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Determination of alpha and beta alumina in ceramic alumina by X-ray

diffraction

Article  in  Spectrochimica Acta Part B Atomic Spectroscopy · July 2000

DOI: 10.1016/S0584-8547(00)00225-1

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 Determination of alpha and beta alumina in ceramic alumina by X-ray diffraction

ABSTRACT

Frank R. FERET (*), Daniel ROY, Clermont BOULANGER

Alcan International Ltd., Arvida Research and Development Center

Jonquière, Québec G7S 4K8

Determination of alpha alumina (-Al2O3) content has been one of the oldest X-ray

diffraction methods of analysis. However, rhombohedral aluminas may have a variety of

morphological forms for which there are marked differences in relative intensities of their

major XRD reflections (the preferred orientation effect). In addition, a specimen X-ray

diffracting power may vary making it difficult or impossible to employ a reference material.

Consequently, comparing intensities of selected reflections from a sample with those of a

reference material may cause a serious analytical error.

A conventional XRD and a Rietveld approach were used to analyze nine commercial ceramic

aluminas, three NIST standards and two special grades of alumina for alpha and beta

alumina (-Al2O3 = Na2O·11Al2O3) content. The samples were also analyzed by Electron

Scanning Microscopy to assess morphology. Increasing the number of XRD reflections

analyzed from two to eight did not improve the reliability of the quantification process. The

morphological differences among samples could not have been minimized that way.

Conventional XRD (2–8 reflections) indicated alpha alumina values varying from 88 to 106 %

while the Rietveld analysis (full pattern) attributed 100 % for all but two. These two samples
were found to contain beta alumina. Initial Rietveld refinements indicate that the beta phase

contains only a fraction of the total Na2O content. The preferred orientation was computed

for 14 specimens and assessed using a relative scale.

The Rietveld least-square refinements would not only provide relatively quick, but also

reliable information on alpha and beta content, as well as unit cell parameters of alpha and

beta phases.

Keywords: Ceramic alumina; alpha and beta alumina determination; X-ray diffraction;

Rietveld refinement

*Corresponding author, tel. (450) 592-6392, E-mail feretfr@gmail.com

 Determination of alpha and beta alumina in ceramic alumina by X-ray diffraction

Introduction

Determination of alpha alumina content in alumina by XRD has been one of the oldest

industrial instrumental methods of analysis. Most XRD methods require that alumina

specimen prepared as a cavity slide is measured together with a very pure, tightly controlled

particle-size-distribution 100% alpha alumina standard. Usually, two X-ray diffraction

reflections are scanned, and the integrated intensity ratio between the sample and the

standard for both reflections are calculated and averaged to determine the alpha alumina

content. Selected (hkl) reflections correspond to d spacings of 3.48 Å (012) and 1.60 Å

(116). The (012) reflection can be considered free of interference from other alumina

phases. The (116) reflection is subject to a weak interference from sub-alpha forms of

alumina, as well as to a stronger interference by sodium aluminate forms.

The Australian AS 2879.3-1991 Method [1] is applicable to smelter-grade alumina

containing alpha phase at levels up to 50%. In this method the integrated peak area of the

(012) lattice plane reflection is measured at 3.48 Å for the test sample and a 100% alpha

alumina standard. The ratio between the net peak area intensities for the test sample and

the standard is determined and the alpha alumina content calculated from this ratio.

Over the years, significant differences in results originating from one or two reflections

have been observed in the case of special aluminas (above 50% alpha). The preferred

orientation effect that varies considerably with sample texture is the main cause. According

to the ICDD* specification (reference pattern number: 46-1212) the theoretical intensity ratio
between the (012) and (116) reflections in 100% alpha alumina should be 0.506. Ratios

much different from this one have been observed in the past.

Al2O3 (Corundum) Structure

Aluminum forms sesqui-oxide with rhombohedral (corundum) structure [2]. In this

structure the metal atom is octahedrally coordinated with oxygen atoms (Fig. 1).

