Chapter Two: Particulate Systems

2.
CHAPTER TWO
PARTICULATE SYSTEMS
2.1 WHAT ARE PARTICULATE SYSTEMS?

 Any systems which contain particles in a fluid.
Particle  dispersed phase (solid, liquid or gas)
Fluid  continuous phase (solid, liquid or gas)
Examples:
System Particle Fluid
Slurry Solid Liquid
Emulsion Liquid #1 Liquid #2
Dust Solid Gas
Mist Liquid droplets Gas
Foam Gas bubbles Solid
Froth Gas bubbles Liquid
 Solid particle-fluid systems are the most common in many processes and unit
operations.
2.2 DESCRIPTION OF PARTICLES

 A good description of particles is essential in any operation involving particulate
systems.
2.2.1 General Properties

i. Chemical Properties:
e.g. Chemical composition, conductivity, surface charge, reactivity...
ii. Physical Properties:
e.g. Particle size, particle size distribution, surface area, shape, porosity...
 Here we are mainly concerned with physical properties in describing particles.
Fluid and Particle Mechanics

Particulate Systems 2.2
2.2.2 Particle Size

 As one of the most important parameters, particle size determines:
- Settling rate
- Filtration rate
- Heat & mass transfer characteristics
- Product quality
 Typical practical size range: 1 m – 100 mm
Approximate Size Classification (by convention):
Class Size Limits Common Units for Particle Size
Coarse particles > 1 mm mm, cm or inch
Fine 0.1 - 1 mm mm or screen (mesh) size
Very Fine 1 m- 1000 m m or Ao

Ultra Fine < 1 m m, Ao, or surface area per unit mass (m2/g)
 Other similar classification, as used in soil mechanics: Rock  Sand  Clay  Slime
a. Particle Size Description

 Only in case of spherical particles, can the size of a particle be described in a single
number: size  diameter.
 For non-spherical particles, need more than one size and shape  equivalent diameter
 Multiple particles: as above + size distribution
b. Equivalent Particle Size (for Non-Spherical Particles)

Defined in terms of an equivalent sphere having the same measurable size-dependent
property as that of the particle.
i. Volume (equivalent) Diameter (dv):
dv: diameter of a sphere of same volume as volume of particle (Vp):
1/ 3
d 3V  6Vp 
Vp   dV   
6   
ii. Surface Area (equivalent) Diameter (ds):
ds: diameter of a sphere of same surface area as surface area of particle (Sp):
1/ 2
 Sp 
Sp  d  dS   
2
 
S

iii. Surface-Volume (equivalent) Diameter (dsv):

dsv: diameter of a sphere of same surface area per unit volume (Sp/Vp) as that of the
particle:
dSV
2
  3  dSV  6  Vp / Sp   d 3V / d S2
Sp
Vp 6 d SV
Examples of other equivalent diameters:
Equivalent Diameter Symbol Reference Size-Dependent Property

Projected area diameter da Projected Area (stable position)
Projected area diameter dp Projected Area (random orientation)
Drag diameter dD Drag force
Stokes diameter dSt Terminal settling velocity
Many other equivalent diameters are available (see, for example, Allen, T., Particle Size
Measurement, 4th ed., Chapman & Hall, New York, 1990).
 Choice of equivalent diameter depends on intended application or process to be
modelled or controlled.
2.2.3 Particle Shape

 Necessary to define geometry of non-spherical particles.
 Shape influences properties such as flowability of powder, voidage of packing etc...
a. Qualitative Description:
e.g. British Standards B.S.2955:
Term Definition of particle shape Term Definition of particle shape
Acicular Needle-shaped Flaky Plate-like
Crystalline Freely developed in a fluid medium Granular Having approximately an
of geometric shape equidimensionsl irregular shape
Fibrous Thread-like (regular or irregular) Modular Having rounded, irregular shape
Flaky Plate-like Spherical Global shape

b. Quantitative Description- Shape Factors:

i. Volume Shape factor (v):
Vp = v x3
x: measured or characteristic linear dimension representing particle ‘size’
- for spherical particles: x = d (particle diameter); v = /6
ii. Surface-Area Shape factor (s):
Sp = s x2
- for spherical particles: x = d; s = 
iii. Sphericity ():
A measure of deviation from spherical shape:

