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D E T E R M I N A T I O N OF M E A N C R Y S T A L L I T E D I M E N S I O N S F R O M X - R A Y D I F F R A C T I O N P E A K PROFILES: A C O M P A R A T I V E A N A L Y S I S OF S Y N T H E T I C HEMATITES
MARIO CROSA,1 VALTER BOERO,t AND MARINELLA FRANCHINI-ANGELA 2 Dipartimento di Valorizzazione e Protezione delle Risorse Agroforestali-Chimica Agraria, Universit5 di Torino, via Leonardo da Vinci 44, I 10095 Grugliasco (Torino), Italy 2Dipartimento di Scienze Mineralogiche e Petrologiche, Universit/a di Torino, via Valperga Caluso 35, 1-10125 Torino, Italy Abstract--X-ray diffraction (XRD) profile analysis of eight synthetic hematite samples was performed to identify the best parameters for determining the apparent mean crystallite dimension (D) and, consequently, surface area. The samples are comparable to soil hematite with respect to crystallinity. The procedure included: a) deconvolution of the XRD peaks to Gauss and Cauchy components and subtraction of the instrumental profile, b) determination of D from full-width at half-maximum, integral breadth, and integral breadth measurements of the Cauchy component, and c) comparison of deduced surface areas with those obtained by the N2-BET adsorption method. As expected, D values are strongly influenced by the broadening parameters. An appropriate selection of peaks is required to obtain size values along the crystallographic axes a (hkl: 110, 300) and c (hkl: 104, 116) and to calculate reliable surface areas. Using the Cauchy component of the above peaks, the calculated surface areas compared well with those measured by the N2-BET adsorption method. Key Words-BET, Hematite, Iron Oxides, Mean Crystallite Dimension, Powder X-ray Diffraction, Surface Area, XRD. INTRODUCTION Hematite (et-Fe203, space group R3c) is a common high-resolution transmission electron microscopy is not satisfactory to obtain data about behavior (e,g., sorption) (Schwertmann, 1987). This is because soil is usually strongly clustered, and the habit of the constituent particles may be easily determined, but not their morphology. Furthermore, only few X-ray diffraction (XRD) peaks of soil hematite do not superpose over peaks from other minerals, thereby making analysis difficult. The XRD method appears to be the only practical and reliable way to describe the surface area, which requires the use of crystal-size measurements. Among suitable XRD parameters, peak broadening is currently used (e.g., Schwertmann and Latham, 1986) to determine the "mean crystallite dimension" (MCD) of hematite, i.e., the size of the coherent scattering domain perpendicular to the diffracting (hkl) plane (Schwertmann and Cornell, 1991), or more recently, the mean coherence length (MCL, Cornell and Schwertmann, 1996), which is equivalent to MCD. The purpose of this work is to investigate how best to evaluate the XRD profile and to determine how the choice of specific XRD reflections may influence the apparent crystal size. We then compare the specific surface area obtained by the method proposed herein and that obtained by the N2-adsorption method. THEORETICAL BACKGROUND The broadening of the XRD diffraction-peak profile h(x) of a microcrystalline substance is assumed to be a convolution of the pure profile f(x) and the instrumental profile g(x) (e.g., Klug and Alexander, 1974,
Fe(III) oxide in soils and sediments of warm climates
(Cornell and Schwertmann, 1996). Even at low (1-10 wt. %) concentrations, hematite may strongly affect chemical-physical properties such as matrix color (Torrent et al., 1983), sorption of anions (e.g., Torrent et al., 1994), organics (Schwertmann et al., 1986) and heavy metals (e.g., Pb, Cu, Zn, Co, Ni, and Mn; Schwertmann and Taylor, 1989), and interactions with phyllosilicates (e.g., soil structure, aggregation, and cementation; Schwertmann, 1987). These properties are strongly affected by surface area and this, in turn, by morphology, habit, and size of the hematite crystals. The "morphology" is defined as the assemblage of the forms present in the crystal without regard to the extent of face development (Hartmann, 1973, p. 369). The "habit" of a crystal depends on the relative development of each form present in the