The corundum structure can be visualized as layers of hexagonal close-packed oxygen

atoms with small Al atoms in two-thirds of the octahedrally coordinated holes between the

oxygen atoms. The atomic positions consist of twelve aluminum atoms and eighteen oxygen

atoms. The unit cell dimensions are: a = b = 4.7588 Å, and c = 12.992 Å. The most

important alpha reflections observed on a diffractogram are listed in Table 1.

The relative intensities (and consequently concentrations) measured for two peaks (3.48 and

1.74 Å) vary a little, because they belong to the same series of parallel planes described by

Miller indices hkl (012) and (024). In other words the (012) and (024) reflections provide

practically the same analytical information (same symmetry planes; the maximum number of

planes of symmetry possible for a crystal is nine).

Interference of alpha peaks by strong peaks belonging to a sub-alpha family was also

considered. Given in Table 2 are those peaks of sub-alpha compounds that have relative

intensities above 50%. Almost all sub-alpha compounds can affect the 1.405 Å alpha peak.

Beta alumina may also influence the 1.374 Å reflection of the alpha phase. Reflections other

than beta have little chance of being present in highly calcined aluminas; hence their

potential interference with alpha reflections is negligible.

Experimental

Sample preparation

Sample preparation plays an important role in alpha alumina determination. Normal

alumina sample preparation consists of hand grinding the sample until it all passes through a

-325 mesh screen. For metallurgical and ceramic aluminas, the hand grinding corresponds

to 0.5 - 1 min of grinding in a puck-and-ring grinder. Grinding a 20-g portion of a typical

alumina in a Shatterbox grinder for 30 seconds reduces the particle size of most of the

sample material to less than -325 mesh. The portion, which does not pass through the 325

mesh, should be ground further. When dealing with ceramic aluminas the grinding operation

becomes more important from the analytical point of view. As the material gets harder the

grinding time should be extended to obtain fine material. However, prolonged or too short

grinding affects final morphology. For example, if the 100% Alcan IBM-85 -Al2O3 is ground

for 2 minutes, the concentration calculated for the two major peaks drops down to 86% and

82%.

For practical reasons the grinding time should be short to avoid cross-contamination.

As a result of grinding, the final texture of various aluminas can be markedly altered; this

affects preferred orientation.

A standard cavity slide preparation technique was used to obtain “ready to analyze”

specimen. The samples were not ground except the PoDFA sample (porous disk used in

filtration of liquid Al). The SRM 1976 flat disc was cut to size. The “as obtained” sample

material was loaded from the top of the cavity, then, excess material was removed with a

sharp edge. As seen in Figures 2 - 9 the particle size distribution is below 40 m (-325
mesh). To minimize the effect of preferred orientation a second sample preparation

technique was tried. Using the standard back loading technique a paper washer about 1 mm

in thickness is added between the top slide surface and the supporting glass. The material is

loaded from the back of the slide. Once the glass is detached, the paper washer is separated

and the excess material is removed with a sharp edge. This operation helps obtain the top

sample layer composed of particles oriented randomly; thus minimizes the preferred

orientation effect. Nevertheless, the new approach did not much affect preferred orientation

as compared with the standard back loading technique.

Experimental conditions

A Siemens D 5000 diffractometer controlled by DIFFRACplus software was used in

the study. The experimental conditions of the instruments and parameters used are given in

Table 3.

To assure good representation of intensities corresponding to selected reflections the

specimens were spun during measurement. Consequently, many more crystallites

participate in the diffraction thus improving accuracy of the alpha alumina determination.

SEM observations

Fourteen ceramic alumina samples were used in the study. One (monocrystal) was

manufactured in Alcan R&D Centre; ELF ATO platelets were purchased from Elf Atochem

North America Inc.; PoDFA discs are used throughout the aluminum industry for liquid metal
filtration; three SRM standards were purchased from NIST; six production samples were

submitted by various plants.