Surface Area of Sphere of Same Volume as Particle 
Surface Area of Particle
2
S d 2  d  d
  V  V2   V   SV
SP d S  dS  dV
Example of Sphericity:
Particle 
Sphere of diameter d 1.0
Cube of side a 0.806
Cylinder with diameter = length 0.874
Disk with (diam/length) = 10 0.471
2.2.4 Mixed Particle Systems

 Particles are seldom uniform in size (and other properties).
 Need to specify distribution of properties based on measurements.
 Particle size distributions (PSD):
- Simplest: bimodal (2 distinct sizes).
- Usually a wide range of sizes exists (polydispersed).
 Description of PSD:
- Graphical presentation
- Average or mean particle sizes
- Size distribution functions

a. Graphical Presentation of PSD

3 ways:
i. Frequency Histogram
Plot of number (dn/dx) or mass (dw/dx) of particles of size between x and x + dx versus
x.
For discrete sizes, n or w may be used within each finite size range between x and
(x + x).
ii. Relative Frequency Distribution Diagram

Plot of relative frequency (number or mass) of particles of size between x and x+ dx
versus x.
1 dn n n
 Number frequency: fn  x    i  i
N dx  ni N
i
1 dw wi w
 Mass frequency: fw  x     i
W dx  wi W
i
where N   ni : total number of particles; W   wi : total mass of particles

i i
iii. Cumulative Distribution Diagram

Plot of % cumulative (number or mass) frequency of particles smaller (undersize) or
larger (oversize) than size x versus x.
  
1 dn ni ( xi ) 
 Number-oversize:  f n (x)dx   N dx
dx = x N  x f n ( xi )
x x i i
x x
1 dw wi ( xi ) xi
xi
 Mass-undersize:  f w (x)dx   W dx
dx = 0 W  0 f w ( xi )
0 0
b. Average or Mean Particle Sizes

i. Mode Diameter (dmode)
Most commonly occurring size, ie. dmode corresponds to maximum frequency of PSD.
ii. Median Diameter (d50)

50% of particles (number or mass) are smaller than this diameter. Can be determined
from the cumulative distribution diagrams. Median diameters in number and mass may
not necessarily be the same.

iii. Arithmetic Average Diameter (dan)

dan: diameter of a sphere equals to the average linear dimension of the whole
distribution.
Ndan = ni xi
 dan = ni xi / N = ni xi / ni = fni xi
where: fni = ni/N = ni/ni is the relative number frequency (number fraction) of
particles having size xi.
iv. Surface Area Mean Diameter (dSn)
dSn: diameter of a sphere with surface area equal to the average surface area of the
whole distribution.
N  d Sn2   ni Si
i
  ni Si    ni Si 
1/ 2 1/ 2
1/ 2
    1 
 d Sn  i  i    f ni Si 
 N    n   i 
   i 
   i 
where: Si is the surface area of particles having size xi.
v. Volume Mean Diameter (dVn)
dVn: diameter of a sphere having same volume as the average volume of whole
distribution.
N  dVn
3
/ 6   niVi
 6 niVi   6 niVi 
1/ 3 1/ 3
1/ 3
    6 
 dVn  i
 i
   f niVi 
 N    n   i 
   i 
   i 
where: Vi is the volume of particles having size xi.
vi. Surface-Volume Mean Diameter (dSVn) (Sauter mean)
dSVn = diam of a sphere with surface area/volume equal to that of whole distribution.
 d SVn
2

n S
i i
 d SVn  6
nV i i
6
f V
ni i

3
dVn

6
3
d SVn  nV
i i n S i i f ni Si 2
d Sn
 All particles are spherical (xi = di = diameter, S = , V = /6)
d SVn    ni di3 /  ni di2 
 Particles are non- spherical with known sphericity (i):

d SVn   ni dVi3 /  ni d Si2   ni dVi3 /   ni dVi2 / i 

Mean Diameters for Spheres:
Mean Diameter Based on number of particles

Arithmetic average   n idi 
  n  
d an    f ni d i
 i  i
  n i d i2 
1/ 2 1/ 2
Surface area average  
    f ni d i2 
  n 
d Sn
 i   i 
  n i d 3i 
1/ 3 1/ 3
Volume average  3
d Vn  
  n 
   ni i 
f d
 i   i 
Surface area-Volume average   n i d 3i    f ni d 3i 
dSVn   
  n d 2    f d 2 
 i i   ni i 
 For the same particles, number- based mean diameters are numerically different from mass-
based mean diameters.
 Note: for engineering calculations, it is common to use mean diameters based on number of
particles rather than those based on mass.
Mean Diameter Conversions:

Number-based mean diameters may be calculated from mass distribution data by using
particle density p as the conversion factor:
w i  p n i Vi  p n i  Vi x 3i where: wi is mass of all particles having size xi
Example:
  n iSi   n i Si x i2
1/ 2 1/ 2
 
1/ 2
  w wi 
d Sn        Si i  
  n   n   Vi x i  Vi x 3i 
 i   i 
 For spheres: xi = d, S = , V = /6, thus:

1
 w i .d i2  2
  n i d i2  2
1
  
1
    i i 
 
3 2
d 6 w d
 
p i
  n 
dSn
 wi    w d3 
     d 3 6 
i   i i 
 p i 
1 1
  n i d 3i  3   w i  3
 
  n    w d 3 
d Vn
 i   i i 
dSVn 
n d 3
i i

w i
n d 2
i i w di i

Significance of Mean Diameters:

Mean Diameter Usage Examples
dSn - Coating applications, e.g covering power of paint and pigment
dVn - Spray drying

- Applications involving bubbles & drops
dSVn - Fluid flow through porous media (in packed column, filtration...)
- Heat and mass transfer
- Catalytic reactions
c. Particle Size Distribution Functions

i. Arithmetic-Normal Distribution:
Frequency distribution is normal (or Gaussian):
 xx
  
2

exp   ;
1
f (x) 
 2  2 2   f  x  dx  1
 
0
where: x  d An (arithmetic average)
 
1/ 2
 
 xx
2
  : standard deviation

 N 1 
 
 
 PSD can be sufficiently described by means of x and 
Features:
 Plot of cumulative size distribution (probability scale) versus particle size (linear scale) is
linear
 x = xmode = x50
  = x84 – x50 = x50 – x16
ii. Logarithmic-Normal Distribution:

Frequency distribution based on ln(particle size) is normal, with log-normal function:
 zz
  
2

1
f (z)  exp   ;
 f (z)dz  1
Z 2  22Z 
 
0

z  ln x
 
z  ln x = ln(d gn ), d gn : Geometric Mean (number-based)
 
1/ 2
 zz 

2
Z    = ln ( )
 N 1  g
 
 g : Geometric standard deviation
Features:
 Plot of cumulative size distribution (probability scale) versus particle size (log scale) is a
straight line.
 z = zmode = z50
 z = ln(g) = ln(x84) – ln(x50) = ln(x50) – ln(x16)
 If number distribution is log-normal, mass and surface area distributions are also log-
normal with the same geometric standard deviation (g).
 Geometric Mean (dgn)
ln(d gn )  z  (ln x) 
 n ln x
i i
N
  n i ln x i  
1/ N
n 
 d gn  exp      x i i 
 N   i 
 For particles having log-normal PSD, it is possible to compute some average diameters
from dgn and g:
Arithmetic Mean: ln dAn = ln dgn + 0.5 (lng)2
Surface-Mean: ln dSn = ln dgn + 1.0 (lng)2
Volume-Mean: ln dVn = ln dgn + 1.5 (lng)2
Surface-Volume-Mean: ln dSVn = ln dgn + 2.5 (lng)2

2.3 PARTICLE SIZE MEASUREMENTS

 Various methods are available for size measurement and analysis. A single method may
not be sufficient for particles of diverse size.
Method Applicable Size Range (m)
Sieving > 50
Liquid sedimentation 10 - 500
Optical microscopy 1 – 500
Electron microscopy 0.001 - 10
Centrifugation 0.01 - 100
Light scattering & transmission 0.1 - 60
X-ray scattering 0.01 – 0.1
 Selection of a particular technique depends on
- Size range of the particles
- Physical & chemical characteristics of the particles
- Purpose & application of the measurement
- Availability & reliability of method
 Three most common methods:
- Sieving
- Microscopy (optical & electron)
- Sedimentation
 Other popular methods:
- Light scattering
- Laser diffraction
- Coulter counter
2.3.1 Sieving
 Established method.
 Simple & rapid, most suitable for particle sizes > 50 m.
 Principle: sizes are sorted by passing the particles through a series of test sieves with
the largest opening on top.
 Stack is shaken (mechanically, or manually) for a fixed period (BS& ASTM
Standards).
 Can be operated dry or wet.
 Size measured is dA : diameter of sieve aperture = width of the minimum square
aperture through which the particle passes.