morphology of the crystal. Therefore, crystals having the same morphology, e.g., prism and bipyramid, may show different habits: prismatic habit, when the prism is the most developed form; bipyramidal habit, when the prism is negligible with respect to the well developed pyramid. Unfortunately, such crystal properties are very difficult to observe directly and to measure in the pedoenvironment because soil hematite consists of very small crystallites and is often present at low concentrations. The direct observation of hematite particles by using scanning electron microscopy, transmission electron microscopy (TEM), or Copyright 9 1999, The Clay MineralsSociety
. fix) originates from the microcrystallinity of the phase and g(x) is obtained from a reference phase free of strain and 2-20 txm in size. must be adopted if a " t r u e " value of D is desired. even though it does not always rep- Table 1.1 17. 291).8 7. f(x) may be regarded as the convolution of a Gauss function (strain component) and a Cauchy function (size component.5 27.2 .8 15.0 14. the integral breadth of the Cauchy component ([3c) can be used in Equation (1) instead of 13 to obtain D. K and D can be calcuhlted for several peaks by l e a s t . which is a function of reflection and crystallite shape.5 29.8 12..9 16. Colombo et al. 1989). an estimation of the surface area in hematite may be obtained assuming a quasi-cylinder shape.8 12. If particle shape and size uniformity are assumed.2 12. FWHM.3 10.7 10. 47.3 25.7 19. Both [3 and [3c were determined here for comparison. i. 1991). using the equation: D = K M13 cos 0 (1) where K is the Scherrer constant. Figure 2. however. as adopted by Stanj ek (1991) for hematite. Da and Dc values (nm) of sample H1 obtained from different hkl and broadening parameters. From these values. because fix) is not independent of either the crystallite shape or size distribution (Wilson.8 16. Relation between the mean sizes D calculated from FWHM and from 13.7 3. 13).3 21.3 22. In a simplified way. 1949. mean crystallite size parallel to crystallographic unit lengths a and c.7 13.5 12.. despite its debated physical significance (Langford and Wilson.8 15.2 9. Langford et al. and the K constant is conventionally set to 0.8 8.s q u a r e s fit. the equation allows the determination of an apparent size. Experimental data of g(x) and h(x) are usually fitted with mathematical functions such as the pseudo-Voigt or the Pearson VII functions (Howard and Preston. which may reduce the number of hematite peaks of satisfactory quality. the mean size. assuming a negligible contribution of strain in fix).4 25. Peaks Paxameter 012 104 110 113 024 116 018 214 300 Da values FWHM [3 13o FWHM [3 13c 9. 1978) is used in the analysis of soil iron oxides. e.g.9 (Scbwertmann and Cornell. 1999 180 160 140 XRD profile analysis and mean size of synthetic hematites 350 R 2 = 0.5 17.2 9.1 12.3 17.9 13.7 21.Vol.2 13. D. 13 the F W H M (in radians). the information of crystallite shape and size as derived from the diffraction peaks is not easy to obtain.6 Dc values 9. In soil samples.2 31. and 0 is the peak angular position.8 12.9 3. Thus.0 12. Jones (1981) adopted this approach for soil hematite and. The most useful information about hematite crystallite size and shape may be obtained from Equation (1) and D by determining D a and D c values. diffraction peaks overlap or overlap partially from other phases. (1994) did the same for synthetic hematite. 1987). 6. can be calculated by the full-width at half-maximum (FWHM) peak characteristic or by the area/height XRD-peak ratio (integral breadth. Relation between the mean sizes D calculated from 13~and from 13.7 18.6 7.4 10. GuErin and Alvarez. Therefore.5 9.5 12.1 10.52 i -r 120 lOO o so 60 40 20 0 $ 20 40 60 D ( f l ) (nm) 80 100 120 0 20 40 60 D ( f l ) (nm) 80 100 120 Figure 1. If strain and size components can be related to well-defined profile shape functions.9 13. Methods may be adopted also to deconvolute f(x) and consequently to determine the crystallite size. No.89 743 300 250 i200 -'%0 15o lOO 50 o o R2 = 0. h the wavelength. In effect. 1995).7 25. p. a proper value of constant K.3 2. With the use of integral breadths and the K constant set to unity.6 10. more recently.e.9 32.