The samples were analyzed by Scanning Electron Microscopy (Jeol MEB and

Cambridge S-360) using secondary electron mode. The samples were mounted on an Al

support and covered with a conductive layer of Au-Pd. Selected SEM images (Fig. 2-9)

clearly represent the material’s morphology and also help to estimate the particle size

distribution. Shapes of particles observed among the samples vary from almost spherical

(Alcan monocrystal), through flakes (3-7 µm ATO, 10-15 µm ATO) to particles of various

shapes and sizes (down to ~1 µm).

XRD measurements

XRD scans were obtained from samples being investigated using measuring

conditions specified in Table 3. The scans were next analyzed using the DIFFRACplus

evaluation program (EVA). Several parameters, such as observed peak maximum position,

maximum intensity, net area, FWHM, centre of gravity, etc, were obtained in the process.

Next, relative intensities were calculated for major reflections in reference to SRM 676

standard and compared with ICDD data (Table 4). Scans corresponding to two selected

samples are shown in Fig. 10. Different lines represent them: PoDFA – dashed line, ATO 3-7

µm – solid line. For a better comparison the two diffractograms are slightly displaced

horizontally. In Fig 10 and Table 4 it is clear that relative intensities of individual reflections

vary considerably.
For determination of alpha alumina concentration with a conventional XRD approach - two,

five, six, seven and eight reflections were selected. Reflections used in the calculations are

listed in Table 5. Concentrations of alpha alumina were calculated using SRM 676 as a

100% reference standard and are given in Table 5. SRM 676 was selected, as reference

because it showed almost non-existent preferred orientation in tests involving SIROQUANT

software. For the phase quantification process dedicated (hkl) files, corresponding to alpha

and beta crystallographic data, were constructed in the software.

The SIROQUANT software employs the Rietveld method [3-7]. This method has

emerged over the last few years in modern XRD quantitative phase analysis because it does

not depend on any calibration standards. Quantitative mineralogical analysis by the Rietveld

method uses all the intensity data in a pattern rather than a few of the most intense

reflections. The method partially compensates for preferred orientation and extinction. In

the quantification process the Rietveld based methods involve structural data for each

phase (atomic coordinates, Lorentz, scattering and polarization factors, physical and

chemical constants, etc.). Least-square refinements are carried out until the best fit is

obtained between the observed diffraction pattern taken as a whole, and the entire

calculated pattern [3].

Alpha alumina concentrations determined with SIROQUANT software are compared

with those determined with conventional XRD in Table 6. In addition to alpha concentration,

the beta phase content is also determined.

 The beta content obtained using Rietveld analysis was compared with beta

concentrations determined by XRF. The Na2O concentrations corresponding to plant special

aluminas were determined with a fusion sample preparation technique. Next, employing the

stoichiometric coefficient (19.095) the concentrations of the beta phase (Na2O·11Al2O3) were

calculated. In order to explain differences between Rietveld and XRF data a hypothesis

assuming that Na2O may be present at trace levels in a phase(s) other than beta (leachable

Al2O3) was tested. Two samples containing the highest Na2O content (Plant 2 and Plant 5)

were leached with H2O, then analyzed by XRF. The Na2O concentrations obtained were

lower (0.18% and 0.12%, respectively). The corresponding concentrations of the beta phase

were 3.5% and 2.29%, as opposed to 4.0% and 3.25% obtained before the leaching

procedure. This confirms that a part of Na2O content in these two ceramic aluminas is

present in a leachable form. Additional parameters, which are also obtained from Rietveld

analysis are global fit, unit cell dimensions, scale factor, preferred orientation, and half-width

(FWHM). These parameters are listed in Table 7.

