Clays and Clay Minerals, Vol.44, No. 5, 658-664, 1996.

T H E N A T U R A L O C C U R R E N C E OF E T A - A L U M I N A ('q-AlzO 3) IN B A U X I T E
DAVID B. TILLEY AND RICHARD A. EGGLETON Centre for Australian Regolith Studies, Australian National University, Canberra, ACT, 0200, Australia Abstract--Approximately 20 wt.% of the bauxite from Andoom in northern Queensland, Australia is composed of material that cannot be accounted for by identifiable well-crystallized phases. This poorlydiffracting material (PDM), found within the core of bauxitic pisoliths, has similar characteristics to that of eta-alumina (-q-A1203); a cubic form of alumina. A differential XRD pattern of the PDM displayed a series of broad diffraction maxima attributed to eta-alumina with a mean crystal size of 9 nm. Unit cell refinement, on the basis of a cubic cell, gave a lattice parameter of a = 7.98 A for Andoom eta-alumina. TEM and selected-area electron diffraction revealed the PDM to be composed of minute (10 nm wide), randomly oriented crystals of eta-alumina in close association with Al-hematite. Chemical analysis using a nanoprobe showed Andoom eta-alumina to be almost pure alumina with < 2 M% Fe, < 1 M% Si and < 1 M% Ti. The closely associated Al-hematite may contain as much as 22 M% A1, however a value closer to the theoretical limit of 17 M% is more likely. A broad absorption band at 3450 cm -1 and 1630 cm 1 in the infra-red spectrum of the PDM indicates the presence of a substantial quantity of I-I/O, strongly adsorbed onto the surface of the crystals. This is presumably due to "q-AlzO3's large surface area of approximately 2200 m2/g. The natural occurrence of "q-A1203 in bauxite may be the result of low H20 activities within the micro-environment of pores at the time of crystallization. The epigenetic replacement of kaolinite with "q-A1203 and Al-hematite is put forward as an explanation for the formation of bauxitic pisoliths at Andoom. Key Words----Akdalaite, Bauxite, Chi-alumina, Eta-alumina, Gamma-alumina, Pisoliths, Poorly-diffracting material, Tohdite. Selected area electron diffraction o f synthetic "q-A1203 b y L i p p e n s a n d de B o e r (1964) r e p o r t e d it to b e tetragonally d e f o r m e d w i t h c/a r a n g i n g b e t w e e n 0.985 a n d 0.993. Z h o u a n d S n y d e r (1991) d e m o n s t r a t e d that the crystal structure o f ~q-AlzO3 is essentially cubic, h o w e v e r s o m e w h a t spinel d e f o r m e d w i t h a = 7.914 A. B r o w n et al. (1953) s h o w e d that "q-A1203 is a transition p h a s e p r o d u c e d b y the t h e r m a l d e c o m p o s i t i o n o f poorly c r y s t a l l i n e b o e h m i t e ( A 1 0 ( O H ) ) or wellcrystallized b a y e r i t e ([3-Al(OH)3). F u r t h e r h e a t i n g o f "q-A1203 leads to the f o r m a t i o n o f t h e t a - a l u m i n a (0A1203) f o l l o w e d b y c o r u n d u m (ct-A1203). EXPERIMENTAL METHODS T h e core o f a b a u x i t i c pisolith f r o m A n d o o m (1 to 1.5 m depth) w a s s a m p l e d u s i n g a dental drill. T h e extracted material w a s finely g r o u n d u s i n g a m o r t a r and pestle a n d t h e n applied to a l o w - b a c k g r o u n d holder. A n X R D p a t t e r n o f the s a m p l e was o b t a i n e d b y s c a n n i n g o v e r a p e r i o d o f 12 h. A differential X R D pattern was p r o d u c e d b y s u b t r a c t i n g the calculated pattern for e a c h o f the w e l l - c r y s t a l l i z e d c o m p o n e n t s , in p r o p o r t i o n to t h e i r w e i g h t fraction. T h e resulting differential X R D p a t t e r n was c o m p a r e d w i t h m i n e r a l s a n d i n o r g a n i c c o m p o u n d s in the P o w d e r D i f f r a c t i o n File p u b l i s h e d b y the J o i n t C o m m i t t e e o n P o w d e r Diffraction Standards. W h e n it was f o u n d that the d-spacing values o f the b r o a d e s t p e a k s in the X R D pattern m a t c h e d well w i t h t h o s e o f eta-alumina, q u a n t i t a t i v e analysis o f the X R D pattern was u n d e r t a k e n u s i n g S I R O Q U A N T , w h i c h is a R i e t v e l d - t y p e quantitative-

