is added to water it will dissolve. If, however,
the addition of salt is continued a point will be
reached when no more can be dissolved; this is
known as the saturation point. In the case of salt
the solid would settle out as white crystals. We
would then have a two phase system one solid
phase (the salt) and one liquid phase (the salt
solution). This is referred to as a saturated salt
solution no more salt can dissolve in the water.
In the case of liquids like oil and water they would
form two phases both liquid.
In the case of certain resins these will only
partially dissolve or swell when mixed with certain
solvents but on addition of a second solvent a
true single phase solution can result. When such
a mixture of solvents is used and a true solution is
obtained, these solvents are referred to as
co-solvents or latent solvents. In effect what is
happening is that part of the resin molecule
dissolves in one solvent and another part in the
other solvent or we have a mixture of two
solutions which are compatible.
It is also quite usual in the surface coating
industry to make binders from two or more resin
systems each with its own solubility parameters.
This often leads to the need to use a mixture of
solvents to get a clear homogenous product, or,
as we term it, compatibility. This compatibility
must be maintained until all the solvent/thinner
has left the coating.
Certain solvents and thinners can consist of a
mixture of substances. One way of telling whether
it is a mixture or not is to look at its boiling point.
If this is a single number, or a range of two
numbers close together, then it will almost
certainly be a pure, or relatively pure, substance.
If there are two numbers, a range, then it will be a
mixture. Always consider the boiling point and the
evaporation rate when comparing solvents, The
evaporation rate alone, being dependant upon the
higher boiling component, can be misleading.
Diluents
In certain cases, once a solution has been made,
then another liquid can be added and the result
will be a clear homogenous solution. If, however,
on further dilution, there is a separation into two
phases shown either by a clouding of the mix or
by a separation into two layers then the liquid
12
being added is a diluent. For these reasons it is
important to ensure that the diluents leave the film
before the true solvents i.e. have a faster
evaporating rate
Diluents are sometimes referred to as a means of
cheapening paints but let us be quite clear that,
whilst some unscrupulous formulators may use
them in this way, it is not to be accepted as a
general rule. These formulators make use of the
fact that diluents do not generally reduce the
viscosity as quickly as solvents and so they deliver
a product with a lower solid content. As it is the
solids which give the protection a proper balance
must be kept. Diluents, properly used, play a very
important part in the formulation of thinners and
their use should never be decried. When used
correctly they can produce more cost effective
formulations and be more environmentally friendly
and less hazardous to health.
As an example consider a paint which is to be
applied by spray. The purpose of the thinner is to
reduce the viscosity to a point where it will atomise
properly. As some 30% of the solvent can
evaporate between the nozzle of the gun and the
surface to which it is applied, one part of the
thinner can be considered to have done its job as
soon as the paint leaves the gun. Providing this has
no other side effects such as blooming, then this
component of the thinner only needs to be a
diluent. A fractionally heavier spray setting to get
the correct film build can give compensation but, in
the case of pigmented coatings, obliteration will
dictate the thickness of the applied film. If the
correct solvent balance is built into the original
paint there should be no problem but it is advisable
to buy thinners from the paint manufacturer or
conduct careful tests as to their suitability. If a high
proportion of diluent is already built into the original
paint, thinner selection can be critical.
In the case of aerosol containers the choice of
propellant for paints is usually Liquefied Petroleum
Gas (LPG) which can be propane or butane (in
South Africa the commercial available version is a
mixture). On a cost/availability basis the choice is
not difficult. Other propellants are di-methyl ether or
fluorocarbons but, due to environmental problems,
the latter is now only used in very specialised
cases. Di methyl ether is favoured, by the cosmetic
industry and other specialised end users, when LPG
is either undesirable or unsuitable.
So far as the paint industry is concerned LPG is
simply a low boiling aliphatic solvent and so
serves the dual purpose of being a propellant as
well as a diluent. Although, in some cases, the
aliphatic might be a latent solvent, the term
diluent is probably more appropriate here as it
plays that role perfectly. The paint system used
must be aliphatic compatible and this can be
achieved by the incorporation of strong solvents
in the orignal base paint.
Compatibility tests on the resin system will be
needed and, if the paint can stand dilution with
pure pentane or hexane to reduce it to spraying
viscosity, then it will probably will accept LPG. The
LPG is usually injected into the can after the
required amount of paint has been filled and the
container capped but cans may also be prefilled
with propellant and the paint injected into the can.
This latter procedure was used for automotive
touch-up paints.
As a point of interest consider the Soda Water
siphon which is, in effect, an aerosol. Here the
propellant (a gas carbon dioxide) is dissolved in
the water and is maintained in solution by
confining it to its receptacle, keeping the gas
under pressure. So, as is the case with the
aerosol, the pressure is sufficient to force the
contents out of the container when the valve is
opened.
General considerations
The pigments and extenders in coatings are
insoluble materials and are dispersed in the paint
whether it be a solution or a dispersion resin
system. They will therefore interfere with the
system and it is always advisable to examine the
binder system without these present to ensure a
proper film is formed. it is also important that the
resin systems themselves remain compatible after
all the solvents/diluents have left and, for these
reasons, tests must always be conducted on the
unpigmented system to ensure that the residual
film is compatible.
Whether using a diluent or a solvent in any system
the dry unpigmented film should be as clear as
possible once formed or coalesced properly, if it
is not, an underbound friable coating may be the
result.
