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X - RAY DIFFRACTION: Instrumentation and Applications

a b c
Andrei A. Bunaciu , Elena Gabriela UdriŞTioiu & Hassan Y. Aboul-Enein
a
SCIENT by CROMATEC_PLUS SRL, Research Center for Instrumental Analysis, 18 Sos.
Cotroceni, Bucharest - 6, 060114, ROMANIA
b
Department of Analytical Chemistry, Faculty of Chemistry, University of Bucharest, 90-92
Sos. Panduri, Bucharest - 5, 050663, ROMANIA
c
Pharmaceutical and Medicinal Chemistry Department, Pharmaceutical and Drug Industries
Research Division, National Research Centre, Dokki, Cairo 12311, EGYPT
Accepted author version posted online: 01 Apr 2015.

To cite this article: Andrei A. Bunaciu, Elena Gabriela UdriŞTioiu & Hassan Y. Aboul-Enein (2015): X - RAY DIFFRACTION:
Instrumentation and Applications, Critical Reviews in Analytical Chemistry, DOI: 10.1080/10408347.2014.949616

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X - RAY DIFFRACTION: Instrumentation and Applications

Andrei A. BUNACIU1, Elena Gabriela UDRIŞTIOIU2 and
Hassan Y. ABOUL-ENEIN3*
1
SCIENT by CROMATEC_PLUS SRL, Research Center for Instrumental Analysis, 18 Sos.

Cotroceni, Bucharest - 6, 060114, ROMANIA

2
Department of Analytical Chemistry, Faculty of Chemistry, University of Bucharest, 90-92 Sos.

Panduri, Bucharest - 5, 050663, ROMANIA

3
Pharmaceutical and Medicinal Chemistry Department, Pharmaceutical and Drug Industries
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Research Division, National Research Centre, Dokki, Cairo 12311, EGYPT

Abstract

X-ray diffraction (XRD) is a powerful nondestructive technique for characterizing

crystalline materials. It provides information on structures, phases, preferred crystal

orientations (texture), and other structural parameters, such as average grain size, crystallinity,

strain, and crystal defects. X-ray diffraction peaks are produced by constructive interference of a

monochromatic beam of X-rays scattered at specific angles from each set of lattice planes in a

sample. The peak intensities are determined by the distribution of atoms within the lattice.

Consequently, the X-ray diffraction pattern is the fingerprint of periodic atomic arrangements in

a given material. This review summarizes the scientific trends associated with the rapid

development of the technique of X-ray diffraction over the past five years pertaining to the field

of pharmaceutical industry, forensic science, geological applications, microelectronics and glass

industry, as well as in corrosion analysis.

Keywords: X - ray diffraction, theory, applications.

*
Corresponding author: Professor Hassan Y. Aboul-Enein ; E-mail: haboulenein@yahoo.com’
Tel.:+00201003678948; Fax:+--2-23337-931.

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1. Introduction

Max von Laue and co., 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 (Friedrich W, et al., 1912).

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
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monochromatic radiation, collimated to concentrate, and directed toward the sample (Figure 1).

The interaction of the incident rays with the sample produces constructive interference

(and a diffracted ray) when conditions satisfy Bragg's Law:

nλ=2d sinθ

 n is an integer

 λ is the wavelength of the X-rays

 d is the interplanar spacing generating the diffraction and

 θ is the diffraction angle.

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 2θ angles, 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-spacings allows identification of the compound

because each compound has a set of unique d-spacings. Typically, this is achieved by

comparison of d-spacings with standard reference patterns.

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X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and

an X-ray detector (Connolly, 2007).

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.

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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. Kα1 and 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 law,

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.

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.

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For typical powder patterns, data are collected at 2θ from 50 to 700, angles that are preset

in the X-ray scan.

X-ray powder diffraction is most widely used for the identification of unknown

crystalline materials (e.g. minerals, inorganic compounds). Determination of unknown solids is

critical to studies in geology, environmental science, material science, engineering and biology.

Other applications include characterization of crystalline materials; identification of fine-grained

minerals such as clays and mixed layer clays that are difficult to determine optically;
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determination of unit cell dimensions; measurement of sample purity.

With specialized techniques, XRD can be used to: determine crystal structures by using

Rietveld refinement; determine of modal amounts of minerals (quantitative analysis);

characterize thin films samples; make textural measurements, such as the orientation of grains, in

a polycrystalline sample (Brindley and Brown, 1980).

There are some strengths and some limitations of X-ray Powder Diffraction (XRD):

Strengths

 Powerful and rapid (< 20 min) technique for identification of an unknown mineral;

 In most cases, it provides an unambiguous mineral determination;

 Minimal sample preparation is required;

 XRD units are widely available;

 Data interpretation is relatively straight forward.

Limitations

 Homogeneous and single phase material is best for identification of an unknown;

 Must have access to a standard reference file of inorganic compounds;

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 Requires tenths of a gram of material which must be ground into a powder;

 For mixed materials, detection limit is ~ 2% of sample;

 For unit cell determinations, indexing of patterns for non-isometric crystal systems is

complicated;

 Peak overlay may occur and worsens for high angle "reflections".

X-ray Diffraction is a high-tech, non-destructive technique for analyzing a wide range of

materials including fluids, metals, minerals, polymers, catalysts, plastics, pharmaceuticals, thin-
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film coatings, ceramics, solar cells and semi conductors. The technique finds innumerable

practical applications in various industries, including microelectronics, power generation,

aerospace, and many more. The XRD analysis can easily detect the existence of defects in a

particular crystal, its resistance level to stress, its texture, its size and degree of crystallinity and

virtually any other variable relating to the sample’s basic structure.

