CHARACTERIZATION

OF
POWDERS

Powder Technology
MM6521
1
Powder Characterization Techniques

POWDER SAMPLING AND

DISPERSION

X-RAY DIFFRACTION
MICROSCOPY
FLOWABILITY
APPARENT DENSITY
TAP DENSITY
PARTICLE SIZE ANALYSIS
SURFACE AREA ANALYSIS

2
 POWDER SAMPLING
• Collection of representative sample of powder for analysis
 Issues to be addressed during sampling:
i. The quantity of powder from which the sample are to be obtained
ii. The amount of sample required
iii. The powder characteristics (flow behavior, particle shape, tendency
to segregate and surface chemistry and mechanical strength)
Sampling

Starting lot: scale 100’s kg

Gross sample: scale kg

Laboratory sample: scale g

Measurement sample: scale mg

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 Sampling
Methods
Static sampling:
1. Scooping- Consists of plunging a scoop into a heaped batch. As the
sample is taken from surface, hence it is prone to error. The whole
sample does not pass through the sampling device.
2. Thieving- Plunging a capture device into the bulk material to retrieve
several small aliquots of the powder.
3. Cone & quartering- powder to be poured into a cone shaped heap
onto a flat surface. The heap is flattened and divided by a flat shaped
metal cutter. One fraction (1/4) is taken and whole procedure is
repeated until the desired amount is obtained.

4
 Dynamic sampling

• Powder is taken from a moving powder bulk.

• Table sampling- Powder flow along an inclined table in which there
are series of holes.
• Spin riffling- The devices uses mechanical energy (vibration) to
provide a constant flow of material from its holder. The steady flow
passes through a divider head that rotates at a constant speed and
thus minimizes segregation.

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 Powder Dispersion
 Most of the powders are cohesive because of their small
sizes. Hence, powder particles are not easily dispersed.
Although Vander Waals forces are small, adsorbed moisture
causes particle agglomeration.
 Let represent the total energy of a particle, V represent the
particle volume and A represent the particle surface area.
The total energy of a particle is

Where  is the surface energy (J/m2) and  is internal energy

(J/m3).
Assuming a spherical particle with diameter D.
Energy per unit volume )
 The energy per particle scales inversely with the size of the
particle, the driving force for agglomeration becomes larger
as the particle size decreases.6
 Powder Dispersion

 To characterize a powder for size or other attributes

requires that it should be properly dispersed.
 Surface active agents (polar molecules typically
carbon chains with charged anionic or cationic
terminal groups like OH-, SO3-, NH4+) can greatly
influence powder cohesion or dispersion.
 The first step is to remove adsorbed moisture or
other agents that cause particle agglomeration.
 Shear forces with the dispersant is most effective in
de-agglomerating fine powder.
 Shear force can be delivered by using ultrasonic
agitation or intense mixing.
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 X-RAY DIFFRACTION

Phase analysis
Crystallite size/lattice strain measurement
Unit cell dimension (lattice parameter)
Dislocation density

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X-RAY DIFFRACTION
PHASE ANALYSIS: XPERT HIGH SCORE-PHILIPS

Adjacent peak W, Mo Both

are BCC in nature

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X-RAY DIFFRACTION
PHASE ANALYSIS: XPERT HIGH SCORE-PHILIPS

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 X-RAY DIFFRACTION
Indexing of X-ray Diffraction pattern λCu= 1.540598 Å

Peak 2θ (°) sin2θ ×2 h2+k2+l2 hkl a (nm)

1 40.2749 0.1183 1 2 2 110 0.31672
2 58.2676 0.2372 2 4 4 200 0.31632
3 73.1982 0.3552 3 6 6 211 0.31659
4 87.0117 0.4733 4 8 8 220 0.31669