dA
Finer
Standard Test Sieves:

 Each sieve has a mesh number corresponding to a fixed size of aperture (opening).
 Aperture size follows a 2 progression.
 BS (British Standards) or Tyler (US) standard test sieves.
British Standard (BS) Sieves Tyler (US) Sieves
Mesh No# Opening (m) Mesh No Opening (m)
18 853 20 833
36 422 35 417
100 150 100 147
150 105 150 104
200 76 200 74
300 53
#
Mesh Number = number of wires per inch
2.3.2 Microscopic Methods

 Invaluable for examination of very fine & ultra fine powder ( d < 100 m)
Method of Microscopy Lower Size Limit (m)

Optical 2
Electron, Scanning (SEM) 0.01
Electron, Transmission (TEM) 0.001
 SEM also allows examination of surface texture.

 TEM gives shadowgraph 2D-image of particles
 Principle: Counting number of particles having sizes within a specified range.
 What dimension measured by microscopic methods?
* Near-Spherical Particles: Compare projected areas with circles of known diameters.
* Non-Spherical Particles: Different methods, e.g.
- Measure largest & smallest linear dimensions and take average of the two.
- Measure largest dimension across particle in a fixed direction.

da: projected area diameter

M: Martin’s diameter
= length of line bisecting
particle image
F: Feret’s diameter
= distance between 2
tangents parallel to
direction of reference
 Accuracy depends on statistically large population of particles.

 Method (both measurement and analysis) is tedious unless equipped with automatic
digitisation & counting facilities.
2.3.3 Sedimentation
 Principle: settling rate of a particle is proportional to its size.
 Apply Stokes' law for a sphere falling under gravity in creeping flow:
18v t v t : Settling velocity

 : Fluid viscosity
d where: P : Particle density
(P  )g  : Fluid density
g : Gravity
 Useful for obtaining cumulative particle size distribution by measuring fraction of

particles passing a fixed distance z as a function of time, viz.
18 z
d2  
(P  )g t
 Fluid is usually liquid; minimum size limit: ~ 1m
 Measured Stokes diameter (dSt) can be directly applied to design of systems associated
with sedimentation, e.g. settlers, thickeners, clarifiers, elutriators, centrifuges.
2.3.4 Combined Methods

 necessary for particles having wide size ranges.
e.g. d > 50m : by sieving
d < 50m: by microscopic or sedimentation
 Since different methods use different principles, measured sizes do not necessarily
overlap. In some cases, it is possible to "convert" one size to another by means of
conversion factor . For example, for some solid powder:
Convert From To Multiplying Factor

Sieving (dA) Sedimentation (dSt) 0.94
Sieving (dA) Microscope (da) 1.4
Thus, a particle passing a 200-mesh BS sieve (75m aperture) would have a Stokes
diameter dSt = 71 m and a projected area diameter da = 105 m.

2.4 SURFACE AREA AND PORE VOLUME

 Two important physical properties of solid particles
 Influence heat & mass transfer characteristics.
2.4.1 Surface Area

 Difficult to define because solids are naturally porous with cracks and cavities in
internal structure.
i. Non-porous solids:
Surface area = area of outer surface = macro or visible surface area
ii. Porous solids:
Surface area = area of outer surface + inner or micro area due to pores
 Pore area can be much greater than outer area in most porous particles
 Essential to define and use appropriate surface area to suit application or situation of
interest:
Outer (macro) surface area: important in hydrodynamic situations, e.g. in particle
sedimentation, flow of liquid through void space between particles...
Internal surface area (due to the porous structure): important in non-hydrodynamic
situations, e.g.. in Heat & mass transfer operations: adsorption, gas-solid reaction,
drying...
 Internal surface area measured by permeametry method using adsorption of nitrogen
gas as standard.
Typical Total Surface Area of Some Common Solids
Material Specific Surface Area (m2/g)
Nylon fibre 0.2
Portland cement 0.3
Quartz sand 0.6
TiO2 pigment 8
Kaolin 18
Silica gel (desiccant) 670
Activated charcoal 870
2.4.2 Pore Volume