The objective of this review ois to present the new developments in applications of XRD

in different analysis, covering the period between 2009 and 2014. It is useful to give a short

introduction to the concept of the XRD, some characteristics of the instruments used and sample

preparation. The quantitative and qualitative determination, in different fields of analysis using

this technique will be presented.

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2. XRD theoretical aspects

A. Instrumentation

The instrumentation that is used for powder diffraction measurements has not changed

much from the instruments developed in the late 1940s. The major difference found in modern

instrumentation is the use of the minicomputer for control, data acquisition, and data processing.

Figure 2 illustrates the geometry of the system.

The geometrical layout of a typical diffractometer system showing source F, Soller slits P
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and RP, sample S, divergence slit D, and receiving slit R. The axis of the goniometer is at A.

This geometric arrangement is known as the Bragg–Brentano parafocusing system and is

typified by a diverging beam from a line source F, falling onto the specimen S, being diffracted

and passing through a receiving slit R to the detector. Distances FA and AR are equal. The

amount of divergence is determined by the effective focal width of the source and the aperture of

the divergence slit D. Axial divergence is controlled by two sets of parallelplate collimators

(Soller slits) P and RP placed between focus and specimen and between specimen and scatter

slit, respectively. Use of the narrower divergence slit will give a smaller specimen coverage at a

given diffraction angle, thus allowing the attainment of lower diffraction angles where the

specimen has a larger apparent surface (thus larger values of d are attainable). This is achieved,

however, only at the expense of intensity loss.

Choice of the divergence slit, plus its matched scatter slit, is thus governed by the angular

range to be covered. The decision as to whether or not the slit size should be increased at a given

angle will be determined by the available intensity. A photon detector, typically a scintillation

detector, is placed behind the scatter slit and converts the diffracted X-ray photons into voltage

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pulses. These pulses may be integrated in a rate meter to give an analog signal on an x/t recorder.

By synchronizing the scanning speed of the goniometer with the recorder, a plot of degrees 2θ

versus intensity, called the diffractogram, is obtained.

A timer/scaler is also provided for quantitative work and is used to obtain a measure of

the integrated peak intensity of a selected line(s) from each analyte phase in the specimen. A

diffracted beam monochromator may also be used in order to improve signal-to-noise

characteristics. The output from the diffractometer is a “powder diagram”, essentially a plot of
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intensity as a function of diffraction angle, which may be in the form of a strip chart or a hard

copy from a computer graphics terminal (Brindley and Brown, 1980).

The powder method derives its name from the fact that the specimen is typically in the

form of a microcrystalline powder, although, as has been indicated, any material that is made up

of an ordered array of atoms will give a diffraction pattern. The possibility of using a diffraction

pattern as a means of phase identification was recognized by 1935, but it was not until the late

1930s that a systematic means of unscrambling the superimposed diffraction patterns was

proposed by Hanawalt, Frevel and Rinn (1986).

B. Sample preparation

Proper sample preparation is one of the most important requirements in the analysis of

powder samples by X-ray diffraction. This statement is especially true for soils and clays that

contain finely divided colloids, which are poor reflectors of X-rays, as well as other types of

materials such as iron oxide coatings and organic materials that make characterization by XRD

more difficult.

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Sample preparation includes not only the right sample treatments to remove undesirable

substances, but also appropriate techniques to obtain desirable particle size, orientation,

thickness, etc. Several excellent books are available that deal with appropriate sample

preparation techniques for clays and soils (Jackson, 1979; Moore and Reynolds, 1989; Bish,

1992; Iyengar, 1997).

Analysis of powders by XRD requires that they are extremely fine grained to achieve

good signal-to noise ratio (and avoid fluctuation in intensity), avoid spottiness and minimize
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preferred orientation. Reduction of powders to fine particles also ensures enough particle

participation in the diffraction process. The recommended size range is around 1-5µm (Klug and

Alexander, 1974; Cullity, 1978), especially if quantification of various phases is desired.

For routine qualitative evaluation of mineral components, the samples are usually ground

to pass through a 325 mesh sieve (45 µm). Grinding is accomplished either through hand

grinding or in a mechanical grinder. The effects of excessive grinding include lattice distortion

and possible formation of an amorphous layer (Beilby layer) outside the grains.

There are two types of mounts normally employed depending on the nature of crystallite

orientation required.

Random mounts are preferred when identification of phases in a specimen is required. In

this type of mount, particles ground to 1-5µm are packed to a flat surface onto a sample holder to

assume different orientations and ensure reflections from various planes (hkl).

Oriented mounts are used when analysing clay minerals which rarely show strong

diffraction effects from Bragg planes other than the (001). In general, these are prepared by

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making a slurry of the sample with distilled water. The water is then allowed to evaporate until

the slurry is smeared into a sample holder (could be a glass slide or ceramic tile).

Important factors in sample preparation

 Sample properties also influence the quality of a powder pattern by either reducing

intensities or distorting intensities;

 Preferred orientation or texture: Texture means that the powder particles do not have an
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arbitrary shape but a strongly regular anisotropic shape, typically platelets or needles. On

preparation these are then preferably oriented along the sample surface massively changing

the peak intensities. Several techniques may be employed to minimize this effect:

 The most efficient way is to form a slurry in a highly viscous liquid such as nail varnish.

In such a liquid, the random orientation is retained on drying;

 Alternatively, the anisotropic particle shape can be reduced by grinding in a ball mill.