𝝀∗ √ 𝒉𝟐+𝒌𝟐 +𝒍 𝟐
𝒂= =𝒍𝒂𝒕𝒕𝒊𝒄𝒆 𝒑𝒂𝒓𝒂𝒎𝒆𝒕𝒆𝒓 𝒇𝒐𝒓 𝑪𝒖𝒃𝒊𝒄
𝟐 ∗ 𝒔𝒊𝒏 𝜽

C Suryanarayana, M.G. Norton, X-ray diffraction- A practical approach,

Plenium press: New York, 1998
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Determination of Crystal structure

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 X-RAY DIFFRACTION
Measurement of XRD Peak Broadening

• Phase analysis is carried out after matching with the JCPDS

(Joint Committee on Powder Diffraction Standards ) data bank.
• Phases are identified on the basis of d spacing, 2θ position.
• Scan range, step size, scan rate are utmost important in X-ray study.
• Broadening is defined as full width at half maximum (FWHM).
Broadening of peak suggests refinement of powder particle.
Intensity

FWHM = ((1/2) Imax

2θ (°) 13
 X-RAY DIFFRACTION
Crystallite size and Lattice strain calculation

Crystallite size is calculated from cryst= , Scherrer Formula

l: average crystallite size, K = 0.94 for cubic crystal , Bstrain = ε tanθ,

Br = cryst + Bstrain = + ε tan θ

Br cos θ = + ε sin θ
Instrumental broadening (BI) is determined by annealing of powder sample
so that particle size is coarser and strain free.
Br2 = BO2 – BI2 (BO = Observed broadening)

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 X-RAY DIFFRACTION
Crystallite size and Lattice strain calculation

Slope= ε = lattice The slope of the linear fit

strain of the curve will directly
Br cos θ

provide: lattice strain

Crystallite size is measured from
Intercept= Intercept

sin θ

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 X-RAY DIFFRACTION
Identification of nature of powder
Intensity

Intensity
Angle (2θ) Angle (2θ)

Crystalline powder Amorphous powder

Ordered and periodicity maintained 16 Lack of ordering and periodicity

 Problem

Ultra fine particles of iron were produced by the evaporation method and their average sizes
are estimated as 25, 50, 90 and 120 nm using the laser particle analyzer. Assuming that the
resultant particles are strain free and peak broadening detected in the measurement with Cu-
K radiation (= 0.15406 nm) arises only from the variation of size of the crystallites,
estimate the peak width (the values of FWHM) of the (110) plane detected by using the
Scherrer equation.

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 Importance of particle size/size distribution

Influence the powder flowability.

• Impact on interparticle friction of powder.
• Effect on particle deformation during subsequent
compaction of powder.
• Particle size influence the green density of the as
compact pellet.

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 PARTICLE SIZE ANALYSIS
Particle shape and size is important in understanding the density and
flow characteristics.
Class Technique Size range (µm)

Sieving Screens/mechanical
agitation/ultrasonic agitation 44-800

Microscopy Micromesh screen 5-50

Visible light 0.2-100

Electron microscopy 0.001-5

Sedimentation Gravitational 1-250

Centrifugal 0.05-60

G. S. Upadhyaya, Powder Metallurgy Technology,

19 Cambridge Int. Science Publishing, 1997
Production Shape Image
technique
Chemical decomposition One dimensional
Acicular

Electrolytic Two dimensional dendritic

Atomization, Three dimensional spherical

Carbonyl (Fe),
Precipitation from a
liquid

Atomization, Irregular
Chemical decomposition

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Production Shape Image
technique

Mechanical Angular
disintegration,
Carbonyl (Ni)

Mechanical Comminution Flake

Chemical Irregular rod shape

decompositions,
Mechanical comminution

Reduction of oxides Porous

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Spheres– Easily flow, Needle shape – very poor flow property
 Particle size distribution
• A particle population which consists of spheres or
equivalent spheres with uniform dimensions is
monosized and its characteristics can be described by a
single diameter or equivalent diameter.
• It is unusual for particles to be completely monosized,
most powders contain particles with a large number of
different equivalent diameters.
• To be able to define a size distribution or compare the
characteristics of two or more powders consisting of
particles with many different diameters, the size
distribution can be broken down into different size
ranges, which can be presented in the form of a
histogram. 22
Frequency distribution graph

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Cumulative frequency distribution graph

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 Various frequency and
cumulative frequency graphs

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Basic principles-particle shape

Imagine I give you a cigarette packet and a ruler

and ask you to tell me what size it is.

