NAME ANEELA AFTAB

CMS ID 49583

SEMESTER THIRD

SUBJECT FIBER SCIENCE

SUBMITTED TO DR. MUHAMMAD QASIM

 XRD TECHNIQUE

Introduction
X-ray diffraction is a powerful nondestructive technique .XRD is a technique used to find
out the nature of the materials as crystalline or amorphous. It will define the
quantification of cementitious materials. The XRD analysis is done with an X-ray source
of Cu Kα radiation (λ = 1.5406 Å). It will analyze and identify the unknown crystalline
compounds by Brag Brentano method. The different parameters such as scan step size,
collection time, range, X-ray tube voltage and current should be fixed based on the
specimen's requirement analysis. The standard database (JCPDS database) for XRD
pattern is used for phase identification for a large variety of crystalline phases in the
concrete specimens.

WORKING
Max von Laue, in 1912, discovered that crystalline substances act as three-dimensional
diffraction gratings for X-ray wavelengths similar to the spacing of planes in a crystal
lattice. X-ray diffraction is now a common technique for the study of crystal structures and
atomic spacing.
X-ray diffraction is based on constructive interference of monochromatic X-rays and a
crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce
monochromatic radiation, collimated to concentrate, and directed toward the sample. The
interaction of the incident rays with the sample produces constructive interference (and a
diffracted ray) when conditions satisfy Bragg's Law (nλ=2d sin θ). This law relates the
wavelength of electromagnetic radiation to the diffraction angle and the lattice spacing in a
crystalline sample. These diffracted X-rays are then detected, processed and counted. By
scanning the sample through a range of 2θangles, all possible diffraction directions of the
lattice should be attained due to the random orientation of the powdered material.
Conversion of the diffraction peaks to d-spacing allows identification of the mineral
because each mineral has a set of unique d-spacing. Typically, this is achieved by
comparison of d-spacings with standard reference patterns.

All diffraction methods are based on generation of X-rays in an X-ray tube. These X-rays
are directed at the sample, and the diffracted rays are collected. A key component of all
diffraction is the angle between the incident and diffracted rays. Powder and single crystal
diffraction vary in instrumentation beyond this.
Parts of XRD equipment
X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and
an X-ray detector. 

https://serc.carleton.edu/research_education/geochemsheets/techniques/XRD.html#:~:text=Fund
amental%20Principles%20of%20X%2Dray%20Powder%20Diffraction%20(XRD)&text=X
%2Dray%20diffraction%20is%20based,and%20directed%20toward%20the%20sample.

X-rays are generated in a cathode ray tube by heating a filament to produce electrons,
accelerating the electrons toward a target by applying a voltage, and bombarding the
target material with electrons. When electrons have sufficient energy to dislodge inner shell
electrons of the target material, characteristic X-ray spectra are produced. These spectra
consist of several components, the most common being Kα and Kβ. Kα consists, in part, of
Kα1 and Kα2. Kα1 has a slightly shorter wavelength and twice the intensity as Kα2. The specific
wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr). Filtering, by foils or
crystal monochrometers, is required to produce monochromatic X-rays needed for
diffraction. Kα1and Kα2 are sufficiently close in wavelength such that a weighted average of
the two is used. Copper is the most common target material for single-crystal diffraction,
with CuKα radiation = 1.5418Å. These X-rays are collimated and directed onto the sample.
As the sample and detector are rotated, the intensity of the reflected X-rays is recorded.
When the geometry of the incident X-rays impinging the sample satisfies the Bragg
Equation, constructive interference occurs and a peak in intensity occurs. A detector
records and processes this X-ray signal and converts the signal to a count rate which is
then output to a device such as a printer or computer monitor.
https://serc.carleton.edu/research_education/geochemsheets/techniques/XRD.html#:~:tex
t=Fundamental%20Principles%20of%20X%2Dray%20Powder%20Diffraction%20(XRD)&text=X
%2Dray%20diffraction%20is%20based,and%20directed%20toward%20the%20sample.