INTRODUCTION Two c r y s t a l l i n e a l u m i n a p h a s e s h a v e r e c e n t l y b e e n r e p o r t e d in A u s t r a l i a n bauxites. Tilley a n d E g g l e t o n (1994) r e p o r t e d that b a u x i t i c pisoliths f r o m Weipa, N o r t h Q u e e n s l a n d c o n t a i n e d material w h i c h yielded v e r y b r o a d diffraction m a x i m a that c o u l d n o t b e acc o u n t e d for b y identifiable w e l l - c r y s t a l l i z e d minerals. Such material, termed poorly-diffracting material ( P D M ) , was s h o w n to b e c o m p o s e d p r e d o m i n a n t l y o f tohdite (5A1203.H20). A r e c e n t letter f r o m the International Mineralogical Association Commission on N e w M i n e r a l s a n d M i n e r a l N a m e s ( C N M M N ) disc o u r a g e d the use o f the n a m e " t o h d i t e " in any prop o s e d p u b l i c a t i o n s due to it b e i n g an i n v a l i d m i n e r a l n a m e . T h e n a m e akdalaite (4AI2Oa.H20) was a p p r o v e d b y the C N M M N for the m i n e r a l c o r r e s p o n d i n g to tohdite, due to their similarity, a n d as a c o n s e q u e n c e , W e i p a tohdite will n o w b e r e f e r r e d to as akdalaite. S i n g h a n d Gilkes (1995) r e p o r t e d the o c c u r r e n c e o f p o o r l y c r y s t a l l i n e chi a l u m i n a ( in the b a u x ites o f D a r l i n g R a n g e , W e s t e r n Australia. T h e authors d e m o n s t r a t e d that x-A1203 f o r m e d b y the d e h y d r a t i o n o f a n a l u m i n o u s gel-like material. E x a m i n a t i o n o f b a u x i t i c pisoliths f r o m A n d o o m , w h i c h is 15 k m n o r t h o f Weipa, h a s r e v e a l e d the p r e s e n c e o f a n o t h e r poorlydiffracting phase, distinct f r o m akdalaite a n d x-A1203. Differential X R D a n d t r a n s m i s s i o n e l e c t r o n m i c r o s c o p y ( T E M ) o f the P D M s h o w e d that the p h a s e has similar characteristics to that o f "q-Al203. S t u m p f et al. (1950) d e s c r i b e d e t a - a l u m i n a as h a v i n g a cubic, spin e l - t y p e structure w i t h a lattice p a r a m e t e r o f 7.94 A. Copyright 9 1996, The Clay Minerals Society 658

Vol. 44, No. 5, 1996

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2000

,,,,,,,,,i,,,,,,,,,i,,,,,,,,,i,,,,,,,,,i,,,,,,,,,I,,,,,,,,,I,,,,,,,,,
h h

1500-

t'-

= 1000o 0 k 500 -

g
h g a r h h h h h h

lilll 'lllrLllJi]llll

J'llllllllilllliLIlillllfil'~llliltlJlLil'iJIIJll

10

20

30

40 ~

50 CuKo

60

70

80

Figure 1. An XRD of PDM-rich bauxite extracted from the core of a pisolith from Andoom in northern Queensland. Key: g = gibbsite, h = hematite, k = kaolinite, a = anatase and r = rntile.

