05/01/2017 09:54 SYRACUSE UNIVERSITY ANNEX PRODUCTION SYSTEM PG = 2 RPT# 00098079 ddeangue cpyrept. EDD RETRIEVAL RECEIPT Order: 012968 Document Nbr: 976659 For: EDD Copied: 05/01/2017 Shipped: 05/01/2017 Deliver To: Internal ILLIAD user Item BarCode: 32911043047414 Item Title: The Mineralogical magazine and journal of the Mineralogical Item Author Item Call Number Item Vol/Part QE351 M3 Article Title: The structure of kaolinite Article Author: Brindley, G. W.,and Robinson, K. Art Vol/Part: 27 Article Issue Beg Page: 242 End Page: 253 Total Pages: 12 Other Info: 976659 Notes: 3|Exempt TOTAL COUNTa : e The structure of kaolinite. th By G. W, Barnuey, MSe., Ph.D., and Kerr Ropsox, BSc. a Physics Laboratories, ‘The University of Leeds. : {Communicated by FA. Bannister; read January 24, 196) ‘i Introduction. i POSSIBLE structure for kaolinite was first put forward by Pauling (19%) * ‘in a paper dealing generally with the structures of layer-type mine, & chlorites, micas, &e, He suggested that the structure consisted of a sheet of Si-O * tetrahedra arranged in a hexagonal network with a superposed sheet of AI-(0,0H) ! ‘octahedra, the two together forming a layer of composition Al,Si,0,(0H), (g.2)- ‘Ross and Kerr (1931), froni a detailed microscopic study of the Kolin minerals, concluded that the symmetry’ of kaolinite is ‘probably monoclinic’. ‘The frst ttenpt at a detailed structure analysis was made by Gruner (19924) from Xay powder photographs. The reflections, some 40 altogether, were indexed on the basis of a monoclinic cell with a B14, 8 8:90, © 1451A., 8 100° 12’. Grunee’s work confirmed Pauling’s suggestion regarding the structure ofthe layer. ‘The vales of the parameters and b are determined by the dimensions of the Si-O network and the ratio of these values, V3, follows from the hexagonal arrangement of the Si-O tetrahedra. The height of the eel, ¢ sin f, is 1-208. and this requires two ALSi,0,(OH), layers per cell. The space-group finally chosen by Gruner wus Cf = Ce; the two layers of atoms are related by the glide planes of symmetry | parallel to (010). Hendricks (1986) obtained additional confirmatory data for Gruner’s structure by both X-ray and electron diffraction methods: be agreed with Gruner’s values fora, b, and e, but gave f 101° 30. Lists of kaolinite reee- tions have also been published by Nagelschmidt (1954) and by Favejee (1959), Dut no further work on the structure of the mineral has been attempted. ‘We have recently hed occasion to examine many kaolinite specimens and in « brief note (Brindley and Robinson, 1945) have reported that more reflections are obtained than Gruner recorded and that there are noteworthy differences bet his and our observations, In particular, we find it impossible to index the reflections with a monoctinic cell. To account for the’ observed reflections it 8 necessary to postulate a trilinic cell having lnlf the height of Gruner’s cel i containing only one layer of atoms. The reflected intensities are in general agreement with this structure, We have so far confined our attention to a laset of ideal type, ie. consisting of regular tetrahedra and octahedra. It is very {questionable whether the structure can be determined in any greater detail from powder photographs alone, since the majority of the higher-order lines are cou posed of several reflections. We believe, however, that the analysis has been carried suficiently far to show that the structure is essentially trictnic and that the unit. cell contains one layer of the type suggested by Pauling,‘THE STRUCTURE OF KAOLINITE 23 X-ray powder diagrams of kaolinite, Forder photographs have been taken with two types of camera; (1) A semi- seg caunern of diameter 20-05 em, has been used for spacings greater than 24. Tematrial to be examined forms a thin fat powder layer at the centre of the ner and is mounted in a dry state without adhesive. (2) A eylindrieal camera ithe Bradley type of diameter 12 em, has also been used; specimens of diameters saging O3-0-13 mtn, were mounted either as dry powders in thin cellophane ‘ts o by couting them on fine glss fibres. Cul radiation filtered by nickel favas employed ‘The more outstanding differences between Gruner’s observations end our own, «sa for spacings greater than 2A, These reflections are also the most useful for ‘atfying knolinte in a mixture of minerals. We have therefore examined ‘sty of kaolinite specimens from widely different localities with the 20 er. ameter camera. ‘The results for spacings greater than 2-LA. are set out in table I, sith gives also the source of the specimens used and, for materials obtained fom the British Museum, their register number. The final columa lists Gruner’ dita, The estimated intensities, which axe indicated by the numbers in small type, depend partly on the experimental arrangement, viz. the use of a fit | ower layers if these intensities are to be compared with, those for cylindrical {Fecimens (as in table TI) allowauce must be made for the different absorptions inthe two caves, Te should fucther be noted that the use of « flat layer tends to Vinod n preferential orientation which enhances the basal reflections at 7-13, Sat, and 237A. Kaolinite from the fllowing sources have also been examined, but the results ane logs satisfactory owing to impurities, but in no case do they conflict with the tata of table L (i) Halle, Province of Saxony (BM. 14402) with quartz impurity. | Gi Rainbow Chiff, St. Kitts, British West Indies (BM. 1924,12,454) with cristobalite and other impurities. | (ii) Shore Hil, Otford, Kent (B.M. 1921,119) with quarts and mica, (iv) Ayrshire, Scotland, with quartz and anatase. ‘The uni cll of bain ‘The fll st of rections now abtsned for kasinie is given in table Hl. These camot be indexed on the bass of the monoclinic call given by Gruner, for not | only are someof thespacingsdifferent but there realso atonal lines. Attempt to interpret the data in terms of a monodlnie cel of somewhat different dimen- sions were unsuccessful, The angle P and also the angle w were varied between 4 and 115°, ‘The parameters w and b of Gruner's structure arise from the dimensions of the hexagonal network of Si-O tetrahedra and closely similar values are found in many layer-type minerals, such as micas and chlorites, If therefore this type of structure exists in kaolinite—and its occurrence in the other kaolin tninerals, dickite and nacrite, strongly suggests that it is so—then the a and b erametors cannot differ geeatly from those given by Gruner. We have examined Yatiations of a from 5/08 to 5:24. and of b from 88 to 914. ‘The height of the cells obtained asa multiple of 7-134. from the basal reflections which are greatly eaanced by the use of orientated layers.aut nosey snqoon SE sez ore ez0g £ ecoe ore aoe Let mee ose airs cole or 10 cue sont mee nose sur Her one Hee sole ouREE eee eee eee eee eee ‘THR STRUCTURE OF KAOLINITE 45 Fring to find a suitable monoclinic eel, we examined the possibility that the sllmisht be triclinic. ‘This seed not unlikely because of the occurzence of ier of doublets, particularly at sinall angles; the closeness of the doublets ‘get tat one angle, either aor , mig be close to 90", The angle between be and farses was kept at 90°. A cell fo ft the observed reflections was eral fom with: i tH, 0899, € TTA 0 918°, 8 1OLS"AO5O, 7 90°. ‘Tie main difference betyoon this coll and Graner's, apart from its trielinie infu, isthe © parameter which is approximately half of Granor's value. The Townes of the agreement between the observed and the ealeulated planar foci shown in table IT; the observed values down to 2-14. are mean values ‘tie ton specimens of table T, and below 2-1. are mean values for specimens L fn 3 only The latter vere slectd for the higher-order measurements beease ‘ive the sharpest Hines and contained hitle oF no obsereuble inspite, tous 11, Compasison of otsereed and ealelated spacings and reflected intensities for Telit Observed Ut dogs B(@)1O*. intensity. | aut an or Tae ass vest Her tim 30 mn tio r = pase wt ib 7 ME sl » wm et ow oe ox ww 01 w ress ms os 1935 wm 2.553 me 02635 28) Sher se © 252 wm rd 208 Bo Tialasa 180 em 2art mt al Tet FN tos vw aasl vw 16 78h e1 rome - = Tse 03 ' a TiS 271718 wt fap 108 4 TOL yw very |S aan w |e \poond which the observed intensities ase enbanced, owing to preferential intensities estimated visually in decressing order of strength, 75,26 AML. dane FQN” 1086 rose 1682 1682 Fost 1679 1636 1076 1075 1608 1669 1660 1650 1654 184 1609 ross 1638 18st 1627 1627 eI Pou 60 160 501 1500 1583 ven Lge 1057 156 ry rey 1599 1558 1a 1a 1535 rs 1505 1500 1401 Las 18h 18s 1n0 