8) 38. All products were washed with 1 N KOH. All samples were step scanned (25-80 ~ 0.g.7 (16.9) 16. and 1~ scatter slit.4) 32.3) 27.9 (72.1 (9.5 (8.9) 38.9) 47.7 (13.4) 31.6 (18.2 (21. dialyzed.9) 26.744 Crosa.1) 26.8 (10.2) 28.4 (3.3 (7.4 (10.4) 33.2) 10.0 (17. 024.8) 40. Data analysis The instrumental profile. 1987).8 (2.2-mm receiving slit.5) 37.2) 11..7) 1 Six peaks for samples H2a and H2b. obtained as average of seven peaks 1. g(x).1 (2. 0.9) 30. Dc values (nm) of the hematite samples.2) 14. Samples Parameter H1 H2a H2b H3 H4 H5 H6 H8 H 11 FWHM [3 [3 c 13. eight hematite samples. and storing at 80~ for 70 d.9) 22.9 (18. PW1820 goniometer) equipped with 1~ diverging slit. adjusting again to pH 7. was obtained based on Stanjek (1991) from a reference sample of synthetic c o m m e r c i a l hematite (Merck.2) 25. 548003) previously heated to 1000~ for 48 h.4) 35.4 (7. no. 110.3 (2.9) 24. then with deionized water.2) 1Eight peaks for samples H2a and H2b. and 20 s counting time per increment) to include nine peaks: 012. each peak was fitted independently and the Marquardt algorithm was used to obtain the best value of goodnessof-fit (GOF%): GOF% = 100[Z (Io .2 (2.5 (7. 116.5) 18.6 (7.0) 35.2) 16. but aged 14 d. 214. resent a close approximation to the actual habit (e.179026 nm) radiation involved a system with an Fe filter at 40 kV and 40 mA.8) 18.0. Boero.1 (18.17988 nm) components. adjusting the pH to 7 --.8) 18.8) 17. were synthesized by various methods (Schwertmann and Cornell. which included the separation of CoKc~ (0.4 (5.8 (11.002 and 0.5) 15. An X R D scan of this size fraction was performed at 0.0) 39.7 (15.1 (5. respectively. Table 3.3 (5.01 ~ interval and 80 s counting time.9 (11. The C o K a (0.3 (27.9) 17.2 (9. The digitized X RD profiles were fitted using a split pseudo-Voigt function (Howard and Preston.4) 34. 1991). Sample H8 was obtained by adding 40 mL 0.2) 20. The standard deviations are reported in parentheses.3) 39. The 2 20-~m size fraction was obtained by sieving and by gravity sedimentation in water.2) 13. Sample H11 was obtained similarly to sample H1.8 (1.001 M HCI. .lc)2/(/o)2]1/2 (2) where Io is the observed intensity and I c is the calculated intensity.1 (16.3) 16.8) 36.4 (7.6) 46.02 ~ intervals. XRD analysis XR D was performed with a Philips diffractometer (PW1729 generator.2.5 (5.8 (9.3) 18.2 (2. Wherever possible.9 m m in thickness to obtain the highest diffraction intensity (Klug and Alexander.2 (1. 018.2) 87. 90~ and oxalic acid (36 h. The standard deviations are reported in parentheses.7 (11. Samples Parameter H1 H2a H2b H3 H4 H5 H6 H8 H 11 FWHM [3 [3~ 16. Da values (nm) of the hematite samples.9 (8.8) 18.1 M AI(NO3)3 to 160 mL 0.8 (48. Samples H I and H2 were obtained by hydrolysis of Fe(NO3)3 and Fe(C104) 3 solutions.8) 15.2) 19.1 M Fe(NO3)3. Torrent et al.8 (11.8) 13. (1985). 113.7) 40. 1989). respectively.3) 31.6) 28.2) 15.2) 16.3 (6. M ATER I A L S A N D M E T H O D S Synthesis o f hematite To obtain reliable X R D and BET measurements. and freeze-dried.1 (13.6) 29. and 300.1 (7.8 (18.l (17. Self-supporting powder mounts were prepared by gently pressing 200 mg of sample into an A1 holder.3 (3.3 (16. 3924.7 (4. The powder mounts were smoothed at >0. 104.0) 21. respectively.2) 21.0 (15. with a modified Q B A S I C program of Enzo et al.4 (6.8 (2. 1974). then washing. 70~ solutions.6 (5. and Franchini-Angela Clays and Clay Minerals Table 2.. lot no. with comparable crystallinity to those of soil.1) 21. obtained as average of nine peaks ~. and aged for 7 d at 98~ H3 and H4 were synthesized from FeC13 solutions in 0.6 (1.9 (5. and aged for 10 d at 98~ Samples H5 and H8 were prepared by transformation of ferrihydrite in the presence of solutions of N a n C O 3 (2 d.
