Powder Characterization

The powder characteristics have a significant influence on the packing

uniformity of the consolidated body and on the micro structural evolution
of the sintered body.

Traditional Ceramics – No need to meet exact property requirements.

Advanced Ceramics – Detailed knowledge of the powder characteristics

is required for adequate control of the microstructure and properties of
the fabricated body.

The important characteristics of a powder can be categorized into four

categories ;

 Physical characteristics

 Chemical characteristics

 Phase composition
SUA/ MT2171/2023 1
 Surface characteristics
 Characterization of Ceramic Powder

Physical Characteristics :
• Particle size and distribution
Chemical Composition :
• Particle shape
• Bulk Composition
• Degree of agglomeration
• Minor Composition
• Surface area
• Trace Impurities
• Density and porosity

Surface Characteristics : Phase Composition :

• Surface Structure • Crystalline Phases

• Surface Chemistry SUA/ MT2171/2023 2

 Physical Characterization
Powders consists of an assemblages of small unit with certain distinct
physical properties. These small units , loosely referred to as particles can
have a fairly complex structure.

Types of particles

• Primary particles

• Agglomerates –
cluster of primary particles

Particles can be viewed as small units that move as separate

entities when the powder is dispersed by agitation and
consists of primary particles, agglomerates or some
combination of two. Most particle size analysis techniques refer
to such particles. SUA/ MT2171/2023 3
 Agglomerate of dense polycrystalline primary particles

Isolated
porosity

Continuous
porosity

Agglomerate
Polycrystalline
primary
particles
SUA/ MT2171/2023 4
 The packing factor of powder particles depends on the following
three factors,
• The arrangement of the powder particles
• The particle shape
• The particle size and particle size distribution

The arrangement of the powder particles

• This factor is beyond our control.

• Packing can be improved by applying a vibration.

- High frequency vibration ( Ultrasonic)

- Vibration amplitude should be same order as the size of the particles.

e.g. Powder ,Particle size distribution 1 mm – 20 mm, Vibration amplitude ~ 10 mm

High frequency (ultrasonic) SUA/ MT2171/2023 5

Particle Shape

Influences the packing of the powder, flowability of the powder

in the filling of dies during compaction.
Shape Packing Factor

Spherical 74%

Cylindrical 91%

Rectangular 100%
SUA/ MT2171/2023 6
The shape of a particle is commonly described in terms of the
shape factor.

Common shapes : More or less spherical, Angular, Platy, Needle

shape
Shape of particles determined partly by the comminution
process and partly by characteristics of material.
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 Particle Size
Particle size or grain size refers to the diameter of a grain
of granular material.

SUA/ MT2171/2023 8
Particle size and particle size distribution
Particle size and size distribution directly affects the consolidation and
sintering of the ceramic powder. Therefore it is necessary to control both
particle size and size distribution to make high dense ceramic products with
efficient manufacturing process.

Ceramic powders generally consist of particles of different sizes distributed

over a certain range.
Narrow particle size distribution –
Prepared by chemical methods under
Powders controlled conditions

Broad particle size distribution –

Milled powder that has not been
separated into narrow size fractions.

SUA/ MT2171/2023 9
Particle Size :

 Particle size influences the sintering behavior of ceramics. The time

taken for sintering depends considerably on the particle size and
the degree of compaction of the green ware. Smaller the particle
faster the densification.
 Particle size influences reactivity /dissolution.

 Particle size influences flow properties of powders. The flow

properties of powders are strongly dependent on particle size and,
in particular, particle shape. Since most powders are moved from
one place to another by flowing, control of flow behavior is highly
important.

 Particle size influences stability of dispersions. The stability of

dispersions, such as suspensions and emulsions, depends on the
size of the dispersed material. The forces between colloidal
SUA/ MT2171/2023 10

particles depend on their dimensions, and the settling.

Particle Size Distribution :

Packing factor can be improved by mixing particles of different sizes.

Ideal distribution for better packing – Fairly narrow size distribution

with lot of large particles and a little amount of smaller particles.
Packing factor can be improved by adjusting the particle size
distribution.

