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Introduction: Fundamentals of
Suspensions & Dispersions
CONTENTS
INTRODUCTION
MECHANISMS OF FLOCCULATION
4.1
4.2
Dilute Suspensions
Concentrated Suspensions
SUMMARY OF STRUCTURES
PARTICLE PACKING
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RHEOLOGY
8.1
8.2
8.3
8.4
Summary of Rheology
Deflocculated Suspensions
Flocculated Suspensions
9.1
9.2
9.3
9.4
10
ELECTROKINETIC BEHAVIOR
11
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12
References
13
Figures
Fig 1a
Fig 1b
Fig 1c
Fig 2&3
Fig 4
Rheological Behavior
Fig 5
Fig 6
Fig 7
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INTRODUCTION
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VA
FA
=
=
- aA/12 (R 2a)
aA/12 (R 2a)2
(1)
(2)
1)
2)
Adsorption of non-potential determining inorganic ions, particularly polyions such as polyphosphates, silicates, etc.
3)
4)
5)
More generally
is proportional to
Ionic strength.
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The range of the electrostatic repulsion thus depends upon the ionic composition
of the medium. For 1:1 electrolytes the range can be judged from the
following table.
Electrolyte Concentration
10E-5 mol dmE-3
10E-3
10E-1
Steric repulsion arises when the particle surfaces are coated with a layer of
solvated molecules of high molecular weight. Suitable species are flexible
polymers and surfactants with oligometric or polymeric head groups. Natural
systems such as biological cells and particles in natural waters may be
adventitiously sterically stabilized, otherwise particles will not normally be
sterically stabilized unless a suitable species has been deliberately added as a
dispersant. Commonly used steric stabilizers include
1)
where X is either an acidic or basic group (in the Lewis sense). These are used
to disperse polar particles in organic solvents with the X group anchoring the
molecule to the surface, and the poly(l2-hydroxystearate) chain (PHS) acting as
the stabilizer.
2)
These are used as dispersants for hydrophobic particles in water with the longchain alkyl groups acting as the anchor and the ethoxylated chain acting as the
stabilizer.
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Molecules of this type with n/m -10 are used as dispersants in water, The acetate
moieties presumably anchor the polymer leaving loops and tails of
polyvinylalcohol penetrating Into solution.
4) Graft polymers, eg
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VTotal = VA + Vi + V
(5)
2)
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The height of the energy barrier depends upon the Ionic strength and
composition of the medium, and the surface potential or surface charge density
of the particles < the two are roughly proportional for surface potentials of 50 mV
or less, generally speaking the potential at the fixed charge boundary is of this
order). It is generally considered that a surface potential of + 20 mV or more is a
necessary but not sufficient condition for stability, this typically corresponds to a
fixed-charge density of the order of one charge per (10 nrn)2 or more. The height
of the energy barrier can be reduced and suspension destabilized by
1)
2)
2)
ccc
0.1 to 0.5 molar
0.1 to 0.5 molar
BaCl2
MgCl2
10(-4) to 5x 10 (-4)
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These data clearly demonstrate the effect of counterlon valency. Notice that
electrostatic stabilization fails In the presence of only modest concentrations of
divalent and trivalent ions.
Electrostatically-stabilized suspensions are also sensitive to mechanical action
(agitation and shear) unless the particles are small (< 0.5 m), this is particularly
the case when the dispersion is concentrated and it is usually difficult to prepare
high solids dispersion relying on electrostatic stabilization alone. A measure of
steric stabilization is normally required. In this context it is appropriate to note
that the maximum in the potential energy curve lies quite close to the surface (of
order 1 to 2 nm). Thus a steric barrier much thinner than that required to impart
stability to an uncharged system can be sufficient to improve the stability of
concentrated dispersions in water (cf Figure 1c). This explains the observation
that particles dispersed with anionic surfactants and bulky polyions such as
polyphosphates, low molecular weight polyacrylic acid salts, sodium Dispersal+,
and the like are more + Sodium Dispersol is the sodium salt of sulphonated
naphthalene-formaldehyde condensate of representative formula
stable than simple charged particles with equivalent Ionic charge densities, the
presence of a bulky charging species imparting some measure of steric
stabilization. With the aid of such agents it is possible to prepare concentrated,
stable dispersions.
Example: Emulsifier-free polystyrene particles with particle diameters between
0.2 and 2 pm can readily be made In water by emulsion polymerization. This is
typically done at 10% v/v solids and the resulting particles are stabilized by SO4and COO- groups at the surface. Attempts to concentrate such lattices, e.g. by
rotary evaporation at reduced pressure, almost invariably result In coagulation.
However if sodium DISPERSOL Is added they can be concentrated without
difficulty.
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MECHANISMS OF FLOCCULATION
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4.1
Dilute Suspensions
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4.2
Concentrated Suspensions
In concentrated suspensions there Is no room for discrete flocs and above some
critical concentration a continuous network will form throughout the available
space. The critical concentration, usually called the gel-point, generally increases
with particle size and with decreasing strength of flocculation, it being easier to
form a continuous network from open floes than it is from condensed clusters.
In the case of spherical particles the gel point can be anywhere between about
0.1 and 0.3 typically when expressed as a volume fraction, 0.1 being
characteristic of strongly flocculated submicron particles and 0.3 being more
typical of cluster percolation In weakly flocculated systems. Gel-points as low as
0.01 can be observed when the particles are highly acicular. The rheological
properties of suspensions change markedly at the gel-point. If the flocculation is
strong a yield stress develops and the viscosity increases rapidly.
