Chapter 4: QUANTITATIVE ANALYSIS

BY X-RAY DIFFRACTION
QUANTITATIVE ANALYSIS (SINGLE PHASE)
CHEMICAL ANALYSIS BY PARAMETER
MEASUREMENT
The lattice parameter of a binary solid solution of B
in A depends only on the percentage of B in the
alloy, as long as the solution is unsaturated. This
fact can be made the basis for chemical analysis by
parameter measurement. All that is needed is a
parameter vs. composition curve, such as curve bc
of the figure shown, which can be established by
measuring the lattice parameter of a series of
previously analyzed alloys. This method has been
used in diffusion studies to measure the change in
concentration of a solution with distance from the
original interface. Its accuracy depends entirely on
the slope of the parameter-composition curve. In
alpha brasses, which can contain from 0 to about Variation of lattice
40 percent zinc in copper, an accuracy of +I constant with composition
percent zinc can be achieved without difficulty. in single phase region (bc
This method is applicable only to binary alloys. In curve) in a binary alloy.
ternary solid solutions, for example, the percentage Assume atom B is larger
of two components can be independently varied. than atom A.
The result is that two ternary solutions of quite
different compositions can have the same lattice
parameter.
 Variation of lattice constans with
composition in binary nitride-carbide
systems. In these systems, the
variation is almost linear, obeying
Vegard’s law. Vegard’s law states
that in some material systems,
lattice constant varies linearly with
composition. If lattice constant is
measured, one can determine
chemical composition of the alloys
by using Vegard’s law.

Vegard’s Law

For example a TiCxN1-x= x a TiC + (1-x) a TiN

Where a TiCxN1-x is the lattice constant of titatnium carbonitride, a TiC is the lattice
constant of pure TiC, a TiN is the lattice constant of pure TiN, x is the mole fraction of
TiC in titanium carbonitride.
 Precise lattice constant parameter measurement

Many applications of x-ray diffraction require precise knowledge of the

lattice parameter (or parameters) of the material under study. In the
main, these applications involve solid solutions; since the lattice
parameter of a solid solution varies with the concentration of the solute,
the composition of a given solution can be determined from a
measurement of its lattice parameter. Thermal expansion co-
efficientscan also be determined, without a dilatometer, by
measurements of lattice parameter as a function of temperature in a
high-temperature diffractometer. Since, in general, a change in solute
concentration or temperature produces only a small change in lattice
parameter, rather precise parameter measurements must be made in
order to measure these quantities with any accuracy.
The process of measuring a lattice parameter is a very indirect one,
and is fortunately of such a nature that high precision is fairly easily
obtainable. The parameter a of a cubic substance is directly
propartional to the spacing d of any particular set of lattice planes. If
we measure the Bragg angle θ for this set of planes, we can use the
Bragg law to determine d and, knowing d, we can calculate a. But it is
sin θ, not θ, which appears in the Bragg law. Precision in d, or a,
therefore depends on precision in sin θ, a derived quantity, and not on
precision in θ, the measured quantity. This is fortunate because the
value of sin θ changes very slowly with θ in the neighborhood of
90°,as inspection of the figure will show. For this reason, a very
accurate value of sin θ can be obtained from a measurement of θ
which is itself not particularly precise, provided that θ is near 90° . For
example, an error in θ of 1° leads to an error in sin θ of 1.7 percent at
θ = 45° but only 0.15 percent at θ = 85°. Stated in another way, the
angular position of a diffracted beam is much more sensitive to a
given change in plane spacing when θ is large than when it is small.
 The variation of sin θ with θ. The error in
sin θ caused by a given error in θ
decreases as θ increases (Δθ
exaggerated).