This should be done with great care as excessive grinding can easily break down the

particle size to the nanometer size and lead to amorphisation. It is recommended to try

the effect of subsequent 5 minute grinding intervals to optimize the process on respective

samples. In the case of coatings or thin films preferred orientation is often a desired

effect. In this case Rietveld refinement can be used to determine the degree of texture;

 Crystallite size and strain: the broadness of a diffraction peak corresponds to the mean

crystallite size in a reciprocal manner. The smaller the average crystallite size, the broader

the reflections and the lower the absolute intensities. This effect becomes visible below and

average crystallite size of less than 200 nm. Related to crystallite size broadening is strain

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broadening. Strain broadening occurs due to the presence of defects in crystals. Such strain

can be introduced via substitution of constituting atoms but also via special thermal

treatment. It is possible to distinguish strain broadening from size broadening as the angle

dependence is much larger than in the latter case;

 Sample preparation height: Rotating sample holders improve the measurement statistics and

thus provide the best results. However, they are not available for all machines. The most

severe error during sample preparation is to fill the sample holder too high or too low. Both
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result in a significant shift of peak positions which can make the interpretation difficult.

3. Applications

A. Pharmaceutical industry

The pharmaceutical industry is one of the most successful industries in the technology

sector and its ability to innovate has seen it launch nearly 1,400 new chemical entities as human

therapeutics over the last 30 years. Despite this success, the research and development (R&D)

process to bring a drug successfully to market remains challenging. Drug development is a risky

and expensive process in order to increase demand for more available and affordable drugs

(generic drugs) and to propose adapted new drug products.

In drug design, discovery, development and formulation process, X-ray powder

diffraction can help to establish a formulation by knowing the morphology and the degree of

crystallinity, to provide unique polymorph identification and determine the quantity of each in

mixture. With XRD, non-ambient analysis can also be performed to study moisture influence on

physical properties of drugs.

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Drugs come in a variety of forms (tablets, pills, capsules, aerosol sprays) and with a

variety of formulations. A single drug may be formulated in dozens of ways to enhance the

ability of the drug to enter your body (fast relief or long-lasting relief) and be delivered to a

targeted area (skin cream, nasal spray, anti-itch, anti-cancer). A formulation could help shelf-life,

provide buffering capability in your stomach, make the medicine taste better, or be part of a

design for time-release of the drug into the blood stream. The first question to ask is what

problem are you trying to solve? Do you want to identify the ingredients or understand the
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effectiveness of a drug coating or packaging material? Are you trying to determine effective

shelf life? X-ray diffraction analyses are used in all these applications.

X-ray diffraction (XRD) can be used to unambiguously characterize the composition of

pharmaceuticals. An XRD-pattern is a direct result of the crystal structures, which are present in

the pharmaceutical under study. As such, the parameters typically associated with crystal

structure can be simply accessed. For example, once an active drug has been isolated, an indexed

X-ray powder diffraction pattern is required to analyse the crystal structure, secure a patent and

protect the company’s investment. For multi-component formulations, the actual percentages of

the active ingredients in the final dosage form can be accurately analysed in situ, along with the

percentage of any amorphous packing ingredients used.

X-Ray Powder Diffraction (XRPD) continues to be an indispensable analytical technique

supporting a wide variety of pharmaceutical development activities. X-ray diffraction (XRD) has

a broad range of applications in various stages of drug development and manufacturing, such as

active pharmaceutical ingredient (API) characterization and identification. API characterization

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is more commonly applied during drug development while API identification is directed more

towards manufacturing, regulatory aspects, and intellectual property (Ivanisevic et al., 2010).

Solid form screening, the activity of generating and analysing different solid forms of

API, has become an essential part of drug development. The multi-step screening process needs

to be designed, performed and evaluated carefully, since the decisions made based on the

screening may have consequences on the whole lifecycle of a pharmaceutical product. The

selection of the form for development is made after solid form screening. The selection criteria
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include not only pharmaceutically relevant properties, such as therapeutic efficacy and

processing characteristics, but also intellectual property (IP) issues (Aaltonen et al., 2009). Basic

principles of solid form screening are reviewed, including the methods used in experimental

screening (generation, characterisation and analysis of solid forms, data mining tools, and high-

throughput screening technologies) as well as basics of computational methods. Differences

between solid form screening strategies of branded and generic pharmaceutical manufacturers

are also discussed.

Solid form screening is commonly performed to find a candidate with optimal properties

for early development or to find a form with different properties to improve a formulation in later

development. A variety of screens can be performed including polymorph, salt, co-crystal,

amorphous, and amorphous dispersion. X-ray powder diffraction (XRPD) is commonly used at

various stages of screening to identify and characterize new forms. It is also used to help

evaluate other properties, such as physical stability and manufacturability, in order to choose the

best form for development (Newman, 2011). The author discusses the use of XRPD during

screening and form selection of pharmaceutical materials.

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Solid phase transitions such as polymorph interconversions are routinely examined by

XRPD using variable temperature sample stages (VT-XRPD). Both sub-ambient and elevated

temperature stages are available. While thermal techniques such as differential scanning

calirometry (DSC) and TGA are also widely used for these studies, VT-XRPD permits the direct

identification of crystalline phase as a function of temperature. Most pharmaceutical laboratories

rely on both technologies. Indeed, instruments are available that permit simultaneous XRPD and

DSC sample analyses (Kishi, 2011).

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VT-XRPD is also widely used to study the thermal stabilities of pharmaceutical hydrates.

