1. COURSE TITLE
Nano Science & Technology
Dr.Shaista Rafique
CourseCode: PHY-608

2. TOPIC:
X-RAY DIFFRACTION
& EDX

3. Group #9
Sabika Zainab 2
Uswa Ismail 26
Maryam Nighat 34
Muqaddas Ghafoor 44
Shehr Bano 48
Samra Sha Jahan 100
Zartasha Rasheed 104
Fizza Fatima 122

4. X-ray Diffraction:
X-ray diffraction analysis (XRD) is a technique used in material
science to determine the crystallographic structure of a material. XRD
works by irradiating a material with incident X-rays and then
measuring the intensities and scattering angles of the X-rays that leave
the material.
XRD has been used extensively for the examination of materials and
thin films. Its effective use depends upon having a crystalline
material. The technique is a bulk sensitive analytical method, but can
be used to provide information relevant to surface changes in suitable
circumstances

5. . For example, XRD can provide useful information on the extent to
which surface treatment of a carbon system has affected the bulk of
the material. It is possible to use XRD in thin film mode, employing
very small take-off angles, to derive some surface information, but
generally speaking it must be regarded as a bulk structural technique.

6. X-ray Diffraction Principle:
X-ray diffraction is based on constructive interference of
monochromatic X-ray and a crystalline sample. These X-rays are
generated by a cathode ray tube, filtered to produce monochromatic
radiation, collimated to concentrate and directed towards the
sample
How does XRD works:
Crystals are regular arrays of atoms, whilst X-rays can be
considered as waves of electromagnetic radiation. Crystal atoms
scatter incident X-rays, primarily through interaction with the
atoms. This phenomenon is known as elastic scattering; the electron
is known as the scatterer.A regular array of scatters produces a
regular array of spherical waves.

7. A regular array of scatters produces a regular array of spherical waves. In
the majority of directions, these waves cancel out each other through
destructive interference, however, they add constructively in a few
specific directions, as determined by Braggs Law.
Bragg’s Law:
2dsinθ = nλ
Where d is the spacing between diffracting planes, θ is the incident angle,
n is an integer, and λ is the beam wavelength. The specific directions
appear as spots on the diffraction pattern called reflections.
Consequently, X-ray diffraction patterns result from electromagnetic
waves impinging on a regular array of scatterers.

8. X-rays are used to produce the diffraction pattern because their
wavelength, λ, is often the same order of magnitude as the spacing,
d, between the crystal planes.
X-ray Diffraction Methods
The phenomenon of x-ray diffraction is useful for the determination
of structure of solid. And as well as for the study of the X-ray
spectroscopy. Bragg’s law is widely used for both these applications.
For applying Bragg’s law for crystal structure determination. It is
required that λ and θ must be matched properly.

9. To do so experimentally, another continuous range of wavelength λ or
θ is provided. So that the value of λ is arbitrarily chosen for a given
value of the orientation ‘θ’. Three methods are generally adopted for
the study of crystal structure. These are Laue Method, Rotating
Crystal method, and powder method.
Laue Method:
It is one of the important methods. Used for the study of crystal
structure and is mostly used for determination of Crystal symmetry.

11. In this method, a beam of polychromatic X-rays of wavelengths
ranging from 0.2Å to 2Å is allowed to fall on a small crystal of
dimension 1 mm * 1mm * 1mm, placed on a goniometer.
The goniometer can be rotated to change the orientation of the
crystal with respect to the beam of X-rays. Generally, the beam is
allowed to fall perpendicular to the plane of the crystal under
study. While passing through the crystal.
The X-ray falls on different Bragg’s planes having a spacing d.
And making different angles ‘θ’ with the incident direction of X-
rays.

12. For some value of d, λ and θ, which satisfy the Bragg’s condition
2d sinθ = nλ constructive interference takes place and increase in
intensity takes place at certain directions producing a diffraction
pattern. This diffraction pattern may be observed by placing a
photographic plate on the other side of the crystal.
Rotating crystal method
In this method a single crystal of dimension 1 mm is mounted on a
rotating spindle. Such that the axis of rotation of the spindle
coincides with either of the axis of the crystal. A beam of
monochromatic X-rays is incident on the Crystal perpendicular to
the axis of rotation of the spindle.

13. The spindle is covered by a Hollow cylindrical holder having its axis
collinear with the axis of spindle. Such that the crystal lies at the
center of this cylindrical holder. For obtaining the diffraction pattern.
A photographic plate is attached inside the cylindrical holder along
with its surface. It may be noted that generally the vertical Axis is
taken as the rotation axis.
Powder Crystal Method
Bragg’s method and the rotating Crystal Method required the precise
mounting of a single crystal on a certain crystal Axis. Which is a
tedious task to do. To overcome this difficulty powder crystal
method is used.