The geometry of an X-ray diffractometer is such that the sample rotates in the path of the
collimated X-ray beam at an angle θ while the X-ray detector is mounted on an arm to
collect the diffracted X-rays and rotates at an angle of 2θ. The instrument used to maintain
the angle and rotate the sample is termed a goniometer. For typical powder patterns, data is
collected at 2θ from ~5° to 70°, angles that are preset in the X-ray scan.

Parts of the machine

The main parts of a powder diffractometer include:

The source

The primary optics

The sample holder & sample stage

The secondary optics

The detector
XRD results analysis for Nylon and cotton
fiber:
Xrd result analysis of cotton:
 The fine structure of cotton cellulose has been most widely investigated by wide-angle X-ray diffraction,
a well-developed and powerful tool for discerning structural organization of polymer solids. The
structural studies of cotton cellulose have been extensively reported, mainly on field grown matured
cotton and those treated in urea and sodium hydroxide. The formation of primary and secondary cell walls
in cotton fibers is distinct
and of relatively long duration, allowing studies of crystalline structure at specific stages of fiber development.
The crystalline structure of developing has been detailed using wide-angle X-ray diffraction and a multi-peak
resolution method previously developed

 .In this method, the total scatter was resolved into peaks over a non-crystalline scatter background,
where crystallinity is the ratio of the summation of all resolved peaks to the total scatter as detailed in our
previous paper. Crystallite dimensions normal to the hkl planes were calculated following peak broadening
corrections caused by structural broadening () and instrumental broadening. The apparent crystallite sizes of
the 101, 101 and 002 reflection planes was based on the Sherrer equation. A typically resolved X-ray
diffraction spectrum of 60-dap Maxxa cotton fibers is illustrated in Fig. 1.10. The multiple peak resolution
method yields seven peaks from the WAXD spectrum collected between 5∞and 40∞. The four peaks located
near 2angles of 14.7∞, 16.6∞, 22.7∞and 34.4∞are

Characteristic of the 101, 101 , 002 and 040 reflections of cellulose I, respectively, and are used for structural
analysis and comparison. The cellulose I crystalline structure is clearly evident near the onset of secondary cell
wall formation, or 21 dpa (Fig. 1.11). The cellulose I crystalline structure has been confirmed on dried SJ-2
and Maxxa cotton fibers at varying

Developmental stages and remains unchanged during secondary cell wall biosynthesis and at maturity. The
degree of crystallinity doubled from the beginning to the end of the secondary cell wall formation, i.e., from
about 30% at 21 dpa to 60% at 60 dpa. The most significant increase in crystallinity, i.e., from 30% to 55%, is
observed between 21 and 34 dpa.
https://tripleis.org/wp-content/uploads/2019/12/cotton-science-and-technology-woodhead-
publishing-1.pdf
 The extensive data on several Acala varieties grown under wellcontrolled green-house conditions show
that significant crystallinity is attained during the first half of the secondary cell wall development. One
early report also showed increased crystallinity with fiber development of a field-grown Indian cotton
variety. The stage studied was in the later stages of secondary cell wall development (35 to 65 dpa). Both
G. barbedense and G. hirsutum series of developing cotton fibers show increased overall crystallinity and
apparent crystallite sizes with fiber development (Table 1.3) . The most significant increases in L 101, L101 ,
and crystallinity occur between 20 dpa and 35 dpa,
corresponding to the first two weeks of cellulose synthesis or the fourth and fifth weeks of overall fiber
development. Fiber development beyond five weeks does not contribute to any change in crystallite
dimensions nor crystallinity. This is consistent with the leveling of tenacities at the later stage of fiber
development. These are consistent with others’ findings that the lateral apparent crystallite sizes and their
orientation increase during the cellulose biosynthesis. Structural studies of native celluloses have also included
the use of high-resolution CP/MAS 13C NMR (Atalla ellulose, where the cellulose is rich in the Iphase, and
that of cotton-ramie-wood cellulose, where the Iphase is dominant.