Borghetti et al. (2012) characterized the flavonoid quercetin obtained from three different

commercial suppliers by a variety of analytical techniques including VT-XRPD. Three samples

of quercetin raw materials were characterized employing variable temperature-powder X-ray

diffraction, scanning electron microscopy, Raman spectroscopy, simultaneous thermogravimetry

and infrared spectroscopy, and differential scanning calorimetry, in order to know their

physicochemical properties, specially the thermal stability in solid state. The results

demonstrated that the raw materials of quercetin analyzed present distinct crystalline structures,

ascribed to the different degree of hydration of their crystal lattice. The thermal stability of these

quercetin raw materials in the solid state was highly dependent on their degree of hydration,

where quercetin dihydrate (QCT) was thermodynamically more stable than the other two

samples.

XRPD is also commonly used to investigate the structure of variable hydrates, which are

crystalline species that contain non-stoichiometric amounts of water held within channels present

in the crystal lattice. The amount of water present in a variable hydrate is typically a function of

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the relative humidity (RH) environment of the sample. Since the XRPD peak positions are

directly related to the dimensions of the unit cell, subtle changes in the size of the unit cell due to

the presence of water may be evaluated by comparison of XRPD patterns collected for the

species under different RH environments. In certain systems, an increase in a particular lattice

parameter may be a direct function of the amount of water present in the hydrated structure

(Vogt and Williams, 2010).

Suzuki et al. (2012) used XRPD along with with other techniques to determine the
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structure of the variable hydrate of sitafloxacin hydrate. Sitafloxacin (STFX) hydrate is a non-

stoichiometric hydrate. The hydration state of STFX hydrate varies non-stoichiometrically

depending on the relative humidity and temperature, though X-ray powder diffraction (XRPD) of

STFX hydrate was not affected by storing at low and high relative humidities. The detailed

properties of crystalline water of STFX hydrate were estimated in terms of hygroscopicity,

thermal analysis combined with X-ray powder diffractometry, crystallography and density

functional theory (DFT) calculation. Single-crystal X-ray structural analysis showed that two

STFX molecules and four water molecule sites were contained in an asymmetric unit.

XRPD may also be used to probe the hydration states of noncrystalline materials. For

example, the structure of the common excipient poly(vinylpyrrolidone) (PVP) was analyzed by

XRPD after equilibration under various RH environments (Teng et. al., 2010). To examine the

effects on molecular scale structure due to polymer chain length and water sorption, different

molecular weights of PVP were studied at ambient temperature and different controlled relative

humidities. Sorption of water determined gravimetrically on drying and changes to the

glasstransition temperature (Tg) measured by modulated differential scanning calorimetry

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(mDSC) were found to be consistent with previous reports. The XRPD results show that the

position of the high- and low-angle halos for PVP change with the sorption of water. The

corresponding characteristic scattering distances display a strong correlation with the measured

water content and to Tg. Chemometric analysis was also performed to extract water content

information from XRPD data and obtained results are correlated with the values measured

gravimetrically, which lends support for the apparent clustering of water in PVP drawn by other

techniques.
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Recent advances in the performance of XRPD instrumentation (particularly with respect

to peak resolution) permit the use of data obtained from conventional laboratory diffractometers.

In addition, the development of direct-space methods for structure solution require only that the

XRPD peak shape and width functions of the XRPD patterns be accurately defined (Harris,

2012).

These techniques were also applied to obtain crystal structures for three out of five

polymorphs of m-aminobenzoic acid (Williams et al., 2012). Given the importance of the

phenomenon of polymorphism from both fundamental and applied perspectives, there is

considerable interest in the discovery of new systems that exhibit abundant polymorphism. The

preparation strategies and structural properties of three new polymorphs of m-aminobenzoic

acid (m-ABA) are reported, elevating this system to the rare class of polymorphic systems with

at least five known polymorphs. The crystal structures of the three new polymorphs have been

determined directly from powder X-ray diffraction data, using the direct-space genetic

algorithm technique for structure solution followed by Rietveld refinement, demonstrating the

opportunities that now exist for determining crystal structures when crystals of sufficient size

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and quality for single-crystal X-ray diffraction are not available. The assignment of the

tautomeric form in each polymorph is confirmed by X-ray photoelectron spectroscopy.

B. Forensic science

Chemical analysis of forensic "specimens" usually means identification and/or

comparison. However, the specimens differ from most of those encountered in other situations in

that they constitute evidence, and as such should be preserved. Powder diffraction is a non-

destructive process, and is therefore well-suited to forensic analysis. It is also versatile, and can
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be used for analyzing organic, inorganic and metallic specimens, and, qualitatively and

quantitatively, mixtures of these materials.

A prime example of its value is in the analysis and comparison of street narcotics

seizures, which, in addition to the drug itself, will invariably contain excipients or adulterants.

Some of these compounds will have been added deliberately by the dealer in order to render the

drugs more palatable, and of course to maximize his profit. In doing so, however, he is creating

an analytical “signature” or profile which can be useful in tracing individual drug seizures to a

common source - him. The more chemical components identified in an individual seizure, the

greater the evidential value of a match between numbers of chemically identical seizures. In

addition, many drugs, and certain excipients or adulterants, exist in different polymorphic forms,

hydrated forms and optically active or racemic forms, and each variation may be successfully

differentiated by powder diffraction, adding to the evidential value of the analysis. The opium

poppy Papaver somniferum is the source of the narcotic analgesics morphine and codeine.

Salutaridine reductase (SalR; EC 1.1.1.248) reduces the C-7 keto group of salutaridine to the C-7

(S)-hydroxyl group of salutaridinol in the biosynthetic pathway that leads to morphine in the

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opium poppy plant. P. somniferum SalR was overproduced in Escherichia coli and purified using

cobalt-affinity and size-exclusion chromatography. Hexagonal crystals were obtained using

ammonium sulfate as precipitant and diffracted to a resolution of 1.9 Å (Higashi et al., 2010).