X R D phase analysis program (Taylor and Clapp 1992). S I R O Q U A N T uses the cubic (Fd3m) structure determined by Shirasuka et al. (1976) when calculating an X R D pattern for eta-alumina. Refinement o f the unit cell parameter from a starting value of a = 7.906 was undertaken during the analysis. The same p o w d e r that was used for X R D , was ultrasonically dispersed in ethanol and then pipetted onto a holey carbon-coated grid. T E M was p e r f o r m e d on the sample using a J E O L 2 0 0 C X transmission electron microscope, operating at 200 kV. Selected-area electron diffraction ( S A E D ) patterns of bauxite particles were obtained at a camera length of 74 cm. An S A E D pattern displaying a series of diffraction rings was indexed and c o m p a r e d to X R D and calculated d-spacing values. Analytical T E M ( A E M ) was undertaken using a nano-probe with a b e a m diameter o f 10 n m in conj u n c t i o n with e n e r g y d i s p e r s i v e X - r a y analysis ( E D X A ) on a Philips 4 3 0 E M transmission electronmicroscope, operating at 300kV.

An infra-red (IR) spectrum of the P D M was obtained using a Perkin E l m e r 1800 F T I R spectrophotometer. RESULTS The X R D pattern (Figure 1) displays relatively sharp diffraction m a x i m a associated with well-crystallized hematite, gibbsite, anatase, rutile, kaolinite and quartz while broad diffraction m a x i m a are attributed to PDM. The procedure for obtaining a differential X R D pattern was reasonably effective in r e m o v i n g the well defined peaks associated with gibbsite, hematite and other well-crystallized phases, e v e n though s o m e residual peaks are still evident. The differential X R D pattern displays a series of broad diffraction maxima, similar in intensity and breadth to Weipa akdalaite, but the diffraction lines do not coincide with those of Weipa akdalaite (Figure 2). The broad peaks have m a x i m a that match well with those of -q-A1203 (Stumpf et al. 1950) (Table 1). The 2.0 .~ peak has a width (at half m a x i m u m ) o f 1.31 ~ which gives a m e a n crystallite

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1400t'''' I'''' I'''' < I'''' 1200 rl -alumina ,~ <

o,i o

i''''

I''''

I''''

~
E

1000
r
t-" 0

,<
oo

o<
h ~

o~
~
~

800

o<
-

~ c.o '~

cJ

c,i
h

tO

400-1
200 0
I , , ,,

600 ~

"..i. ill

~_
~,

akdalaite
I , I ,, I, ,, , 1, ,, , I , ,, , I' , , J I ' ~ '' I

10

20

30

40 50 ~ CuKo~

60

70

80

Figure 2. A differential XRD pattern of Andoom -q-A1203 compared with Weipa akdalaite. Under- and over-calculated hematite peaks (h) are labeled.

size o f 9 n m w h e n u s i n g the S c h e m e r equation. Q u a n titative X R D u s i n g S 1 R O Q U A N T indicates that the core o f the a n a l y z e d pisolith c o n t a i n s greater t h a n 70 wt.% xi-A1203 (Table 2 a n d F i g u r e 3). U n i t cell refine-

Table 1. Comparison between the d-spacing values of the PDM determined by electron diffraction, differential XRD and those calculated by Stumpf et al. (1950).
PDM electron diffraction I/I~t dA PDM differential XRD UII~ d A .q-alumina (Stumpf et al. 1950) Ijl I d/~ hkl

merit o f A n d o o m -q-A1203, o n the basis o f a c u b i c cell, gives a lattice p a r a m e t e r o f a = 7.98 ,~. E x t r e m e l y fine crystals o f a p p r o x i m a t e l y 10 n m in w i d t h are e v i d e n t in the T E M i m a g e (Figure 4). T h o s e crystals that h a v e lattice fringes o f 2.3 a n d 2.4 ,~ are associated with "q-A1203. T h e crystallite size o f - q A1203 d e t e r m i n e d f r o m the T E M i m a g e is close to that calculated u s i n g the S c h e r r e r e q u a t i o n ( ~ 9 n m ) a n d is slightly larger t h a n that o f W e i p a akdalaite ( ~ 6 nm). T h e d - s p a c i n g values o b t a i n e d f r o m the S A E D pattern (Figure 5) c o i n c i d e well w i t h the X R D pattern o f the p o o r l y - d i f f r a c t i n g material, i n d i c a t i n g that the finely Table 2. quantitative XRD analysis of the PDM-rich material using SIROQUANT.
Phase Wt% Error %