Stable sediments and coherent filter cakes form above the gel-point and so the
location of the latter is a very important processing consideration.
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SUMMARY OF STRUCTURES
PARTICLE PACKING
0.74
0.74
0.68
0.636
0.524
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RHEOLOGY
The concern here will be primarily with the shear flow behavior of
suspensions. Simple molecular liquids in shear flow obey Newtons law.
This states that the shearing stress Q required to maintain a uniform
laminar shear-flow characterized by a velocity gradient or shear-rate Is
proportional to p the constant of proportionality being the shear viscosity
. Two-phase fluids such as suspensions generally show more complex
behavior and may have a variable Viscosity. The viscosity of suspensions
typically depends upon shear stress or shear-rate (whichever is chosen to
be the independent variable characterizing the strength of the flow) and
may also depend upon time and previous history. Suspensions are often
found to be shear-thinning, that is have a viscosity that decreases with
increasing shear-stress or shear-rate, very concentrated suspensions can
however show the converse behavior, shear thickening or dilatancy.
Various types of shear-rate dependent behavior commonly encountered
are illustrated in Figure 4. Type 1, where the viscosity varies between two
extreme Newtonian limits, is typical of weakly flocculated suspensions and
moderately concentrated stable suspensions (although in the latter case
the difference between (0) and rho Is often oo small as to be of little
consequence). Type II behavior, where (O) IS essentially "Infinite" and
the material, in effect, shows a yield stress, is characteristic of strongly
flocculated suspensions, or more generally concentrated suspensions in
which there are strong interparticle Interactions. Types III, IV and V, VI are
typical of very concentrated suspensions; Types III, IV and V are shown
by concentrated, stable suspensions of ever-increasing concentration. In
the case of flocculated suspensions the tendency to shear-thicken at very
high concentrations is often masked by the shear-thinning that flocculation
tends to introduce and something like type VI can be observed.
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Colloidally-Stable Suspensions
8.2.1 Spherical Particles with diameters of the order of 1 m
or more
Stable suspensions of spherical particles with diameters > 1 m are
found to be Newtonian provided the volume fraction of the solid
phase is less than 0.5 or so. In this concentration regime the
viscosity depends only upon volume fraction and the nature of the
particle size distribution, and not on shear-rate or absolute particle
size. Viscosity/volume-fraction curves for monodisperse particles
conform to the Dougherty-Krieger equation:
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It is probably fair to say that most sub-micron suspensions met in industry are
hard-sphere-like rather than soft-sphere-like, since for significant departure from
hard-sphere-like behavior to be seen one or more of the following conditions has
to be observed:
(a)
and/or (b)
and/or (c)
the ionic strength of the medium has to be very low (In the case of
aqueous suspensions).
8.3
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2)
3)
4)
A recent study by Mills [5] on model dispersions has shown that the following
observations can be made:
1)
B Is typically twice y.
2)
3)
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4)
For larger particles (> 1 m) the plastic viscosity tends to differ little
from the viscosity of a deflocculated suspension. For smaller
particles It can be larger. Nevertheless the Bingham yield stress
usually makes a major contribution to the stress. This is thus a key
parameter.
2)
3)
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2)
3)
The latter means that structured suspensions that appear quite fluid can
be rather "solid-like" In compression and difficult to dandify by mechanical
means P is a very important parameter in solid-liquid separation theory
(cf Chapter 3).
8.4
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9.1
Expressions are available for other shapes of particles, for example for
ellipsoids with semi axes a, b,c the settling velocity is reduced as
compared to that of a sphere of the same volume by a factor
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However, K lies In the range 0.95 < K < 2 for aspect ratios (a/bc)
between 0.125 and 16 so that the settling velocity of a volume equivalent
sphere Is a good approximation for most purposes.
9.2
Concentrated Systems
There is a lot of experimental evidence to the effect that the initial settling rate of
a concentrated system of volume fraction goes like
9.3
Polydisperse Systems
It is often stated in the literature that whereas dilute mixtures of differing particle
size tend to move more or less independently, concentrated systems ( > 0.2)
undergo hindered settling and move en-masse. There is however no evidence
for this in systems that are deflocculated and particles are observed to move
more or less independently unless the volume fraction is very high (> 0.5).
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9.4
Flocculated Systems
In dilute systems flocculation Increases the settling velocity by increasing the size
of the sedimenting unit. In concentrated systems (above the gel-point 1 the
converse Is true. In this regime sedimentation, If It occurs at all, occurs by the
network of particles collapsing under Its own weight. For sediments with a yield
stress
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10
ELECTROKINETIC BEHAVIOR
11
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Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com
Refinery Process Stream Purification Refinery Process Catalysts Troubleshooting Refinery Process Catalyst Start-Up / Shutdown
Activation Reduction In-situ Ex-situ Sulfiding Specializing in Refinery Process Catalyst Performance Evaluation Heat & Mass
Balance Analysis Catalyst Remaining Life Determination Catalyst Deactivation Assessment Catalyst Performance
Characterization Refining & Gas Processing & Petrochemical Industries Catalysts / Process Technology - Hydrogen Catalysts /
Process Technology Ammonia Catalyst Process Technology - Methanol Catalysts / process Technology Petrochemicals
Specializing in the Development & Commercialization of New Technology in the Refining & Petrochemical Industries
Web Site: www.GBHEnterprises.com