The result of cooperation between a police forensic laboratory and an academic

institution, outlines the possibility of applying single-crystal X-ray diffraction analysis as an

effective method of identifying designer drugs in forensic analysis. The description of the

relationship between the geometrical parameters of moieties and the analysis of intermolecular
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interactions occurring in crystals of the title compounds extends knowledge about the synthetic

derivatives of cathinone and may play a role in future studies, leading to a better understanding

of their characteristic properties (Trzybinski et al., 2013).

The possibility to discriminate between sheets of paper can be of considerable importance

in questioned document examinations. 19 similar types of office paper were characterized by

infrared spectroscopy and X-ray diffraction to individuate the most discriminating features that

could be measured by these techniques. The discriminating value associated to them was also

assessed. By using a sequence of these two techniques, all the samples could be differentiated

(Causin et al., 2010).

Powder X-ray diffraction (PXRD) is used widely in forensic science laboratories with the

main focus of qualitative phase identification and validation of PXRD in the field of forensic

sciences. According to EN ISO/IEC 17025, the method has to be tested for several parameters.

Trueness, specificity, and selectivity of PXRD were tested using certified reference materials or

a combination thereof. All three tested parameters showed the secure performance of the method.

Sample preparation errors were simulated to evaluate the robustness of the method. These errors

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were either easily detected by the operator or nonsignificant for phase identification. In case of

the detection limit, a statistical evaluation of the signal-to-noise ratio showed that a peak

criterion of three sigma is inadequate and recommendations for a more realistic peak criterion are

given (Eckardt et al., 2012).

XRD is used mainly in contact trace analysis. Examples of contact traces are paint flakes,

hair, glass fragments, soils, stains of any description and loose powdered materials. Identification

and comparison of trace quantities of material can help in the conviction or exoneration of a
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person suspected of involvement in a crime.

Soils may constitute evidence that connects a person or object to a particular location.

The value of soil stems from its ubiquity and transferability to objects or persons. Due to the

complexity of soil, the analysis of its inorganic and organic components can provide

complementary and independent types of information about its geological origin, dominant

vegetation, management and environment. There is a work that present an overview of a range of

soil characterisation methods including chemical analysis,mineralogy and palynology, alongwith

new approaches such as DNA profiling and profiling of other digital data such as that obtained

from X-ray powder diffraction, infrared spectroscopy and organic marker analysis. Individual

analytical techniques have different scales of resolution and relevance depending on the nature of

the criminal case and context. Each method has its strengths and weaknesses. As more methods

have become digital and quantitative, their use in combination as digital profiles will help to

characterise soils more accurately and at different scales.

These new approaches can be tested using existing soil databases, and database

development and use will help to refine and narrow probable origin of a questioned sample in

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police intelligence, as well as giving increasingly robust sample comparisons for evidence

(Dawson and Hillier, 2010).

In view of the difficulties in extracting quantitative information from burned bone, a

study suggest a new and accurate method of determining the temperature and duration of burning

of human remains in forensic contexts. Application of powder X-ray Diffraction approach to a

sample of human bone and teeth allowed their microstructual behaviour, as a function of

temperature (200-10000C) and duration of burning (0, 18, 36 and 60 min), to be predicted. The
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experimental results from the bones and teeth determined that the growth of hydroxylapatite

crystallites is a direct and predictable function of the applied temperature, which follows a non-

linear logistic relationship. This will allow the forensic investigator to acquire useful information

about the equilibrium temperature brought about by the burning process and to suggest a

reasonable duration of fire exposure (Piga et al., 2009).

Conservation science relies on measurements of physical and chemical properties. In

Europe in last decades, non-invasive (integrity of the object is preserved, no sampling is

necessary) and non-destructive micro-analytical (sample is taken, but analyzed as is, not

consumed or modified) methods were widely tested in cultural heritage field – especially in the

case of paintings. This growing trend can easily be demonstrated on the increasing number of

publications in top-impacted analytical journals. Current developments can be divided into two

directions:

 developments in physical principles and instrumentation – e.g. portable instruments

(Grieten and Casadio 2010; Miliani et al., 2010);

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 developments in measuring and interpretation strategies – including unconventional

approaches (Cardell et al., 2009; Palmieri et al., 2011).

The uniqueness and limited amounts of forensic samples and samples from objects of

cultural heritage together with the complexity of their composition requires the application of a

wide range of micro-analytical methods, which are non-destructive to the samples, because these

must be preserved for potential late revision. Laboratory powder X-ray micro-diffraction (micro-

XRD) is a very effective non-destructive technique for direct phase analysis of samples smaller
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than 1 mm containing crystal constituents. It compliments optical and electron microscopy with

elemental micro-analysis, especially in cases of complicated mixtures containing phases with

similar chemical composition. However, modification of X-ray diffraction to the micro-scale

together with its application for very heterogeneous real samples leads to deviations from the

standard procedure (Švarcová et al., 2010).

C. Geological applications

XRD is the key tool in mineral exploration. Mineralogists have been amongst the

foremost to develop and promote the new field of X-ray crystallography after its discovery.

Thus, the advent of XRD has literally revolutionized the geological sciences to such a degree that

they have become unthinkable without this tool. Nowadays, any geological group actively

involved in mineralogical studies would be lost without XRD to unambiguously characterise the

individual crystal structures. Each mineral type is defined by a characteristic crystal structure,

which will give a unique X-ray diffraction pattern, allowing rapid identification of minerals

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present within a rock or soil sample. The XRD data can be analysed to determine the proportion

of the different minerals present.