20 80 20 90 20 100 10 20 10 10 10

2.79 2.40 2.28 1.96 1.52 1.39 1.19 1.13 0.98 0.88 0.80

10 30 80 20 90 20 100

4.62 2.82 2.45 2.29 2.01 1.55 1.41

40 20 60 30 80 20 100 10 20 10

4.6 2.8 2.40 2.27 1.97 1.52 1.40 1.21 1.14 1.03

111 220 311 222 400 333 440 533 444 553

t Intensities by visual estimation.

eta-alumina Al-hematite gibbsite kaolinite rutile quartz anatase

71.6 16.7 8.6 0.7 1.6 0.3 0.5

0.26 0.18 0.18 0.11 0.07 0.04 0.05

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Eta-alumina in bauxite

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4000
30002000cO 0

1000-

calculated

difference
I I I I I I

10
Figure 3.

20

30

40 50 o20 CuKo

60

70

80

Rietveld-type quantitative-XRD analysis of the bauxite sample containing approximately 70 wt.% -q-A1203.

crystalline material observed using TEM is the same material identified in the X R D pattern. A E M of randomly selected crystals in the PDM-rich sample revealed the presence of 2 mineral phases: 1) an aluminium-bearing ferruginous phase; and 2) an almost pure aluminous phase (Table 3). The most ferruginous particle analyzed contained 22 M% AI while the most aluminous one had < 2 M% Fe. A transmittance infra-red spectrum of the material containing approximately 70 wt.% PDM, shows a broad absorption band at 3450 cm -~ due to O-H stretching and at 1630 cm -I associated with O-H bending vibrations (Figure 6). DISCUSSION The XR D patterns of synthetic eta- and gamma-alumina are known to very similar (Spider and Pollack 1981; Zhou and Snyder 1991). However, there are small but measurable differences that can be used to distinguish between the 2 phases. The most useful discriminator is at approximately 1.98 _~, where -q-AlzO3 has 1 strong line while ~-A120 ~ has a doublet consisting of a strong line at 1.98 .~ and a strong shoulder at 1.95 A. We conclude that PDM from Andoom is com-

posed of -q-A1203 rather than ~/-A1203 because although slightly asymmetric, the 1.98 .~ peak appears single. Though as yet undiscovered, the existence of ~/-A1203 in bauxites is highly probable. The aluminium-bearing ferruginous phase analyzed by A E M is ascribed to Al-hematite while the almost pure aluminous phase is attributed to "q-A1203. A EM indicates the Al-hematite may contain up to 22 M% A1. Unit cell refinement of the hematite gave cell parameters of a, b = 5.0118 A and c = 13.7120 .~, indicating an A1 substitution of between 20 and 23 M% (Schwertmann 1988a; Stanjek 1991), assuming a formation temperature of between 25 and 40 ~ However, Schwertmann (1988b) reported that no soil hematites have been found that contain greater than 18 M% AI. In fact, Al-substitution in hematite may be limited to 76 of the possible octahedral positions, that is, 17 M% A1 (Schwertmann 1988a). Although every effort was made to ensure that the analyses were obtained from individual crystals, it is possible that characteristic AI X-rays from an adjacent alumina grain may have led to an apparently high A1 content for the hematite. Due to this inconclusiveness, a value of 18 M% A1 was chosen for hematite's site occupancy. A

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Figure 4. A TEM of one particular area in the poorly diffracting material. The crystal size of the PDM is approximately 10 nm. Lattice fringes of 2.3 and 2.4 ~ indicate -q-AI203.

close match between the observed and calculated X R D patterns was obtained using this value. Quantification of the bauxite's mineralogy was also performed using the same site occupancy.