Discussion

The 676 Standard Reference Material from the National Institute of Standards &

Technology appears to be the least affected by the preferred orientation effect. The SRM

676 powder material consists of sub-micron equi-axial alumina grains, which have been de-

aggregated and calcined. Therefore, it seems to be the best standard for evaluation of the
preferred orientation effect and quantification of alumina phases. Alcan nearly spherical

monocrystal alumina comes a close second, as it also displays the isometric form of the

grains. All other materials show a moderate, strong or very strong preferred orientation

effect, which hampers the phase quantification process.

Several samples with assigned alpha alumina concentrations have been made in various

laboratories in the past. If the analytical methodology used involved one or more diffraction

reflections, these samples cannot be considered as reference materials. Consequently, we

suggest that users do not depend on these standards any more.

In order to balance the preferred orientation effect various combinations of reflections

were used. Gradually increasing the number of reflections from two to eight did not improve

the reliability of the quantification process. The morphological differences between samples

could not have been minimized that way. In general, using a reference alpha standard in the

quantification process may lead to highly erratic results. Alphas content much different from

100% (88-106%) may be obtained for samples that are surely composed of 100% alpha. In

addition, it is difficult to assign the beta phase content using conventional XRD. It is clear

now, that calculation of the alpha and beta contents in ceramic aluminas should not be

recommended when employing a reference standard. Instead, a tool such as SIROQUANT

software using full pattern and Rietveld analysis would be the most suitable option. The

Rietveld least- square refinement approach does not depend on any calibration standards.

This tool would not only provide relatively quick, but also reliable information on alpha and

beta content, as well as unit cell parameters of alpha and beta phases.
 Employment of the Rietveld method comes at a price. First, it is necessary to record a

complete diffractogram (6-90 °2). This can still be tolerated because modern XRD

instruments are equipped with automatic sample changers allowing analysis of many

samples without operator involvement. Certainly, diffractogram acquisition will take more

instrument time than previously. Second, each sample must be interpreted individually. This

process might take up to two minutes with the Rietveld method, whereas standard method

calculations following one or two peak intensity measurement can usually be automated.

However, in a typical aluminum industry laboratory no more than a few samples per day

need to be analyzed.

As long as the alpha phase occurs at concentrations close to 100% and the complementing

phase is beta - the Rietveld method should apply well. However, uncertainty arises as to the

presence of phases other than alpha and beta (sub-alphas) which might be amorphous.

Their occurrence is unlikely, given the process conditions, but possible. A study on two

selected samples (Plant 2, Plant 4) using ZnO, as an internal standard did not confirm

occurrence of sub-alphas. Nevertheless, more work is needed in order to confirm levels of

sub-alphas occurrence. If there is a major concentration of the amorphous phase(s), they

need to be taken into account in the Rietveld refinements. If not, the refined concentrations

would be larger than otherwise expected. Also, a question on lower application limit of the

Rietveld method needs to be clarified in the future.

One could estimate the -Al2O3 content using only one or a few of the strongest

reflections provided that the 100% standard and all routine samples are of the same

morphology (plant specific method). The same would apply to a calibration with mixtures of
100% -Al2O3 and 100% -Al2O3. If a sample contains -Al2O3 and it can be quantified,

suitable peak overlap correction should apply in the intensity measurement of the -Al2O3

peak, which is affected. When the -Al2O3 content is below 50% the preferred orientation

effect is much less important. Then, intensity measurements of only two major peaks should

provide a good approximation of the -Al2O3 content.

The authors wish to thank Dr. F.M. Kimmerle, Alcan Chief Analytical Chemist, for reviewing

the manuscript and his valuable comments. We also thank Mrs. H. Dufour for the SEM

images and to Mr. Y. Boissonneault for XRF data.

References

1. AS 2879.3-1991 – Australian Standard – Alumina; Part 3: Determination of alpha

alumina content by X-ray diffraction.

2. Galasso, F.S., “Structure and Properties of Inorganic Solids”, Pergamon Press Inc.,

Oxford, 1970.