What will be your reply ?

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 Basic problems

You may reply

“100x50x20mm”

It is not possible to describe the 3-dimensional

cigarette packet with one unique number

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 Grains of sand...

What size are

they ?

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 Nomenclat Definition Image
ure
dF Maximum length of particle
measured in fixed position
(Feret’s Diameter)
dM Length of line which bisects
area of the particle (particles
measured in same direction)
(Martin’s diameter)
Fmax Maximum diameter of
particle, (no set direction)-
Longest diameter.
dL Longest line through a particle
in a fixed direction. (maximum
horizontal intercept)

dF/dM = shape function=1 (for spherical particle) and > 1 for irregular shape

O.D. Neikov, N. A.Yefimov, Powder Characterization and Testing In: Handbook of Non-Ferrous Metal Powders
29
Technologies and Applications, O. Neikov (Ed.), 2 nd Edition, 2019, Elsevier.
PARTICLE SIZE ANALYSIS

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PARTICLE SIZE ANALYSIS

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 Equivalent Sphere

20
µm
32
Volume of a cylinder =
r h 10000m
2 3

4 3
Volume of a sphere = X X=equivalent volume radius

3
3V
 X 3 0.623 V
4

X 3
30000 3
 7500 19.5
 D2 39.1m
4

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Equivalent spherical diameters by volume,
surface area and projection area

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35
• Depending upon which property we take
from our particle to use in our calculation will
make a significant difference to our answer
• Different techniques use different properties
of the particle to calculate their size

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37
SCREENING

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 Data for cumulative undersize and
oversize plot

Mesh Screen Opening, Mass % Mass Mesh Screen Opening, Cumulative wt Cumulative
Dpi Retained on Retained Dpi % undersize wt% oversize
(mm) Screen, (mm)
(g)
14 1.400 0.000 0.00 14 1.400 100 0.00
16 1.180 9.12 1.86
16 1.180 98.14 1.86
18 1.000 32.12 6.54
18 1.000 91.60 8.40
20 0.850 39.82 8.11
30 0.600 235.42 47.95 20 0.850 83.49 16.51
40 0.425 89.14 18.15 30 0.600 35.54 64.46
50 0.300 54.42 11.08
40 0.425 17.39 82.61
70 0.212 22.02 4.48
50 0.300 6.31 93.69
100 0.150 7.22 1.47
140 0.106 1.22 0.25 70 0.212 1.83 98.17
Pan - 0.50 0.11 100 0.150 0.36 99.64
Total 491.00 100
140 0.106 0.11 99.89

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Cumulative undersize and
oversize plot

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PARTCLE SIZE MEASUREMENT BY
LIGHT/LASER SCATTERING

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42
 Sedimentation Technique
• Particle settling in a fluid (liquid or gas) reach terminal velocity dependent on both the
particle size and the fluid viscosity.
• Particle size can be estimated from the settling velocity.
• Particle size in the range of 0.02-100 µm can be measured depending on particle density
and shape.
• The technique uses a predetermined settling height and places a dispersed powder at the
top of a tube.
Gravitational force
Buoyancy force
Viscous drag force
=
Terminal velocity
Particle size
D- particle diameter Stokes
-fluid density Law
- particle density
-viscosity of fluid
H-column height
t-time
43
 Contd.