PORE  all cracks, fissures, holes, cavities, channels etc.. within a body up to surface
level.
PORE VOLUME
Define:  POROSITY( )
TOTAL PARTICLE VOL.
if  is large  solid particle is highly porous

 Pore size (diameter) determines the difficulty of movement of fluid (liquid or gas)
within a porous particle:
Larger pores generally provide less obstruction to internal fluid flow & diffusion, e.g.
less time & energy for drying of wet solids.
 Good knowledge of pore size and pore size distribution is very important.
 Measurement of pore volume (and hence pore size) may be made by mercury
penetration, or by gas adsorption-desorption method using He or N2.
___________________________________________________________________________
References on Particle Characterisation

Allen T 1990, Particle Size Measurement, 4th Edition, Chapman & Hall, New York.
Orr C Jr & Dallavalle JM 1960, Fine Particle Measurement, McMillan, New York.
Foust AS et al 1977, Principles of Unit Operations, Appendix B, Wiley, New York.

Chapter Two: Particulate Systems

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2.

2.1 WHAT ARE PARTICULATE SYSTEMS?

2.2 DESCRIPTION OF PARTICLES

2.2.1 General Properties

 Here we are mainly concerned with physical properties in describing particles.

Fluid and Particle Mechanics

2.2.2 Particle Size

Class Size Limits Common Units for Particle Size

Coarse particles > 1 mm mm, cm or inch

Fine 0.1 - 1 mm mm or screen (mesh) size

Very Fine 1 m- 1000 m m or Ao

a. Particle Size Description

b. Equivalent Particle Size (for Non-Spherical Particles)

Fluid and Particle Mechanics

iii. Surface-Volume (equivalent) Diameter (dsv):

Examples of other equivalent diameters:

Equivalent Diameter Symbol Reference Size-Dependent Property

2.2.3 Particle Shape

Fluid and Particle Mechanics

b. Quantitative Description- Shape Factors:

2.2.4 Mixed Particle Systems

Fluid and Particle Mechanics

a. Graphical Presentation of PSD

ii. Relative Frequency Distribution Diagram

where N   ni : total number of particles; W   wi : total mass of particles

iii. Cumulative Distribution Diagram

b. Average or Mean Particle Sizes

ii. Median Diameter (d50)

Fluid and Particle Mechanics

iii. Arithmetic Average Diameter (dan)

 All particles are spherical (xi = di = diameter, S = , V = /6)

d SVn    ni di3 /  ni di2 

 Particles are non- spherical with known sphericity (i):

Fluid and Particle Mechanics

Mean Diameters for Spheres:

Mean Diameter Based on number of particles

Mean Diameter Conversions:

 For spheres: xi = d, S = , V = /6, thus:

Fluid and Particle Mechanics

Significance of Mean Diameters:

dSn - Coating applications, e.g covering power of paint and pigment

dVn - Spray drying

c. Particle Size Distribution Functions

where: x  d An (arithmetic average)

  : standard deviation

ii. Logarithmic-Normal Distribution:

Fluid and Particle Mechanics

Surface-Mean: ln dSn = ln dgn + 1.0 (lng)2

Volume-Mean: ln dVn = ln dgn + 1.5 (lng)2

Surface-Volume-Mean: ln dSVn = ln dgn + 2.5 (lng)2

Fluid and Particle Mechanics

2.3 PARTICLE SIZE MEASUREMENTS

Fluid and Particle Mechanics

Standard Test Sieves:

2.3.2 Microscopic Methods

Method of Microscopy Lower Size Limit (m)

 SEM also allows examination of surface texture.

Fluid and Particle Mechanics

da: projected area diameter

 Accuracy depends on statistically large population of particles.

18v t v t : Settling velocity

 Useful for obtaining cumulative particle size distribution by measuring fraction of

2.3.4 Combined Methods