The surface layer of soil consisting of the mixture of mineral and organic matter reflects

the nature and properties of the soil. Weathering the minerals of the earth crust originally derived

most of the substances including plant nutrients. Among various substances, clay is an important

soil constituent that controls its properties and also influences its management and productivity.

In addition to commercial applications of clay minerals, it has great potential to fix pollutants
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such as heavy metals organics and plays an important role in cleansing the biosphere. Despite the

fact that excess clay induces unfavorable property and required more energy for tillage operation,

clay immensely improves soil fertility. In this respect, it is important to carry out quantitative and

qualitative analysis of clay minerals in soil. X-ray diffraction has shown to be one of the best tool

for the identification and quantification of minerals present in soil (Shrivastava, 2009).

In another study the sand deposits from River Niger in Anambra State, South Eastern

Nigeria, were characterized for its potential utilization as industrial raw materials for ceramics

and enamel wares. Physical, chemical and mineralogical characteristics of the sand sample were

determined. X-ray diffraction (XRD) was used in the mineralogical characterization. Results

obtained were analyzed using Bragg-Wolf equation and International Centre for Diffraction Data

software. The results show that the sample contain the phyllosilicate minerals of mica group and

identified as shirozulite (KMn3 [Si3Al]O10[OH]2) a new manganese dominant of monoclinic

arrangement. The physicochemical analysis of the deposits confirms the XRD results.

The results concluded that the samples could be utilized as industrial raw materials for

ceramic and enamel wares (Eunice et al., 2013).

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X-ray diffraction analysis of black shale of Upper Triassic Member Chang 7 of the

Yanchang Formation in southeastern Ordos Basin showed that black shales were deposited in

brackish, strongly reducing, semi-deep-deep lacustrine facies, and mainly composed of quartz,

feldspar, carbonate (dolomite), clay minerals (illite and illite/ smectite) and a certain amount of

pyrite. The mineral composition characteristics of this set of black shales are similar to those of

highly productive shale gas in North America, for example shallow burial, low clay mineral and

abundant brittle mineral, so the strata are conducive to the development of cracks and fractures.
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Thus, this area is favorable for shale oil/gas exploration and development (Zhigang et al., 2014).

Andreeva et al. (2011) studied Middle Devonian (Givetian) dolomites occur in three well

sections: OP-2 Mihalich, R-119 Kardam and R-1 Vaklino (Northeastern Bulgaria). Two general

genetic dolomite groups are distinguished and interpreted on the basis of performed XRD

analyses and petrographic observations. The first one is represented by early diagenetic crypto-

to microcrystalline dolostones that are characterized by nearly stoichiometric composition (from

51.0 to 51.7 mole % CaCO3) and degree of order ranging from 0.50 to 0.91. They are interpreted

as products of rapid precipitation in an arid peritidal (sabkha) environment with hypersalinity of

the water milieu and elevated Mg/Ca ratio of the dolomitizing solutions. The second group

includes late diagenetic medium crystalline dolostones that have almost stoichiometric

composition (from 50.0 to 51.3 mole % CaCO3) and higher degree of order (from 0.77 to 1.18)

indicating a possible slow crystallization process and precipitation from dilute solutions at

elevated temperatures in an open diagenetic system. A part of them might have also resulted

from neomorphic alteration of precursor metastable dolomite phases.

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D. Microelectronics industry

As the microelectronics industry uses silicon and gallium arsenide single crystal

substrates in integrated circuit production, there is a need to fully characterize these materials

using the XRD. XRD topography can easily detect and image the presence of defects within a

crystal, making it a powerful non-destructive evaluation tool for characterizing industrially

important single crystal specimens.

The engineering of strained semiconductor materials represents an important aspect of

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the enhancement in complementary metal-oxide semicondictor (CMOS) device performance

required for current and future generations of microelectronic technology. An understanding of

the mechanical response of the silicon (Si) channel regions and their environment is key to the

prediction and design of device operation. Because of the complexity of the composite

geometries associated with microelectronic circuitry, in situ characterization at a submicron

resolution is necessary to verify the predicted strain distributions. Of the measurement

techniques commonly used for strain characterization, synchrotron-based X-ray microbeam

diffraction represents the best nondestructive method to provide spatially resolved information.

The mapping of strain distributions in silicon-on-insulator (SOI) features induced by overlying

silicon nitride structures and embedded heteroepitaxial features adjacent to SOI device channels

are presented. The interaction regions of the SOI strain were observed to extend large distances

from the SOI/stressor interfaces leading to significant overlap in the strain distributions at

technically relevant dimensions. Experimental data were also compared to several mechanical

models to assess their validity in predicting these strain distributions. (Murray et al., 2010)

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The recent development of bright X-ray sources, reliable X-ray focusing optics, large X-

ray detectors and X-ray data modelling and processing, have improved X-ray techniques to the

point where many are being introduced in metal-on-silicon(MOS) transistor manufacturing lines

as new metrology methods. The fudamental X-ray physical properties, such as their small

wavelength and their weak interaction with solid-state matter satisfy basic in-line metrology

requirements: non-destructiveness, speed, accuracy, reliability and long-term stability. The

capability of X-ray based metrology methods to monitor critical 65 and 45 nm processes such as

ion implant, nitrided SiO2 gate dielectrics, NiSi, Cu/porous low-κ interconnects and MIM
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capacitors is highlighted (Wyon, 2010). 