 A spherical Ni powder is to be analyzed for particle size

using sedimentation. It is suspected that the particle size
is near 8 m. If the powder is dispersed in water at the top
of a settling column 100 mm high, then what is the
expected time?
 Given, H= height= 0.1 m
 g= gravitational constant= 9.8 m/s2
 D= particle size= 8 m= 8x10-6 m
 m= Ni density =8.9 g/cc= 8.9 x103 kg/m3
 f = water density=1 g/cc= 103 kg/m3
 = water viscosity= 10-3 kg/m/s
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 Reynolds No.= 2.2x10 -3
 Problems

The particle size of tungsten is measured by

sedimentation technique using air. Calculate the
limiting size of tungsten (Dmax) that can be measured
by this technique. Given, RN Reynolds no (lower limit of
0.2),  is fluid viscosity (1.8x10-5 kg/m/s), g is the
gravitational constant (9.8 m/s2), f is the fluid density
(1.2 kg/m3) and m is the metal density (19.3x103
kg/m3)
If water is selected instead (viscosity of 10-3 kg/m/s and
density of 103 kg/m3), then find the upper particle size
that can be measured.
45

=
 Limitation of Sedimentation Technique

 The container walls should not interact with particles

during settling.
 The particle-particle interaction must be zero.
 Concentration should be kept below 1 vol. % (no
agglomeration)
 Fluid and powder can not react chemically

46
 MICROSCOPY (SEM)
• The particles can be seen by optical (either reflected or transmitted
light), SEM or TEM.
• Intelligent discrimination between single or multiple particles is a
common problem.
• Counting two or more small particles as a large particle will skew the
distribution toward the coarse sizes.

Commercial powder of W Commercial powder of nano

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(0.6-1 µm size) Y2O3
 MICROSCOPY (SEM)

W-Ni-La2O3 powder mechanically alloyed W-Ni-Al2O3 powder mechanically alloyed

for 5 h. for 5 h.

EVIDENCE OF FLAKY SHAPE POWDER PARTICLE DURING

MECHANICAL ALLOYING OF POWDER PARTICLES

48
 MICROSCOPY (TEM)

POWDER SAMPLE PREPARATION FOR TEM ANALYSIS

 Powder sample has to dispersed in isopropyl alcohol.

 Magnetic stirring has to be carried out for minimum 1 h with heating.
 Ultra sonication has to be performed for minimum 1 h with 5 min interval after
every 15 min run.
 The powder has to be placed on Cu grid, care has to be taken in placing the amount
to minimize agglomeration effect.

49
 MICROSCOPY (TEM)

TEM characterization of W-Ni-Al2O3 SAD pattern of W-Ni-Al2O3

powder ball milled for 10 h powder ball milled for 10 h

rd = lλ (camera constant)
d= interplaner spacing
50
 MICROSCOPY

• Calculated “d” spacing from SAD pattern has to be matched with

the nearest “d” spacing in the XRD phase analysis.
• Indexing SAD pattern is a powerful method to identify the
elements/compound crystal structure, plane etc.
• Increasing size of the particle forms only spots rather than
continuous ring pattern.
• Refinement of crystallite size results in diffused rings.

51
Comparison of Particle Size Measured by
Different Techniques

• Microscopy techniques give

D50 = 42 the population of the particles
m vs. their size. Sieving
technique provides a weight
distribution.
D50 = 72 • The weight distribution is
m skewed to the coarser particle
sizes in comparison to the
population based distribution.
• Direct comparison of weight
and population based particle
size distribution is invalid.
52
 POWDER FLOWABILITY:
INTERPARTICLE FRICTION
• Ability of powders to flow rapidly and smoothly without sticking and
bridging.
• The friction between particles is dominated by the surface area, surface
roughness, and surface chemistry.
• The density or packing properties decreases because of poor flow past
neighbouring particles.

C. Calvin Sun, Powder Flow Fundamentals,53

Characterization, and Pharmaceutical
Applications, University of Minnesota, 2015.
 FLOWABILITY
Comprehension of flowability

• Compressibility index
• Angle of repose

Evaluation of flowrate : Hall flowmeter Orifice

(time required in s for 50 g of powder to
pass through a small orifice. Cylinder

Powder
Finer particle higher surface area higher interparticle friction  less flowability
And packing.

54
 FLOWABILITY
• Presence of coarser and finer particle in appropriate proportion exhibit decreases
the flow time.
Compressibility index/Carr Index ( C) :
C.I = × 100
= tap density (density of powder after mechanical vibration or
tapping),
= bulk density/apparent density/volumetric density.