We can obtain the same result directly by differentiating the Bragg law with respect
to θ. We obtain
λ = 2d sin θ
For a given error in θ
0 = 2 sin θΔd + 2d cosθΔθ
Δd θà90°, cot θ à 0
= − cot θΔθ
d Error Δa/a à0
a = d h +k +l
2 2 2
For cubic system
In summary 2θà180 °
Δa Δd
= = − cot θΔθ errorà0
a d
Although the parameter error disappears as 2θ approaches 180° ,we cannot
observe a reflected beam at this angle. But since the values of a calculated
for the various lines on the pattern approach the true value more closely as
2θ increases, we should be able to find the true value of a simply by plotting
the measured values against 2θ and extrapolating to 2θ = 180°.
Unfortunately, this curve is not linear and the extrapolation of a nonlinear
curve is not accurate. However, it may be shown that if the measured values
of a are plotted against certain functions of θ, rather than against θ or 2θ
directly, the resulting curve is a straight line which may be extrapolated with
confidence.
The general approach in finding an extrapolation function is to consider the
various effects which can lead to errors in the measured values of θ, and to
find out how these errors in θ vary with the angle θ itself.
The chief sources of error in θ are the following are Off-centering of
specimen, absorption in specimen, misalignment of the diffractometer,
unparalled X-rays, Unflat specimen surface.

•Some extrapolation functions used

– sin2θ or cos2θ or cos2θ/sinθ
Example 1:To illustrate this extrapolation method, we shall consider a
powder pattern of tungsten made with unfiltered copper radiation. Using
the data given below calculate lattice constant of tungsten.

Pik hkl Radyasyon θ (°) sin2θ a(A°)

(Cu)
6 400 Kβ 61.71 0.7754 3.162
5 321 Kα 65.91 0.8334 3.160
4 411,330 Kβ 69.05 0.8722 3.162
3 400 Kα1 76.73 0.9473 3.166
2 400 Kα2 77.48 0.9530 3.164
1 420 Kβ 79.67 0.9678 3.164
Extrapolation of measured lattice constants against sin2θ (or cos2θ)
Calculate lattice constant of Ni-Fe powder and
determine the chemical composition of the alloy.
QUANTITATIVE ANALYSIS IN MULTIPHASE MATERIALS-MESUREMENT
OF RETAINED AUSTENITE

Mıcrotructure of a steel
containing retained austenite
(light areas) along with
martensite.
The hardening of steel requires two operations: (1) heating to a high
temperature to form a homogeneous, face-centered-cubic solid solution
called austenite, and (2) quenching the austenite to room temperature to
transform it to a hard, metastable, body-centered-tetragonal solid solution
called martensite. In practice, the quenched steel may contain some
undissolved carbides and, because of incomplete transformation, some
austenite is often retained at room temperature. The effect of this austenite
on the service behavior of the steel is usually detrimental, but sometimes
beneficial. At any rate there is considerable interest in methods of
determining the exact amount of austenite present. Quantitative
microscopic examination is fairly satisfactory as long as the austenite
content is fairly high, but becomes unreliable below about 15 percent
austenite in many steels. The x-ray method, on the other hand, is quite
accurate in this low-austenite range, often the range of greatest practical
interest.

Assume that a hardened steel contains only two phases, martensite and
austenite. The problem is to determine the composition of the mixture,
when the two phases have the same composition but different crystal
structure.
Partial diffractometer pattern of an oil-quenched NiVsteel,containing
about 30 volume percent austenite (γ). Chromium radiation, V filter.

γ = Ostenit

α = martenzit
 Assume that a hardened steel contains only two phases, martensite and austenite.
The problem is to determine the composition of the mixture, when the two
phases have the same composition but different crystal structure.

Iαhkl / Iγhkl = (Rαhkl Vα)/(Rγhkl Vγ ) ................ (1)

Where Iαhkl =Integrated intensity of a Martensite (α) peak

Iγhkl=Integrated intensity of an austenite (γ) peak
Rhkl= A correction factor which depends on diffraction plane (hkl), diffraction
angle (θ), crystal structure and lattice constant. R values are calculated.

Vα= Martensite volume fraction

Vγ= Austenite volüme fraction

We need another equation to find volume fractions of martensite and austenite.

The equation is

Vα+ Vγ= 1 ................ (2)

• Example: A diffraction pattern of a quenched steel reveals martensite and
retained austenite phases. Using the data given below, calculate the amount
retained austenite (vol%).

Peak α (200) γ (200)

I (Intensity) 1.00 1.00
R (Correction 20.73 34.78
factor)

Answer:
From equation (1):
1/1=(20.73 Vα ) / (34.78 Vγ ) ◊ Vα = 1.68 Vγ
From equation (2)
1.68 Vγ+Vγ=1 à Vγ=0.373
37.3 % retained austenite.