A particle size distribution data represented in terms of a histogram and the

SUA/ MT2171/2023 11
cumulative number percent finer than a given size.
 Measurement of Particle Size and Size Distribution

(1) Microscopic Methods

Direct measurement of the particle size coupled with simultaneous

observation of the particle shape and the extent of agglomeration.

Optical microscopes - particle sizes down to ~ 1 mm

Electron microscopes - particle sizes down to ~ 1 nm

 Able to examine each particle individually has led to microscopy being

considered as an absolute measurement of particle size.
 Can distinguish aggregates from single particles
 When coupled to image analysis computers each field can be examined
and a distribution obtained.
 Microscopic based particle size distribution is a number based
distribution.
SUA/ MT2171/2023 12
 Powder Dilute suspension Microscopic sample Observation

When samples are prepared in this manner particles takes

their most stable position, revealing their greatest dimensions

Particle size analysis using

Optical Microscope

SUA/ MT2171/2023 13
Particle size analysis using SEM
(2) Sieve Analysis

 Sieving consists of passing a known weight of material successively

through finer sieves and weighing the amount collected on each sieve.

 Sieving can be done under both wet and dry conditions.

 Typically, several sieves are stacked together, with the coarsest mesh
aperture at the top and the smallest at the bottom.

 Sieves can be referred to either by their aperture size or by their mesh

size (or sieve number). The mesh size is the number of wires per linear
inch.

 Sieve analysis can be used to classify powders with a significant fraction

of particles greater than ~ 40 mm.
Sieve analysis is a fast and simple method to analyze the particle size
distribution of powders.
The measurement data obtainedSUA/
from sieve analysis may depend on the
MT2171/2023 14
several factors.
SUA/ MT2171/2023 15
 (3) Sedimentation Methods
Sedimentation of suspensions (Stokes’ diameter)

The sedimentation techniques of particle size distribution are based on the

rate of settling of powder particles dispersed in a liquid.

Measurement of sedimentation rate can be used to determine the particle

size from Stokes’ equation. When particle shapes other than spheres are
tested, the measured particle size referred to as the stokes diameter or
the equivalent spherical diameter.

Sedimentation methods can be divided into two categories ;

I. Those that measure the cumulative sedimentation through a fixed

distance as a function of time.

II. Those that measure the concentration of particles in a plane at fixed

height in a dilute suspension as a function of time.
SUA/ MT2171/2023 16
 A spherical particle in a viscous liquid with a sufficient small velocity soon
reaches a constant velocity called terminal velocity. The effective weight
of the particle is balanced by the frictional force exerted on it by the liquid.
4/3pr3rlg
(Up trust)

6phrv (viscous flow)

4/3pr3rg
(Weight)

9hh
2
Stokes equivalent spherical diameter =
2t1 r  r 1 

For a given material and a given liquid at a particular temperature, it

is possible to find the time taken by particles of different sizes to
fall through known distance. SUA/ MT2171/2023 17
Particle size measuring techniques using sedimentation
methods
I. Beaker decantation
dilute powder suspension is carefully placed on a column of settling
liquid and the fraction of particles that settle to a fixed depth is measured as
a function of time.
In this technique, a beaker is used to place the powder suspension
and samples of constant volume are syphon off at regular intervals. Then the
samples are dried and weighed.

SUA/ MT2171/2023 18
 The material under test is uniformly dispersed in low concentration in
water contained in a beaker. A wetting agent may need to be added to
ensure complete dispersion of the particles.

 A syphon tube is immersed into the water to a depth of ‘h’ below the
water level, corresponding to about 90% of the liquid depth ‘L’.

 The terminal velocity ‘v’ is calculated from Stokes' law for the various
sizes of particle in the material, say 35, 25, 15, and 10 μm.

 The time required for a 10 μm particle to settle from the water level to
the bottom of the syphon tube, distance ‘h’, is calculated (t = h/v).

 The pulp is gently stirred to disperse the particles through the whole
volume of water and then it is allowed to stand for the calculated time.

 The water above the end of the tube is syphoned off and all particles in
this water are assumed to be smaller than 10 μm diameter.
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II. Andreasen Pipette method
Same technique as beaker decantation but special equipment
called Andreasen pipette is used.