Another method for flowability measurement :

Hausner ratio (H) :

• Hausner ratio is useful in categorizing relative interparticle
friction. For spherical powder, (H) will be slightly above unity.
More irregular particle shapes undergo a larger density
increase with vibration, resulting in a higher Hausner ratio.
55
 FLOWABILITY

Carr, R.L. Evaluating Flow Properties of Solids. Chem. Eng. 1965, 72, 163–168

56
 FLOWABILITY

Improving flow characteristics

Avoid moisture contact in powders.

arger powder size
Spherical powders have more flowability due to more
rolling action.
Using flow additives in dispersed form for highly cohes
powders.

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 FLOWABILITY
• Related with interparticle friction of powder.
Angle of repose
• Success of measurement of angle of repose
depends on formation of symmetric cone.

Angle of repose r

𝒉
𝐭𝐚𝐧 𝜶=
𝒓
Carr, R.L. Evaluating Flow Properties of
Solids. Chem. Eng. 1965, 72, 163–168
58
 FLOWABILITY

Angle of repose (Factors)

Angle of repose

Internal

Particle size

Particle shape

Cohesiveness

External

Method of measurement

Moisture

59
 FLOWABILITY
Angle of repose (Factors)
 In general fine particle exhibit higher angle of repose.

 Cohesiveness of very fine particles enhances the angle of repose.

 Spherical particle shows lesser angle of repose as compared to irregular

shaped ones owing to higher affinity to roll.

 Moisture increases angle of repose.

 Compaction process enhances angle of repose.

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 APPARENT DENSITY

• Defined as density of loose powders (non vibrated or tapped).

• Powders can be free flowing or non free flowing through hall flowmeter.

• For free flowing powder : ASTM B212 -17 and for non free flowing
powder ASTM B417-18.

• Strongly influenced by particle size and surface roughness.

• Density increases with increase in particle size.

• Density decreases with increasing surface roughness and irregular shape.

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 APPARENT DENSITY/BULK
DENSITY/VOLUMETRIC
DENSITY
PROCEDURE • Measure the mass of density cup.
• Pouring of loose powder through
the funnel.
Funnel • The powder should fill the density
cup.
• Excess powder in the density cup
should be removed and leveled.
• Mass of powder filled density
Density cup cup is measured in a microbalance
with three decimal precision.

• Apparent density is measured :

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 TAP DENSITY
• Cylinder with 100 mL volume employed for the
measurement (upto 4 g/cm3 apparent density).

• Pour powder in required amount in the cylinder

based on apparent density.
50 g (< 1 g/cm3), 100 g (> 1 g/cm3).

• Insert the cylinder in mechanical apparatus.

• Tapping has to be done till no further decrease of

powder volume is observed.

• Amplitude of taping : 3 mm, frequency : 100-300

impulses/min.

• Tap density :

O.D. Neikov, N. A.Yefimov, Powder Characterization and Testing

63
In: Handbook of Non-Ferrous Metal Powders
Technologies and Applications, O. Neikov (Ed.), 2 Edition, 2019, Elsevier.
nd
 TAP DENSITY
Material Powder Apparent density Tap density
Shape/Method (g/cm3) (g/cm3)
of fabrication
Copper Spherical 4.5 5.3
Irregular 2.3 3.14
Flake 0.4 0.7
Iron (-100 Electrolytic 3.31 3.75
+200 mesh)
Atomized 2.66 3.26
Sponge 2.29 2.73
Aluminium Atomized 0.98 1.46
(-200 mesh)

Spherical shape provide the highest apparent and tap density.