 XRD results analysis for Nylon fiber:

 The analysis of the various polymers tested are discussed under the following two
categories:
1. x-ray diffraction and
2. x-ray Compton scattering.
X-ray diffraction of Nylon 66 fiber:

 Nylon is a polyamide and is produced from the mutual reaction and polymerization of adipic
acid and hexamethylene diamine. Nylon is a mixture of chains of different lengths and of
polymer homologues, but its valuable properties seem to arise from the unusual regularity of
the molecules which permits the well-crystallized structure. Because of low solubility and
high stability of the polymer, nylon fibers are spun not from viscous solution, but from the
melt at 270 to 280°C, under conditions of tension such that the solidifying filament is
extended three to five-fold. This promotes the unusual degree of preferred orientation, as
shown by the x-ray diffraction picture in Figure 3.1 and displayed in the physical and
mechanical properties that are shown in Table 3.1 in comparison with those of natural fibers.
Staudinger has shown that the strength of fibers does not increase in proportion to the degree
of polymerization

A=π r 2

file:///C:/Users/b%20c%20a/Desktop/xrd%20for%20nylon.pdf

 .The nylon sample was tested using a Mo target at 45Kv, lOrnA and the exposure was 1
hour. The sample to the film distance was 50mm. The interesting deduction from Figure 3.1
is that the film does not show any continuous diffraction ring like polypropylene and
polyethylene, but it does show two sharp rings with stronger intensities in four discrete
patches onto the circular ring which confirms the orientation effect.
 The most important feature from the film is that all the invisible crystals in the nylon fiber
are all pointing the same way and, moreover, directly along the axis of the fiber. Another
deduction from the film is that the crystals of the nylon fiber are always longer than they are
thick and lie lengthwise along the fiber.
 The highly crystalline nature of nylon 66 is attributable to the large number of polar groups
in the molecule which leads to the formation of hydrogen bonds. The formation of the
hydrogen bonds between adjacent chains increases the interchain forces of attraction and
facilitates tighter packing and excellent secondary bonding of the chain elements with each
other

Analysis calculation and working formulas:

The unit cell parameters for nylon which has a triclinic system a

a= 4.90 A, a= 38.5°

b = 5.40 A ~ c= 77.0°

c = 17.2 A

For a triclinic system the interplanar spacing of the hkl plane is given
file:///C:/Users/b%20c%20a/Desktop/xrd%20for%20nylon.pdf

By measuring the radii "R" of the rings, and since the sample to the film distance is known, we
can calculate the angle e

file:///C:/Users/b%20c
%20a/Desktop/xrd %20for
%20nylon.pdf

Agreed well with those reported for the

unit cell parameters. The margin of
error was about 0% to 0.24%.

 General analysis of nylon 66 by XRD:

 [3]

References:

 https://tripleis.org/wp-content/uploads/2019/12/cotton-science-and-technology-
woodhead-publishing-1.pdf

 file:///C:/Users/b%20c%20a/Desktop/xrd%20for%20nylon.pdf

 https://www.google.com/search?
q=x+ray+diffraction+for+nylon+66&rlz=1C1CHBD_enPK907PK907&source=lnms&tb
m=isch&sa=X&ved=2ahUKEwifyO_5yozuAhXsQkEAHfXuDY0Q_AUoAXoECAMQ
Aw&biw=1600&bih=767#imgrc=Emc6P59yWCzuBM

 https://myscope.training/legacy/xrd/applications/

 https://www.slideshare.net/bharathpharmacist/81347482-xraydiffractiontechnique-
39635806

 https://www.sciencedirect.com/topics/materials-science/x-ray-diffraction

 https://www.researchgate.net/figure/XRD-patterns-of-nylon-6-6-A-40-wt-n-HA-nylon-6-
6-composite-B-60-wt-n-HA-nylon-6-6_fig3_51636060
 https://biomedpharmajournal.org/vol10no4/effect-of-the-addition-of-polyamide-nylon-6-
micro-particles-on-some-mechanical-properties-of-rtv-maxillofacial-silicone-elastomer-
before-and-after-artificial-aging/

 https://myscope.training/legacy/xrd/background/whatisxrd/