3. Young, R.A., The Rietveld Method, Oxford University Press, New York, 1993.

4. Hill, R.J., Applications of Rietveld analysis to materials characterization in solid-state

chemistry, physics and mineralogy, Adv. in X-ray Anal., Vol. 35 (1992), 25-37.

5. Taylor, J.C., Computer programs for standardless quantitative analysis of minerals

using the full powder diffraction profile, Powder Diffraction, Vol. 5, No 1 (1991) 2-9.

6. Bish, D.L., Howard, S.A, Quantitative phase analysis using the Rietveld method, J.

Appl. Crystallogr., Vol. 21 (1987) 86-91.

7. Bish, D.L., Post, J.E., Quantitative mineralogical analysis using the Rietveld full-

pattern fitting method, Am. Mineral., Vol. 78, (1993) 932-940.

8. Dollase, W.A., Correction of intensities for preferred orientation in powder

diffractometry: application of the March model, J. Appl. Cryst., Vol. 19 (1986) 267-

272.
 Figure 1. The corundum structure (Al – small sphere, O – large sphere)

Fig. 2 Alcan Monocrystal Fig. 3 Alcan IBM-85 Alumina

Fig. 4 3-7 µm ATO Alumina Fig. 5 10-15 µm ATO Alumina

Fig. 6 PoDFA Alumina Fig. 7 SRM 674a Alumina

Fig. 8 Plant No. 1 Alumina Fig. 9 Plant No. 4 Alumina

 5880
3-7 m ATO
PoDFA

Intensity
Li n ( Count s)

(Counts/sec)

6 10 20 30 40 50 60 70 80 90
2- Theta - Scal e

Angle (°2Θ)

Figure 10 Superposition of two diffractograms: PoDFA and NIST 1976

Table 1 Al2O3 (Corundum) - major XRD reflections (JCPDS-ICDD File No 46-1212)

d (Å) Rel. Intensity (hkl) Angle 2

Cu K1 Co K1
3.48 45 012 25.59 29.80
2.551 100 104 35.14 41.04
2.379 21 110 37.78 44.17
2.085 66 113 43.36 50.81
1.740 34 024 52.55 61.87
1.601 89 116 57.52 67.93
1.405 23 214 66.55 79.15
1.374 27 300 68.20 81.24
Table 2 Interference of alpha peaks (Å) by strong sub-alpha peaks (Å)

ICDD – JCPDS Reference

43-1484 10-414 46-1131 12-539 10-425 21-10 11-517 47-1292 4-880 4-875 26-31 37-1462
47-1770 29-63 23-1009 13-373
46-1215 47-1308 35-121 34-493
4-877 47-1771

          Al2O3 Al2O3
alpha beta delta tau gamma eta theta sigma ksi kappa

3.48 3.470

2.551 2.558

2.38

2.086

1.740

1.602

1.405 1.403 1.39x 1.400 1.397 1.398 1.400 1.400 1.397 1.40

1.374 1.369
Table 3 The Siemens D 5000 measuring conditions
Radiation - Co K Wavelength - 1.7889Å

Detector - Kevex, Peltier cooled PHD window - 20 - 80%

Monochromator - no Sample changer - 40 position

Generator - 40 kV, 40 mA Sample spinner - on

Divergence slit - fixed, 2 mm Receiving slit - 0.6 mm

Scattering slit - 2 mm Step size - 0.02 °2

Measuring time - 1 sec per step Scanning range - 6 - 90 °2

Table 4 Relative intensities (%) calculated for major reflections and compared with
ICDD data and 676 SRM

Reflection 2d [Å]
Sample
3.480 2.551 2.379 2.085 1.740 1.601 1.546 1.515 1.404 1.374