Size distribution is determined by allowing a

homogeneous suspension to settle in a cylinder
and taking samples from the settling suspension
at a fixed horizontal level at intervals of time.
The concentration of solid in a sample taken at
time t is determined by centrifugation of the
sample followed by drying and weighing or
simply by drying and weighing.
The concentration of solid particle sample is
expressed as a percentage of the initial
concentration (w/w0).
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 (III) Sedigraph (X-ray sedimentation particle size analyser)

Principle of operation is based on the measurement of concentration

of particles remaining in suspension, as a function of time and depth
with in a sedimentation.

I0 I
Incident beam Transmitted
beam

Intensity of the transmitted beam (I) = f ( Volume of particles

interposed)
Largest size of the particle in suspension = f (h,t)
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 (4) Laser Light Scattering
The scattering of light from a monochromatic source can be used to
determine the particle size and particle size distribution.

When a beam of light strikes an assembly of particles, some of it is

transmitted, some is absorbed and some is scattered. Particle size data
can be found by measuring the variation in the intensity of the forward
scattered light.

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SUA/ MT2171/2023 23
Smaller particles scatter a small, definite amount of light through a
fixed but larger angle. Conversely, larger particles scatter a greater
amount of light but through a smaller angle.

Most light scattering instruments for particle size analysis employ

measuring techniques that give particle size based on the volume
or projected area of the particle.

The light source is usually a laser e.g. Helium-neon laser with a

wave length of 0.63mm.

Laser Light scattering methods have the advantages that the

measurement can be made accurately and fairly rapidly, only a
small amount of the sample is required and the results can be
recorded automatically. SUA/ MT2171/2023 24
 (5) Electrical sensing zone techniques ( The coulter counter)

In the coulter counter, the number and size of particles suspended in

an electrolyte are measured by causing the particles to flow through a
narrow orifice on either side of which an electrode is immersed.
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As a particle passes through a orifice, it displaces an equivalent
volume of the electrolyte and causes a change in the electrical
resistance, the magnitude of which is proportional to the volume of
the particle. The changes in resistance are converted to voltage
pulses which are amplified, sized and counted to produce data for
the particle size distribution of the suspended particles.

This method is suitable for particle sizes in the range of 1-100 mm.
However blocking of the orifice by larger particles can be a tedious
problem.

Originally applied to the counting of blood cells, coulter counter

technique has become fairly popular for particle size analysis of
ceramic powder. This method is a volume based technique.
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 (6) Peak Broadening of XRD patterns

Broadening of X-ray diffraction peaks provides a convenient method

for measuring particle size.

SUA/ MT2171/2023 27
The width of the diffraction peak (or the size of the diffraction spot) is
inversely proportional to a parameter that is a measure of the size of
the crystal. As the size of the crystal increase, the width of the peak
decreases.

In addition to size , other factors such as lattice strain, instrumental

factors can produce the broadening of the x-ray peaks.

The size of the crystal, D , is obtained from the Scherrrer equation,

Where C’ is a constant, l is the wave length of the X rays, b is the width

of the peak at half maximum corrected for instrumental broadening, q
is the Bragg angle reflection. SUA/ MT2171/2023 28
This technique gives the measure of the size of the crystals
regardless of whether the particles consists of single crystals,
polycrystals or agglomerates.

If primary particles consist of single crystals, then the crystal size

determined by X-ray line broadening will be comparable to the
particle size.

For poly crystalline primary particles or agglomerates, it will be

much smaller than the size determined by other methods.

SUA/ MT2171/2023 29
 Surface Area
The surface area of powder particles can be many times the apparent
geometric area depending on the presence or absence of surface
irregularities, pores, cracks and other imperfections. The higher the surface
area the better the reactive of the particles are in general.

The general techniques for the determination of the surface area of a

powder are based on the phenomenon of gas adsorption. In the
determination of surface area, the amount of gas adsorbed is measured at a
fixed temperature for different gas pressures.

Common tests used to determine the particle shape,

 BET gas adsorption test

 Dye adsorption test

Average particle size can be obtained from the surface area.

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