Figure 5.

An SAED pattern of Andoom "q-A1203.

The H20 contained within the crystal lattices of gibbsite is 34.6 wt.%, boehmite is 15.0 wt.%, and akdalaite is 4.4 wt.%. The theoretical crystalline structure of ~-A1203 contains no chemically-bonded water. B o t h akdalaite and a3-A1203 contain a p p r e c i a b l e amounts of strongly adsorbed H20 as evidenced by their transmittance IR spectra, but the actual amount is not determinable from the spectra alone. The reason for the large amount o f adsorbed water is presumed to be mainly to their large surface areas. For example, the surface area o f 1 g of l]-A1203 (p --" 3.63 g / c m 3) assuming it consists of an aggregate of cubic crystals, is approximately 2200 m2/g. The d i s c o v e r y o f akdalaite and -q-A1203 in the bauxites of Weipa and A n d o o m has greatly e x p a n d e d our k n o w l e d g e and understanding o f bauxite mineralogy and the role n 2 0 activity m a y play in the e v o lution of bauxitic pisoliths. The majority of concentrically-banded bauxitic pisoliths and those with P D M - r i c h cores e v o l v e in a similar m a n n e r to that p r o p o s e d by Tardy and N a h o n (1985), except that ak-

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Eta-alumina in bauxite

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Table 3. Nano-probe analyses of individual crystals in the PDM-rich bauxite sample. The analytical total has been recalculated to 100%.
eta-alumina 1 2 3 4 5 eta-alumina + Al-hematite 6 7 8 9 Al-hematite 10 11

wt% A1203 SiO2 TiO 2 Fe203 cation % A1 Si Ti Fe

96.4 0.6 0.7 2.3 97.6 0.5 0.4 1.5

95.7 0.8 1.1 2.4 97.0 0.7 0.7 1.5

95.5 1.4 0.9 2.2 96.8 1.2 0.6 1.4

95.1 0.8 1.0 3.1 96.6 0.7 0.6 2.0

91.1 0.0 0.1 8.8 94.1 0.0 0.1 5.8

88.5 0.9 0.0 10.6 92.1 0.8 0.0 7.1

36.3 0.0 1.3 62.5 47.2 0.0 1.0 51.8

29.8 0.6 2.6 67.0 39.9 0.7 2.2 57.3

23.0 0.3 2.2 74.4 31.9 0.4 2.0 65.8

18.6 0.0 2.4 78.9 26.4 0.0 2.2 71.4

15.4 0.0 2.4 82.3 22.2 0.0 2.2 75.7

d a l a i t e or "q-A1203 m a y e p i g e n e t i c a l l y r e p l a c e k a o l i n ite d u r i n g n o d u l e d e v e l o p m e n t as w e l l as A l - h e m a tite. T r o l a n d a n d Tardy ( 1 9 8 7 ) s h o w e d t h a t at 25 ~ the c h e m i c a l a c t i v i t y o f w a t e r w a s a m a j o r f a c t o r in d e t e r m i n i n g t h e d e g r e e o f h y d r a t i o n in b a u x i t e m i n erals. I f the k a o l i n i t e g r a i n s w i t h i n t h e d e v e l o p i n g n o d u l e are v e r y small, t h e n the i n t e r c r y s t a l l i n e v o i d s are c o r r e s p o n d i n g l y so. A s the w e a t h e r i n g profile dries out, w a t e r is r e t a i n e d in p r o g r e s s i v e l y s m a l l e r

p o r e s w i t h c o r r e s p o n d i n g l y l o w e r H 2 0 activities (Tardy a n d N a h o n 1985). T h e a c t i v i t y o f H20 w i t h i n p o r e s m a y b e so l o w t h a t a n h y d r o u s p h a s e s s u c h as A l - h e m a t i t e a n d -q-Al203 m a y f o r m . W h e r e p o r e sizes are a little l a r g e r a n d a slightly h i g h e r H 2 0 activity prevails, b o e h m i t e b e c o m e s the d o m i n a n t A i - r i c h m i n e r a l . In the l a r g e s t v o i d s g i b b s i t e n o r m a l l y c r y s tallizes, as the H20 a c t i v i t y is u s u a l l y t o o h i g h for t h e less h y d r a t e d p h a s e s to f o r m .