It should be borne in mind that all solvents and
thinners are VOCs and are becoming a cause for
global pre-occupation. This is due to the
contribution they are making to photo-chemical
smog, high atmospheric ozone levels (not to be
confused with the Ozone Layer problems), and
global warming. For these reasons legislation is
being introduced in many parts of the world to
13
regulate the quantity of these substances which is
emitted to the atmosphere.
Ozone what is it?
There appears to be a certain amount of confusion
concerning the role of solvents and their
relationship to problems of the Ozone Layer, global
warming amongst other environmental issues.
These notes are aimed at clarifying the position.
Oxygen can exist in two molecular forms O
2
or O
3
that is either two or three atoms in the
molecule. Ozone has three atoms and is relatively
unstable returning to the more stable O
2
form
easily. As it gives up its third atom very easily it is
a strong oxidising agent and, as such, a potent
bleach and disinfectant. It is active in the
breakdown of plastics and surface coatings. It has
a distinctive smell and can be detected in a
concentration of 0.01ppm in air. It is highly
poisonous at a concentration of 0.1 ppm. It is
about a hundred times as poisonous as carbon
monoxide!
Ozone is formed in the air around us by the action
of ultraviolet light. In rural areas it may reach a
level of 0.02 to 0.03 ppm. In cities, there is
usually less because there is less sunlight
unless there are certain chemical impurities in the
air. The greatest effect is from oxides of nitrogen
NO
x
coming predominantly from exhaust
emissions. This is broken down by ultraviolet rays
to give nitric oxide, NO, and atomic oxygen O.
The atomic oxygen then reacts immediately with
molecular oxygen to form ozone. Under normal
circumstances this ozone reacts again with the
NO to give NO
2
and the cycle keeps repeating and
a stable state should result. However the
presence of hydrocarbons interferes with this
second reaction by scavenging the nitric oxide
thus increasing the levels of nitrogen peroxideand
ozone in the atmosphere. This results in
photochemical smog and concentrations of ozone
as high as 0.5 ppm (above the danger zone) have
been reported on smoggy days.
Whilst it was first thought that only hydrocarbons
were responsible, it has now been found that, to a
greater or lesser extent, all volatile organic
substances take their part hence the concern
with solvents.
It is of interest to note that many people think that
the need for lead free petrol is to reduce lead
pollution in the air. While this may be true to some
extent, the principle role of lead free fuel is to
minimise the poisoning of the catalyst used in the
exhaust system to cut down hydrocarbon
emissions.
When fluorocarbons first came into use it was felt
that their great advantage lay in their relatively
stable nature. They are not broken down in the
troposphere (the first 10Kms. of air above us).
Instead they migrate to the upper level of the
stratosphere (50 Kms.) where the ozone layer is
found. Here the ultraviolet breaks down what little
oxygen there is to form ozone. The reaction of
CFCs with the ozone means that the total
oxygen/ozone levels are depleted and this allows
the penetration of ultraviolet light to the earths
surface. The presence of the ozone layer, by
preventing ultraviolet rays penetrating, has made
life, as we know it, possible. In addition to other
side effects the penetration of ultraviolet rays
gives rise to the high ozone at ground level as
discussed earlier. The high levels of tropospheric
ozone cannot cancel out the imbalance. Ozone is
not only unstable but there is also no mixing of the
tropospheric and stratospheric layers
Ozone, carbon dioxide, methane, halogenated
solvents and oxides of nitrogen, because they all
retain heat, contribute to global warming and the
greenhouse effect.
The two ozone problems are different but the hole
in the ozone layer and the greenhouse effect is
interrelated.
Solvents and vehicle emissions alone are not the
only source of VOCs. Natural sources include pine
needles, gum trees and camphor as well as
natural oil and gas wells. There is also a
considerable production of Methane from natural
decomposition and the digestive processes of
ruminants. This is not classed as a VOC. This is
nevertheless, quite a cause for concern
especially when we hear of forests being burnt to
provide beef pasture.
Hydrocarbon emissions from automobiles have,
as we have mentioned, been targeted. Efforts are
being made, to a greater or lesser extent, to
reduce the venting of tanks to the atmosphere.
This depends, to a great extent on the smog
situation and the action of pressure groups.
The use of solvents could be reduced even with
present day technology. One of the reasons for
the slow transition being that many people look at
the price rather than the cost. Our industry must
face up to the fact that this problem must not be
allowed to get worse it is certainly not going to
go away. I
Titles in the Student Monograph Series
Honorary Technical Education Officer: A T Hopgood FTSC
Honorary Editor: P S Thukral PhD CChem FTSC
Chairman Special Publications Committee: R H E Munn BSc LRSC FTSC
Oil & Colour Chemists Association
1st Floor, 3 Eden Court, Eden Way, Leighton Buzzard, LU7 4FY, UK
Tel: 01525 372530 Fax: 01525 372600
Email: publications@occa.org.uk
No. 1 Basic Science for Students of Paint Technology
No. 2 Corrosion
No. 3 Water-borne Resins
No. 4 Colour Physics
No. 5 Dispersion and Dispersion Equipment
No. 6 Additives for Water-borne Coatings
No. 7 Standards
No. 8 Water-borne Coatings
No. 9 The Basics of Solvents and Thinners