43-1484 ICDD ( c ) 72 98 44 100 48 96 4 6 38 57

46-1212 ICDD ( * ) 45 100 21 66 34 89 1 2 23 27

SRM 676 (NIST data) 58 87 36 100 47 96 - - 36 56

SRM 676 (this study) 59 92 38 100 46 95 2 10 36 58

Monocrystal 63 92 39 100 48 96 2 11 38 52

Alcan IBM-85 62 96 38 100 46 98 2 11 36 55

3-7 µm ATO 54 100 26 80 38 97 1 13 27 37

10-15 µm ATO 60 99 34 96 45 100 2 12 35 49

PoDFA Disk 96 50 56 88 82 31 10 9 27 100

PoDFA ground 61 84 14 100 43 83 2 8 34 53

SRM 674a 59 90 38 100 46 93 2 9 36 58

SRM 1976 flat disc 33 100 13 53 28 95 1 18 21 22

Plant 1 54 100 29 84 40 98 1 12 30 40

Plant 2 47 100 23 71 34 90 0 14 25 31

Plant 3 58 100 33 93 44 100 2 10 33 47

Plant 4 60 100 35 94 46 100 2 13 32 48

Plant 5 54 100 29 85 40 97 2 13 31 41

Plant 6 60 91 37 100 44 92 1 8 26 50

(c) – calculated pattern

(* ) – star quality, experimental pattern
Table 5 Selection of alpha reflections for phase quantification

Number of Reflections Used

Reflection
(Å) 2 5 6 7 8
3.48 + + + + +

2.551 + + + +

2.38 + +

2.086 + + + +

1.740 + + + +

1.602 + + + + +

1.405 +

1.374 + + +
Table 6 Concentrations of alpha and beta phases (%) determined with conventional and
Rietveld approaches, as well as XRF

Conventional XRD Rietveld XRD XRF

Alpha Alpha Beta Na2O Beta
Sample
2 Peaks 5 Peaks 6 Peaks 7 Peaks 8 Peaks Full pattern % %

Monocrystal 98.0 96.3 94.4 94.6 95.2 100 0 - -

Alcan IBM-85 103.0 101.6 100.3 100.1 100.0 100 0 0.02 0.39

3-7 µm ATO 105.1 100.4 95.1 92.2 90.9 100 0 - -

10-15 µm ATO 100.3 98.6 95.9 94.5 94.2 100 0 - -

PoDFA Disk 44.3 47.0 52.2 54.5 51.9 100 0 - -

SRM 674a 95.4 95.4 94.5 94.8 94.7 100 0 - -

SRM 676 100 100 100 100 100 100 0 - -

SRM 1976 50.7 49.5 45.3 42.0 41.4 100 0 - -

Plant 1 104.9 102.5 97.9 95.6 94.8 100 0 0.030 0.57

Plant 2 100.3 98.1 92.0 89.0 87.9 97.1 2.9 0.21 4.0

Plant 3 105.6 104.3 101.0 99.8 99.2 100 0 0.020 0.38

Plant 4 96.2 94.7 91.7 91.1 90.0 100 0 0.029 0.55

Plant 5 102.8 100.5 96.2 94.2 93.6 98.4 1.6 0.17 3.25

Plant 6 98.4 97.8 95.7 95.9 92.9 100 0 0.053 1.01

 Table 7 Crystallographic Data Obtained for Alpha Phase in Investigated Samples

Global Fit Unit Cell Scale Reflectivity Pref. FWHM

Sample Orient.
Chi2 a = b [Å] C [Å] Cps · °2 W° [°2]
Monocrystal 3.91 4.758 12.987 0.0080 909 0.979 0.028
Alcan IBM-85 3.83 4.758 12.989 0.0117 963 0.943 0.030
Elf 3-7 3.83 4.758 12.991 0.0080 993 0.773 0.030
Elf 10-15 3.70 4.758 12.992 0.0081 1000 0.872 0.030
PoDFA 5.56 4.761 12.999 0.0036 449 1.974 0.030
SRM 674a 3.40 4.758 12.988 0.0079 905 1.024 0.047
SRM 676 3.09 4.758 12.988 0.0083 1040 1.006 0.039
SRM 1976 3.54 4.751 12.972 0.0037 447 0.652 0.029
Plant 1 3.06 4.758 12.988 0.0081 941 0.794 0.032
Plant 2 4.50 4.758 12.989 0.0076 1066 0.733 0.030
Plant 3 3.31 4.758 12.988 0.0085 1054 0.855 0.033
Plant 4 3.59 4.758 12.989 0.0076 958 0.871 0.030
Plant 5 3.77 4.760 12.991 0.0080 928 0.799 0.031
Plant 6 3.84 4.759 12.988 0.0076 981 0.969 0.084