100

80--1
tD

tO

t.-

60-

E t./}
tI.-

40-

I--

203 4 5 0 c m -1

0 4000

i 3500

~ 3000

i 2500

I 2000

I 1750

I 1500

I 1250

I 1000

I 750

I 400

Wavenumber (cm-1)
Figure 6. A transmittance infra-red spectrum of bauxitic material containing approximately 70 wt.%

xI-A1203.

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Tilley and Eggleton

Clays and Clay Minerals

ACKNOWLEDGMENTS This work was supported by a research grant from COMALCO Aluminium Limited, for which we are most appreciative. SEM was performed using the facilities of the EM unit at the Research School of Biological Sciences, ANU. D. Bogshnyi of the Research School of Chemistry, ANU acquired the infrared spectrum. Analytical TEM using the nano-probe was undertaken at the Research School of Earth Sciences, ANU. REFERENCES Brown JE Clark D, Elliott WW. 1953. The thermal decomposition of the alumina trihydrate, gibbsite. J Chem Soc 13:84-88. Lippens BC, de Boer JH. 1964. Study of phase transformations during calcination of aluminium hydroxides by selected-area electron diffraction. Acta Crystall 17:13121321. Schwertmann U. 1988a. Some properties of soil and synthetic iron oxides. In: Stucki JW, Goodman BA, Schwertmann U, editors. Iron in soils and clay minerals. Dordrecht, Holland: D. Reidel Publishing Company. p 203-250. Schwertmann U. 1988b. Occurrence and formation of iron oxides in various pedoenvironments. In: Stucki JW, Goodman BA, Schwertmann U, editors. Iron in soils and clay minerals. Dordrecht, Holland: D. Reidel Publishing Company. p 267-308. Shirasuka K, Yanagida H, Yamaguchi G. 1976. The preparation of "q-alumina and its structure. Yogyo Kyokai Shi 84:610-613.

Singh B, Gilkes RJ. 1995. The natural occurrence of x-alumina in lateritic pisolites. Clay Miner 30:39-44. Spitler CA, Pollack SS. 1981. On the X-ray diffraction patterns of "q- and ~/-alumina. J Catal 69:241. Stanjek H. 1991. Aluminium- und Hydroxylsubstitution in synthetischen und natiirlichen H~matiten. Buch am Erlbach, Germany: Verlag Marie L. Leidorf. 194 p. Stumpf HC, Russell AS, Newsome JW, and Tucker CM. 1950. Thermal transformations of aluminas and alumina hydrates. Ind Eng Chem 42:1398-1403. Tardy Y, Nahon D. 1985. Geochemistry of laterites, stability of Al-goethite, Al-hematite, and Fe3 in bauxites and ferricretes: an approach to the mechanism of concretion formation. Am J Sci 285:865-903. Taylor JC, Clapp RA. 1992. New features and advanced applications of SIROQUANT: A personal computer XRD full profile quantitative analysis software package. Adv X-ray Anal 35:49-55. Tilley DB, Eggleton RA. 1994. Tohdite (5A1203.H20) in bauxites from northern Australia. Clays Clay Miner 42: 485-488. Troland E Tardy Y. 1987. The stabilities of gibbsite, boehmite, amorphous goethites and aluminous hematites in bauxites, ferricretes and laterites as a function of water activity, temperature and particle size. Geochim Cosmochim Acta 51:945-957. Zhou R, Snyder RL. 1991. Structures and transformation mechanisms of the "q, ~/ and 0 transition aluminas. Acta Crystall B47:617-630.

(Received 29 June 1995; accepted 31 December 1995; Ms. 2665)