on the D c value and vice versa.6 77.6 38. 1982).5 78. [3. the values of D a and D c were computed from D and the related cosine function. the 018 peak often showed an overlap by a spurious peak. (1988).5 25. in terms of D. the FWHM/[3 ratio (the so-called Voigt parameter) may range between 0. and [3c using Equation (1) with K = 0. the average parameters based on all reflections. (1987): Specific surface area (m2g 1) = 7 6 0 / D a + 3 8 0 / D c RESULTS AND DISCUSSION Experimental profiles From all reflections in all the samples. Details of this procedure are in deKeijser et al. see Benedetti et al.3 nm.4138. was obtained from the FWHM. The Cauchy and the Gaussian component of the broadening were then separately deconvoluted. suitable reflections for determining D a are 300 and 110. Because the standard deviation of D a in some of the samples is greater than this range and.7 47. The reference sample showed a GOF% slightly higher than that of each hematite. Therefore.2 23.2 42.4 28. the [3J[3 ratio may range from 0 to 1 and the FWHM/[3c ratio may vary consequently. Table 4 shows for each sample the D a value (from [3) obtained from the above peaks. in a Voigt profile (deKeijser et al. 6. Moreover. Differences are evident for each peak and for the broadening parameter used. Therefore. In these hematite samples.0 56.0(1)% by volume of the total sample and H2b for the re- As an example. obtained from different peaks. Tables 2 and 3 give. H2a was estimated at 32.6 43.0 78. the values of D a and D c for sample HI.1 53. H2a and H2b.6 27. Using [3 as a broadening parameter. 2) the estimation of D a from an hkl plane not perpendicular to a is dependent. For all the samples. Scattering increases strongly above the size limit (Figures 1 and 2). a near linear regression exists between D obtained from FWHM vs. D a a n d D c estimation (3) The GOF% of all the profiles was comparable.9394 (pure Gaussian).7 25.97) and D obtained from [3~ vs. Influence o f b r o a d e n i n g p a r a m e t e r s o n D The specific surface area was measured by N 2 adsorption on samples that were outgassed (at 60~ using a FISON Sorptomatic 9000 apparatus. respectively. particularly for the 012 reflection.4 to 31. the Voigt function was obtained from the pseudo-Voigt parameters for h(x) and g(x) of both K a I and K~xz.6 For all the samples and for each peak. Samples 745 Peak H1 H2a H2b H3 H4 H5 H6 H8 H 11 110 300 Mean 22.58-1. the best D a or D c estimation may be obtained from peaks with hkO-hO0 and 00l Miller indices. considering also the limitations of the XRD method (to 100-200 nm) the error in the use of [3 as a broadening parameter may be high. at least partially. 47.9 when the value for F W H M was calculated. The crystallite shape (and also structural strain) .09). where c~ is the angle between the hkl plane and the crystallographic direction under consideration (Schwertmann. and K = 1 when the value of [3 or [3c was used. of different mean size.0 50. the ratio of D values obtained from FWHM and [3 may range from 0. a very asymmetric peak.1 24. The estimation of the surface area from XRD data. perpendicular to hkl planes.90). and [3c of the Voigt f(x) was obtained. based on the K-constant values adopted.6 45. these differences are caused by the nature of f(x) (Gauss/Cauchy ratio) and by the K values [Equation (1)]. Values were obtained with the BET isotherm and the software from the manufacturer. These values were judged satisfactory for all peaks in the samples (GOF%: 0. Figures 1 and 2 show the effect of FHHM. was obtained from the formula of Torrent et al. or [3c on the D values.3 66.6 48. From preliminary TEM photographs. Furthermore. From peakintegrated intensities. Specific s u r f a c e a r e a maining. 1999 XRD profile analysis and mean size of synthetic hematites Table 4. [3. In general.8 24. are reported in Table 1. if the size is < 6 0 nm.6366 (pure Cauchy) and 0. there is good agreement between XRD and TEM-size determinations. the average value of D a ranges (excluding sample H2a) from 13. The thickness of the crystal (domain) along any crystallographic axis can be derived from D by multiplying by cosc~. In effect. (1982) and Crosa (1996). For a similar procedure.4 26.0 22. No.7 71.9581 to 1.7 28. Sample H2 showed negative values of the Gaussian component: each peak was therefore assumed to be the sum of two Gaussian components as derived from two populations of crystals. 1987). for comparison. and the FWHM. The value of D. by using a cylindrical shape approximation. Differences among reflections may be related to the following: 1) the D value is related to an apparent size rather than an actual size. Da (nm) evaluated from [~ of selected peaks (100 and 300). 13. D obtained from [3 (R e = 0.Vol. Consequently.0 62.4 21. Also. D from [3 (R 2 = 0.