14. This method was developed independently by Deby, Scherrer, and
Hull. In this method, the crystalline material is ground to powder
form Show that the Crystallites assume random orientation.
A small sample of this powder is placed in a small capillary tube.
Made of non-Diffracting material or the sample is just stuck on a
hair with the help of non-diffracting binding material. And is placed
in the path of a fine monochromatic beam of X-rays.
The principle involved in the crystal method is that since there are a
large number of crystallites with random orientation. All possible
diffraction plain shall be available for Bragg’s diffraction to occur.
For the diffraction to occur in accordance with the condition 2d
sinθ = nλ. λ being a constant in this case.

15. Therefore, the reflection will occur from the family of parallel planes
which are inclined to the x-ray beam at different angles.
Also, the higher order of reflection apart from the first order, second-
order reflection. Will also be produced. Since for a given value of
angle θ. A large number of orientations of a given family of planes are
possible.
The X-ray diffracted corresponding to the perpendicular value of d and
θ will lie on the surface of a cone. Whose Axis lie along the direction
of the incident beam. And apex is at the sample with semi-vertical
angle 2θ as shown in fig.

17. X-ray diffraction
studyFigure 1 shows the
XRD pattern of PPy/Cu
NPs films deposited on
stainless steel substrates.
The peak attributed43.5⁰,
50⁰ and 74⁰ is of stainless
steel rest peak observed
are of Cu nano particles.
In addition the peak of Cu
NPs are overlapped on
the peaks of stainless
steel substrate.

18. It confirms the presence of coppernano particles particularlyat
300⁰C, which we attributeto a combination of partial
Crystallizationat low temperatureand peak spreading caused
by the nano particulatenatureof the material. On the other
hand, Cu2o deposited for different times that is i.e 10,20,30
and 40s, Respectively exhibit the XRD patternsas shown in
figure 1 b-e. Amongst all the diffractograms, prominent peaks
are observed in figure

19. 1-e, peaks observed in figure 1-d, e go on reducing maybe
due to large crystallitesize of Cu2O. No diffraction lines
associated with impurities work detectedin the present study.
these XRD results match well with JCPDS 05-0667with
cubic fcc structureof Cu2o representing (111),(200)and
(220)planes. From XRD results, It can be explain the
mechanism of reducingCuSO4 with solutionof NaOH and
the reduction of CU2+ ions in the solutionto Cu+ ion which
is deposited as Cu2O particles on PPy electrode.

20. Surface morphological studyThe morphology of PPy and
PPy/Cu NPs films was investigated by FE-SEM shown in
figure 2. Figure 2a shows that the irregular grain like
morphology of copperparticleswere dispersed randomly on
PPy films for 10s.

22. Figure 2b the agglomeration of grain like structure forms
clusterof coppernano particles which provides much space to
coppernano particlesto interact with glucose due to
interconnectingleaf like structurebetween the clusters, while
figure 2c reflects the Change in morphology in terms of size
and shape of the particle and slowly become compact with
losing leaf like structure between them. When time of

23. deposition copperon PPy films increase morphology gradually
changes and finally becomes flower like, as shown in figure 2-
d. This kind of morphology PPy/Cu NPs shows comparatively
less amperometmatric responsethan that of figure 2b second
type electrode. Figure 3 shows that the stoichiometry of
PPy/Cu nano composite films is studied by EDS study
analysis,

24. As number of copper oxide cycle on PPy increases, and
atomic percentage of Cu nano particles for the first and second
Black PPy films becomes blackish brown and Cu nano
particles are dispersed uniformly on the PPy.

25. Electro catalyticactivity To achieve optimal conditionsfor
voltametric determinationof glucose, main perimeters related
to the films formation and solution characteristicswere
evaluated.
Optimal conditionswere explained by means of measuring
the peak currentsof both compoundswith one variable at
time method and determined as follows: 0.2M pyrrole, 0.1M
NaOH, 10 cycles for electrodepositionCu of nano particles
and pH 7.0 for electrolytemedium, respectively.

28. Without Cu NPs, bare PPy film (figure 4) shows no any
oxidation or reductionpeaks while applied for CV study in
10mM glucose for different scan rates. It reveals that PPy film
shows very poor electrolyticactivity.
Hence, Cu NP decorationsis needed to improve the electrolytic
performance and intense non enzymatic glucose sensing of
PPy/Cu NPs on stainless steel substrates.

29. Clear background signal was obtained in the absence of glucose
( figure 5 black line ) for the PPy electrode modified by Cu nano
particles. Upon the addition of glucose of about 10mM in the cell,
oxidation and subsequent reduction peaks have appeared at -0.6 and -
1.0V, respectively indicating a quasi reverse able electrode process
probably due to the diffusion barrier of the polymeric film ( figure 5
black and red lines, respective).