Interfacial microstructures of thermosonic Au wire bonding to an Al pad of die were

investigated firstly by high-resolution transmission electron microscopy (HRTEM) and X-ray

micro-diffractometer. The equal-thickness interference structures were observed by HRTEM due

to diffusion and reaction activated by ultrasonic and thermal at the Au/Al bond interface. X-ray

diffraction results showed that three different interplanar crystal spacings ("d" value) of the

interfacial microstructures were 2.2257 Å, 2.2645 Å, and 2.1806 Å respectively from the high

intensity of diffraction to the low intensity of diffraction. These indicated that the intermetallic

phase AlAu2 formed within a very short time. It would be helpful to further research wire

bonding technology. (Junhui et al., 2011).

The manufacture of ultra-large scale integration technology can impose significant strain

within the constituent metallization because of the mismatch in coefficients of thermal expansion

between metallization and its surrounding environment. The resulting stress distributions can be

large enough to induce voiding within Cu-based metallization, a key reliability issue that must be

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addressed. The interface between the Cu and overlying capping layers is a critical location

associated with void formation. By combining conventional and glancing-incidence X-ray

diffraction, depth-dependent stress distributions that develop in Cu films and patterned features

are investigated. In situ annealing and as-deposited measurements reveal that strain gradients are

created in capped Cu structures, where an increased in-plane tensile stress is generated near the

Cu/cap interface. The interplay between plasticity in Cu and the constraint imposed by capping

layers dictates the extent of the observed gradients. Cu films possessing caps deposited at
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temperatures where Cu experienced only elastic deformation did not exhibit depth-dependent

stress distributions. However, all capped Cu samples exposed to temperatures that induce plastic

behavior developed greater tensile stress at the Cu/cap interface than in the bulk Cu film after

cooling, representing a clear concern for the mitigation of metallization voiding (Murray et al.,

2012).

E. Glass industry

While glasses are X-ray amorphous and do not themselves give X-ray diffraction patterns, there

are still manifold uses of XRD in the glass industry. They include identification of crystalline

particles which cause tiny faults in bulk glass, and measurements of crystalline coatings for

texture, crystallite size and crystallinity.

The effects of high pressures on the structure of silica glass have been elucidated using

high-energy x-ray diffraction up to 43.5 GPa. A decrease in the first two peak positions in the

real-space pair-distribution functions up to 15 GPa indicates an initial shrinkage of the

tetrahedral units. Above this threshold pressure the Si-O bond peak shape becomes asymmetric

and the average Si-O bond length and coordination number both increase linearly with pressure.

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Also, strained geometries in the O-O correlations lead a pronounced topological rearrangement

of the second and third nearest neighbors (Benmore et al., 2010).

The crystallization behaviour of aluminosilicate glasses of lanthanum, yttrium and

scandium has been studied by DTA, XRD, SEM-EDX and EPMA analysis. Young modulus E

and hardness H have been measured by using nano-indentation and elastic modulus C11 and C44

by Brillouin scattering. The Young modulus measured by nano-indentation agree to those

determined by Brillouin scattering and those calculated using Makishima-Mackenzie and

Rocherullé model’s. The results of DTA analysis indicate that (a) the glass transition
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temperatures Tg are higher for yttrium and scandium containing glasses than their lanthanum

counterparts, the melting observed in the yttrium glasses and recently in the scandium glasses

correspond to the ternary eutectic Ln2O3-Al2O3-SiO2 (Ln = Y, Sc) (b) the thermal stability is

strongly related to the ionic radii of the rare earth. The last results obtained on scandium

containing glasses confirm this hypothesis. The XRD results show that the nature of the observed

crystallised phases is consistent with the phase diagrams. (Sadiki et al., 2010).

Molecular dynamics simulations and complementary neutron and x-ray diffraction

studies have been carried out within the single phase glass forming range of

(Y2O3)x(Al2O3)(100−x), for x = 27 and 30. An R-factor analysis showed that the simulation models

agreed to within ~6% of the diffraction data in both cases. The Al–O polyhedra are dominated by

fourfold and fivefold species and the Y–O local coordinations are dominated by sixfold,

sevenfold and eightfold polyhedra. Analysis of the oxygen environments reveals a large number

of combinations, which explains the high entropy of single phase yttrium aluminate glasses and

melts. Of these, the largest variation between x = 27 and 30 is found in the number of aluminum

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oxygen triclusters (oxygens bonded to three Al) and oxygens surrounded by three Y and a single

Al. The most abundant connections are between the AlOx and YOy polyhedra of which 30% are

edge shared. The majority of AlOx–AlOx connections were found to be corner shared (Du et al.,

2009).

A high-energy X-ray diffraction study has been carried out on a series of

0.5Li2S+0.5[(1−x)GeS2+xGeO2] glasses with x=0.0, 0.1, 0.2, 0.4, 0.6 and 0.8. Structure factors

were measured to wave vectors as high as 30Å−1 resulting in atomic pair distribution functions
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with high real space resolution. The three dimensional atomic-scale structure of the glasses was

modeled by reverse Monte Carlo simulations based on the diffraction data. Results from the

simulations show that at the atomic-scale 0.5Li2S + 0.5[(1−x)GeS2+xGeO2] glasses may be

viewed as an assembly of independent chains of (Li+-S)2GeS2/2 and (Li+-O)2GeO2/2 tetrahedra as

repeat units, where the Li ions occupy the open space between the chains. The new structure data

may help understand the reasons for the sharp maximum in the Li+ ion conductivity at x∼0.2

(Messurier et al., 2009).