Poster AR, (ed.), Handbook of Metal Powders, Reinhold,

64 New York, 1966.
 SURFACE AREA MEASUREMENT
• Surface area provides insight into the powder behaviour during
chemical reactivity, catalysis, friction, adsorption,
contamination, pressing and sintering.
• Two measurement techniques are widely used:
• Gas adsorption surface area analysis
• Gas permeability surface area analysis
Gas adsorption surface area analysis (BET analysis)
• The clean powder surface is exposed to varying partial pressure of
known adsorbing vapors.
• The technique is based on the amount of gas adsorbed on the
powder surface versus the partial pressure.
• This technique is popularly known as BET specific surface area
measurement technique, after Brunauer, Emmett and Teller who
developed the technique in 1938.
• The technique measures the quantity of gas needed to saturate the
powder surface.
• It is assumed that gas molecule occupies a precise area, the surface
area of the powder is calculated.
65
 Gas adsorption surface area analysis
(BET analysis)

Let P = partial pressure of absorbate

Po = saturation pressure of absorbate
X= amount of gas adsorbed at pressure P
Xm= monolayer capacity of the powder (amount of
gas necessary to form a saturated surface coating of
one atomic layer thick)
C= constant

66
 Contd.

= BET equation

The BET can be rewritten as general form

=B+ A
Linear
A- slope and B- intercept equation
=

Specific surface area /(

M- molecular wt. of adsorbate

Ao – average occupational area of an
adsorbate molecule
No-Avogadro no 67
W- weight of sample
 Gas permeability surface area analysis

 Darcy equation for flow in a porous material

gives the flow rate Q in m3/s based on
pressure drop

L-sample length, A-cross sectional area

Gas velocity exiting from the low pressure side

- flow rate per unit area (

68
 Contd.

 Using Kozeny and Carmon equation, surface

area can be calculated as

- porosity
m-theoretical density of the material

69
 Particle Shape
 Particle shape influences packing, flow and
compressibility.
 Particle shape varies with size and manufacturing
technique.
 A particle size analysis assumes a constant shape
and have large error.
 The most straightforward quantitative shape
descriptor is the aspect ratio (maximum particle
dimension divided by the minimum particle
dimension).
 For sphere, the aspect ratio is unity, for a ligamental
the value is near 3 to 5. A flake particle can have an
Particle shape of irregular shape
aspect ratio
particle can >10. Generally,
be expressed by the ratio microscopy techniques
are
D0/DAmost appropriate for quantifying
70
shape.
The projected image of an irregular particle and two forms of measuring the size in terms of circular diameters.
 Surface Area as a Shape Index

Consider a monosize sphere

Surface area
Volume
The area per unit solid volume is 6/D
The weight W of a solid particle

Area per unit weight == Specific surface area

If a different particle shape is considered, then the
relation between particle size and surface area would
be

Ks is particle shape factor 71

 Problem

Consider a cylinder shaped particle with a length twice

the diameter D. Calculate the shape factor Ks.

72
 Compressibility

 Compressibility measures the ability to densify a

powder under an applied load.
 The die is loaded with powder and the density is
measured after compaction at a predetermined
pressure.
 The density is measured as green density.
 ==
- volume of loose powder, -volume of compacted
powder, -green density and -apparent density, M-
mass of powder
73
 Problem

 A typical atomized iron powder has an apparent

density 2.9 g/cc and compacts to a density of 6.78
g/cc at 414 MPa pressure. If the powder was
compressed to a height of 18 mm, find the initial
powder fill depth for uniaxial compaction.

74
 Some Useful Terminologies

 Apparent density (a)- density of loose

powder mass
 Tap density (t)- density after tapping
(vibration)
 Green density (g)- density of green compact
after compaction
 Sintered density (s)- density of compact
after sintering
 Theoretical density (th)- handbook density
 (th)> (s)>(g)> (t)> (75a)
 Summary

Microscopy is more powerful technique to measure the particle shape in lower

range.
Spherical shape, larger particle has more flowability as compared to uneven and
particles.
Powder fabrication method is utmost important to achieve desired particle shape
Particle size and size distribution is also vital in view of density of green and
sintered pellet.
Powder fabrication method and particle shape influences the apparent and tap
density of powders.
Presence of optimum distribution of finer and coarser particles enhances the tap
density or density of pellet after compaction (more details will be provided in
powder compaction lecture).

76
THANK YOU

77
QUESTIONS

78