Glossary:

Global fit Global fit (Chi-squared 2) is a figure of merit used for determining the fit of a
calculated pattern to the observed data. The 2 parameter approaches 1 for a perfect fit; hence
values close to 3 obtained in the course of this study indicate well refined patterns.

Unit cell parameters The standard unit cell parameters used in SIROQUANT for the alpha alumina
phase are: a = b = 4.7628 Å, and c = 13.0032 Å. The a and c parameters [Å] obtained in this study
are slightly below the standard values, probably due to the limited number of data points acquired for
each sample.

Scale factor In SIROQUANT, approximate Rietveld phase scales have been computed from
crystallographic data, assuming a 20% concentration. The default scales for the alpha and beta
alumina phases are 0.00223966 and 0.000027864, respectively. The Rietveld scales generated in
the refinement process (Table 8) vary greatly among the samples. Because a uniform sample
preparation technique was employed, large scaling differences indicate marked variation in X-ray
reflectivity of specimens. Therefore, the quantification process based on a reference material should
only be allowed for samples featuring similar scaling factors. Fortunately, all plant ceramic aluminas
tried in this study have similar scaling factors.

Reflectivity Reflectivity is the average integrated intensity (cps·°2) obtained for 12 major
reflections of the alpha phase.

Preferred Orientation If the thickness of the layer of material participating in the X-ray diffraction is of
the same order as the particle size, preferred orientation becomes a problem. The principal reason
for variation of relative intensities of practically every reflection in XRD analysis of special aluminas is
preferred orientation and particle size effects. Both are related to the morphology of average grains.
Rhombohedral aluminas may have a variety of morphological forms and sizes for which there are
marked differences in relative intensities of their respective XRD patterns. At high -Al2O3
concentrations approaching 100%, no interference can be responsible for the intensity variations
among the major peaks.

The SIROQUANT software allows correction of profile intensities for preferred orientation of alpha
alumina crystallites in the sample. The method used in the software is that of Dollase[8], which
employs the March distribution function in phase quantification. The refinable orientation parameter,
r, is less than 1 for plates and greater than 1 for rod morphology. The (104) plane selected as
corundum’s orientation plane resulted in very good refinements for all samples except one (PoDFA).
In the case of the PoDFA sample the (012) reflection is abnormally strong (the “plate” reflection) and
was also tried. The (012) reflection, however, did not improve the global fit. This suggests that the
March function used in SIROQUANT is not powerful enough to correct extreme preferred orientation
effects.

Usually, reduction of particle size by prolonged grinding is the single most effective means
for minimizing preferred orientation errors. Most of the specimens used in the study already feature a
very small particle size. In spite of grinding they would still orient preferentially. Regardless of
specimen preparation it may be difficult or impossible to arrive at a truly random distribution of
orientation with ceramic aluminas.

FWHM Halfwidth (FWHM – full width at half maximum) obtained in this study depends not
only on crystallinity but on other factors including instrument parameters, particle size, morphology
and strain. Although SIROQUANT software allows calculation of crystallinity with a Sherrer formula,
we are sure that results obtained that way would not be realistic. The instrument resolution, defined
 mainly by the selection of slits (Table 4), was not set for this objective. The instrument contribution to
the FWHM determined using Arkansas stone was 0.1 °2. Also, for alumina produced within the
same plant, the calculated numbers may not vary much.

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