Nasu et al.(2009) investigated the micro-mechanism of deformation behavior of metallic

glasses. The authors reported the results of direct observations of short-range and medium-range

structural change during tensile deformation of metallic glasses by high energy X-ray diffraction

method. Cu50Zr50 and Ni30Zr70 metallic glass samples in the ribbon shape (1.5mm width and

25μm) were made by using rapid quenching method.

Tensile deformation added to the sample was made by using special equipment adopted

for measuring the high energy X-ray diffraction. The peaks in pair distribution function g(r) for

Cu50Zr50 and Ni30Zr70 metallic glasses move zigzag into front and into rear during tensile

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deformation. These results of direct observation on atomic distribution change for Cu 50Zr50 and

Ni30Zr70 metallic glass ribbons during tensile deformation suggest that the micro-relaxations

occur.

F. Corrosion Analysis

XRD is the only analytical method that readily provides information about the phase-

composition of solid materials.

The most important versatile and widely used method for corrosion protection of
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steelworks is by paint or organic coatings. Information about microscopy of a protective coating

is essential to understand the basic determinants of its attributes and improvement requirements.

Bitumen has been an important material for the protection of steelworks in the world’s petroleum

or other chemical and water industries. Bitumen is however attended with some undesirable

characteristics and it can vary widely in quality from one source to another. The results show that

about 3.75 to 4.847% of each coating is constituted by five to seven of 14 listed different mineral

phases; and there is variation in quantity and types of these phases even in coatings produced at

the same temperature with bitumen from the same source (Guma et al., 2012).

Three bronze vessels from the ancient Chinese art collection at the Art Institute of

Chicago (AIC) were examined with the advanced non-invasive characterization capabilities of

high-energy synchrotron X-ray diffraction performed at the Advanced Photon Source (APS) of

Argonne National Laboratory (ANL) - to create a comprehensive overview of each object’s

manufacture as well as subsequent corrosion processes. Findings were also complemented with

traditional non-invasive characterization techniques, including optical imaging, X-ray

radiographic imaging, and X-ray fluorescence (XRF) spectrometry. The results- obtained without

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sampling—allow a clear distinction between genuinely ancient Chinese bronzes from those with

modern restorations and from “archaistic” objects made many centuries later, in emulation of

ancient styles (Young et al., 2010).

The inhibition behavior of Momordica charantia seeds extract (MCSE) as an

environmental benign corrosion inhibitor for J55 steel was investigated in 3.5 wt.% NaCl

saturated with CO2 solution by means of polarization curve, AC impedance and X-ray

diffraction (XRD). The results showed that MCSE can inhibit the corrosion of J55 steel. The
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maximum inhibition efficiency is achieved when MCSE concentration is 1000 ppm by weight in

this study. The adsorption of the studied inhibitor obeyed the Langmuir’s adsorption isotherm

(Singh et al., 2013).

Corrosion ID can help to locate the origin of corrosion in a facility and, at the same time,

provide solutions to the problem. The formation of scale deposits (e.g., scale deposits, corrosion

deposits, formation materials, reaction products, catalysts and refractory materials) in sulfur

recovery unit (SRU) process equipment is one of the major operational problems in the oil and

gas industry. Thick deposits of various types of mineral scales can grow within these units.

Subsequently, these deposits end up adversely affecting the production rate and quality. Zaidi et

al. (2012) conducted a study of 13 types of scale deposits that build up in the different regions

(converter, condenser and vessel) using X-ray diffraction, which is the best available technique

for the identification and quantification of all compounds present in deposits. Additionally, the

recent application of the Rietveld refinement method in X-ray diffraction quantitative phase

analysis has produced great advantages over conventional methods such as the reference

intensity ratio method for accuracy and convenience. The refinement results showed that while

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iron oxide (magnetite and hematite) corrosion products are found in the steam drum, several case

studies show sulfates (iron, sodium, and ammonium) are the major deposit compounds built up

in the condenser. A high weight percentage of hematite indicates the presence of dissolved

oxygen in the boiler feed water. The deposits accumulated in the converter are titanium and

aluminum oxide, which indicates the leakage of a catalyst. Sulfur and carbon are also detected

from the line. The findings will help the engineers to overcome the problems by devising the

right corrective procedures.

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4. Conclusion

X-ray diffraction (XRD) is an analytical technique used to characterize crystalline phases

of a wide variety of materials, typically for mineralogical analysis and unknown identification.

Powder diffraction data are fundamentally derived by the atomic and molecular arrangements

explained by the physics of crystallography.

There are several advantages of XRD techniques in science laboratories:

 Non-destructive, fast, easy sample preparation in XRD;

 High-accuracy for d-spacing calculations;

 Can be done in-situ;

 Pemit single crystal, poly, and amorphous materials;

 Standards are available for thousands of material systems.

In the last few years, powder XRD systems are becoming more and more efficient for the

pharmaceutical industry due to innovation or improvement of detection or/and source emission

technology. X-ray diffraction methods are especially significant for the analysis of solid

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materials in the forensic science. They are often the only methods that allow a further

differentiation of materials under laboratory conditions.

Minerals are the building blocks of the solid Earth. Some minerals are readily recognized

by their distinctive colors or crystal forms, but in most cases, powder X-ray diffraction is the

primary and most definitive method used to identify minerals. The high flux and density of x-

rays produced at synchrotrons provide the microelectronics industry with a powerful probe of the

structure and behavior of a wide array of solid materials that are being developed for use in
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devices of the future. X-ray diffraction studies are used to obtain information on the short and

intermediate range structure of glasses.

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Figure 1 - Schematic diagram of a diffractometer system

Figure 2. Geometry of the Bragg–Brentano diffractometer

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