or hkl peak. which can be obtained from Da. In general..g.0 47. Dc. habit and morphology of hematite in a soil are not always obtainable. the use of apparent size does not appear to prevent a reliable surface area estimation. and their effect on the D c estimation. the strain effect on soil iron oxides is unknown. underestimation of D c may be avoided. Because peaks with 001 indices are unavailable.2 16. hOl. the application of F W H M or ~ may produce an incorrect evaluation of crystal size. Despite these potential problems. may explain residual differences between values obtained from the 110 and 300 reflections. and morphology of the (uniform) crystallites are known.5 12. although these two broadening parameters are the appropriate parameters to use as demonstrated by others (e.3 18.3 22.3 20. 0 10 20 30 40 Da 50 60 (nm) 70 80 90 100 Figure 3.0 19. Maximum measurable values for Dc estimation with the Okl. The D c values obtained from the 116 and 104 peaks are.. Consequently.0 32.4 17.4 34. hOl and hkl peaks as a function of Da. especially for soil hematite. but this is possible when both habit. Boero. The best agreement between the specific surface area values obtained by N2BET and XR D is observed when the 13c parameter is used.5 30. Figure 3 shows the maximum value for Dc. The 018 peak. but only if D c figures so obtained are lower than their corresponding m ax i m u m value.7 45. the 116 and 104 peaks are used to estimate D c (Table 5). for all hematite samples. Cauchy-broadening parameter) to obtain the size effect from a peak profile. the estimates using Okl and D a values. in the present work. 1994).0 15.746 Crosa.3 32. whereas ~ requires a higher quality peak profile and a fitting procedure. and Franchini-Angela Clays and Clay Minerals 1 0 0 ~ 9 0 80 60 / / ~ 1 0 4 012 / 024 so high that any comparison is not significant (data not shown). when the specific surface area estimation is based on all X R D peaks. As noted by Borggaard (1990). In each sample. 3) The combination of proper peak selection with a "single-peak m e t h o d " (e. Sarnples Peak H1 H2a H2b H3 H4 H5 H6 H8 H 11 116 104 Mean 12. appears to be the best procedure to determine surface area values which closely fit those of the N2-BET method.4 32.7 34.. may be calculated. which is the most favorable theoretically. Torrent et al. the reliability of D a and D c values depends on the use of an appropriate peak.0 49.4 33. but only in the absence of strain.g. In addition. the use of the mean value for D a may be considered reliable.3 32. differences are evident with respect to various broadening expressions. 4) The use of F W H M and 13 can be applied rigorously. may be estimated from an appropriate Okl. the adoption of a single-peak method is to be recommended. Obviously. although it requires accurate data collection and sophisticated computation procedures. the differences are Table 5. always lower than the maximum values obtained from Figure 3 and. as a function of Da. Nevertheless. However.7 12. the differences in these D c figures are probably due to shape and irregularities of the crystals. in general only well-resolved peaks from planes perpendicular to crystallographic axes allow the determination of a reliable D a and D c value. hence. both of which can be affected by strain. 2) As expected. the F W H M parameter is commonly used probably because it is measurable even for low-quality X R D profiles.0 29.1 18. Therefore. The D a and D c values so obtained are only apparent sizes. As expected. Specific surface area estimation Table 6 reports the specific surface areas calculated using XRD data and those by the N2-BET method. In fact.7 15. Dc (nm) evaluated from [3 of selected peaks (104 and 116). However. CONCLUSIONS We conclude that: 1) the evaluation of apparent crystallite size D is clearly affected by the choice of the parameter used in the X R D analysis. it is difficult to convert these values to actual size.1 .8 19. lacking any 001 peak.2 15. The D c estimation is more complex. uncertainties about g(x) suggest the exclusion of the 012 reflection and the higher order 024 peak. Unfortunately.6 14. does not appear as a well resolved reflection.
4 21.5 37. 41. 45.D.. and Battagliarin. 127 pp.J. Schnitzer.D.J. Series 217. J.. In Interactions o f Soils Minerals with Natural Organics and Microbes. Italia. (1987) Some properties of soil and synthetic iron oxides.1 50. 137 pp.H. II. London. Hartmann. 22. Volume 20. Mittemeijer.5 55. and Barron.B. 203-250. 15. E. Delhez. U. and the anonymous referees and S. 100 pp. (1986) Mutual interactions between organics and iron oxides. Cornell.C. In Modern Powder Diffraction.. Buch am Erlbach.1 28. Schwertmann. Universit~ degli Studi di Torino. Bish and J. (1978) Scherrer after sixty years: A survey and some new results in the determination of crystallite size. O. D. deKeijser. Zeitschriftfiir Kristattographie. REFERENCES Benedetti.C. U. (1996) Ottimizzazione dell'analisi dei profili XRD per la misura delle dimensioni medie dei cristalli di ematite e goethite.5 43. (1988) A profile fitting procedure for analysis of broadened X-ray diffraction peaks. G.0 41. Verlagsgesellschaft.C. Madison. 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