30. AMPEROMETRIC RESPONSE OF PPy/Cu sensorFigure 7
illustratethe amperometric response of PPy/Cu NPs for
10,20,30and 40 mM glucose concentrations.As it is
observed from amperometric curve,we have taken the
optimized film from cyclic voltammetry study of fig. 6b.the
current time curve were recorded for optimized film.As the
successive addition of glucose lead to increse in current, as
shown in fig.7, the maximum current obtained 5.4 mA for
40 mM of glucose.

33. DETERMINATION OF GLUCOSE SENSOR Detection limits
for optimize film second in glucose were estimated to be 3.0
miuM which comparatively less than rest of the first,third and
fourth films of LOD values 7.1,5.28 and 11.4 miuM.Fig. 8
indicates linearity curve of optimaized 2nd electrod which
shows stable peak observations at fixed concentrationwhile
increasing the glucosw analyteconcentrationindicated that the
oxidation of glucose by PPy/Cu NPs/stainless steel electrodeis
calculated using formula slop/areaof electrod.

34. The sensitivity of PPy/Cu NPs/stainless steel electrode for the
1st,2nd,3rd and 4th represented in table 2. The optimum
sensitivity of 2nd electrode is 100 miuM mM-1 cm-2 with LOD
3miuM and regression coefficient RR= 0.9951

35. STABILITY,REPEATABILITY,REPRODUCIBILITY
STUDIES The problemoccurred in glucose detection for a
PPy/Cu NPs non-enzymaticsensor is the electrochemical
oxidation of meddling species such as fructose, lactose, and
urea in physiological conditions. For selectivity of glucose, we
should go for the amperometry study PPy/Cu NPs (fig 9) which
reveal excellent selectivity towards glucose than lactose,
fructose and urea at potentialseven 650 mV

36. . Fig. 9 shows the selective determination of glucoseat the
PPy/Cu NP electrode by successive addition of 0.1 mM fructose,
0.1 mM lactose,0.1 mM urea and 0.1 mM glucose to 0.1 M
NaOH solutoin at an applied potential of 650 mV.

37. The addition of lactose, fructose and urea does not lead to any
observable response or less than the response of glucose. Fig. 10
represents the stability curve of optimized PPy/Cu electrode of the
proposed 2nd electrode. Moreover. for glucose sensing, glucose was
propped in air saturated PBS (pH 7.0) and its oxidation peak current
response was monitored and registered periodically

38. . The 74.27% of the initial oxidation peak current response remains
withstand even after 10 days in the air at ambient temperature. It
implies the unique stability of the repotted 2nd sensor for glucose.
On the other hand, the responsibility and repeatability of oxidation
peak currents in the presence of glucose. In this context, relative
standard deviation

39. was measured of about 4.16% which indicates the better reproducibility
and retaintivity of PPy/Cu electrode toward glucose sensing. The
PPy/Cu nonenzymatic glucose sensor chose three individual as prepared
modified electrodes and measure the corresponding. In the present
study, constructed PPy/Cu NP sensor shows very excellent performance
in sensitivity,linear range, and selectivity. The results demonstrate that
the PPy/Cu NP electrode is a promising candidate for non-enzymatic
glucose determination

41. CONCLUSION
In the present study. a new composite electrode PPy/Cu NPs/stainless steal
was prepared by electro polymerization and electro position vectors.it was
shown that this composite electrode improved the electrocatalytic activities
towards the oxidation of glucose. The catalytic activity of PPy/Cu
NPs/stainless steel electrode towards glucose oxidation was improved by
formation of a uniform PPy film which was in cooperated with Cu nano
particles on the electrode surface due to the increasing effective surface area.

42. the detection limits of glucose were estimated for the 1st,2nd,3rd
and 4th electrodes, 3 miuM is optimized LOT for 2nd film which
also shows better amperometry response, respectively. Thus, the Cu
nano particle modified polypyrene film electrode showed better
sensitivity of 100 miuM miuM^-1 cm^-2.

43. XRD Benefits and Application:
XRD is non-destructive technique used to:
➢ Identify crystalline phases and orientation
➢ Determine structural properties:
a) Lattice parameter:
b) Strain
c) Grain size
d) Epitaxy
e) Phase composition
f) Preferred orientation
➢ Measure thickness of thin film and multi-layers
➢ Determine atomic arrangement

44. Application of XRD
1. Measurement of sample purity
2. Determination of unit cell dimension
3. Characterization of crystalline materials and determine structural
properties including:
4. Lattice parameter-Strain-Grain size-Epitaxy-Phase composition-
Preferred orientation
5. Characterize thin film sample and measure the thickness of thin
film and multi-layers
6. Determine atomic arrangement
7. Identification of fine-grained mineral such as clays and mixed
layer clays that are difficult to determine optically
8. Determine of model amount of minerals