166 ac 142 v2 * {000 relstions for which the observed intensities are enhanced, owing to piefeeatil orientation. Observed intensities estimated yn rrp pec Observed dng intensity i. a 2 a lies vases Ke ul 2 a a 7 o 7 a a yoo} 16 1581 wm : B 8 7 es i: Le 7 ie 3 Fe a 7 8) mse 88 saan) 43) awe nae Fe # Sms; mm, Wm, Wey wy 1455, Tat 1453 1452 bar rar 1439 1439 1435 137 Lats ri 101 100 a0 rai us lyn decreasing order of strength, 8 "8 W, BRINDLEY AND K. ROBINSON Ow Oserv tae, FINO — dam intensity. | ' 89 {3 48) : 27 78 ; TS} a0 1-449 xeon) | 18 8 I 41 ' 16 | 82 1420 wma) | ts as} 68 00 w 2 Fa os a ° 33 s ts ti “3 2208 ploy 08 "ar 8 ha an ‘pnt 30a|eno ae win ts atc ot 2 a it Bhene 1200 maaan is a jars xemObserved ae FF6(@)102, tensity. 122 203 oe “thes Bi rem 18; 20. oo on Lest wm 1am 126 ww 14, 1s re on 18. 12 on 09 13 eats a 02 24 26) 03 16. 09 nm 1188 wm* or ‘aharp) ot oo 46 46 1108 wm 351180 wl nat or kaouivire Bi daa FSO, hier 1m on siso 19) 1168 k0 116s 20 1165 1-0/6 1165 25 1102 25 Mel 25 18 ro os, os. 15 15 4 22 02. 61 oO 10 1 10 19 06 6 rise 18 reso viz ava}is7 Liao 17 12008 11g 00 1s 08 Ti 00 1 16 Tuo 3 1 08 41 Lio 03 42 Lis 07 Ost ios 04 24 Lor 08 a1 10a 08 382 Lon 12 S16 Lost 04 ost Lorr o4 2ot L005 92 2 Loo 00 35 108 $5 9 als 1001 03 402 1000 fo 10s 03 43 bos? 1 ose 1106 sage 002 27 Observed intensity. + (00 reflections for which the observed intensities are enhanced, owing to preferential voutation, Observed intensities estimated visually in doereesing order of strength, WW ¥, $s, my mony Wty Why Wy Woy YW248 6, W, DRINDERY AND K, ROBINSON ON Observed Observed dane F'KONO% dom intensity. as FINO dow intersty st 08 raw) ost 2 102 00 Tose Gap 10s w eas 0 ase 1646 hist 102 16 une Lo 06 uno o3 uno a ' w bn ay 10s 7 106 re a 08 ey 19} 67 Loo wt 03 ross a ross 15 1055 Shing 1055 vw ot Tost 04 1 ou O8 06 bs 12 | 58 TOT 33) 4, | os ee ce 09 1s Tshes 10 102 50 roe o1 roa os ‘ 13s 18 2071035 o1 O40 Los bos too ol ‘totes 1 root 08 1 Vo 00 inn 96 380 Lost 48 Hees ios ot * (00) reletions for which the observed intensities are enhanced, owing to preferentil covientation. Olserved intensities estimated wisually in decreasing oder of strength, © The structure of kaolinite. As regards the detailed erystal structure we have limited our considerations to the question whether a layer structure of the type suggested by Pauling (1930), and subsequently found in dickite and nacrite, will explain the observed intew- sities of the reflections, assuming the lattice to he trielinie with the dimensions given above, ‘A projection of the layer structure on (001), the basal cleavage plane, is show in fig. 1: the heights of the atoms above the basal plane are indicated in the key ‘The oxygen atoms at heights 0 and 2-19. are assumed to form regular tetraledra bout the silicon atoms at height 0-604, and the (OH)s and oxygen atoms at heights 219 and 4-314. to form regular octahedra about the aluminium atoms at height 8254. he base of the unit cell can be fitted into this structure in three different ways inclined at 120° to each other in the manner indicated. Since the height of the cell is 7-13A., there is one layer of atoms per eel as compared with‘TIE StRUCTORE OP KAOLINITE, 49 oye in Geuner's cel Te remains to ind how euccesive layers of atome are tile with respect to eal othe i. to find the divetion of the esi or eke base in fig 1 there for posible dictions ofthis axis conesponding the four ays of contig selaive dxplncenents of adjsnt layers paral tke wean axes, Te woul therfore appear that there are 43<9"= 12 pos Heights of atoms above(001) Ooaygensto Oonarsa © alarge5d. @® » 219 Gv ataia © Siat O60 Ho. 1, Prjeton ofthe faint layer om (01 shoring the tree posible essen tut et the ell adpied vem fal ines Iiltes to be considered, but on determining the atomic co-ordinates re find fetully uly six diferent sets of co-ordinates; of these, only one set leads to tiated intensities which are a all closely related to the observed values. ‘he outlive of the wnt ell finally selected is shown by the full lines in Sg. 1 the ceigin ofthe cll i at the point marked *, The atomie co-ondinates expressed initia with respect to thevo axes aro given in table IHL, A projection ofthe { structure on a plane perpendicular to the a-axis is given in fig. 2, whieh shows also the direction of the c-axis relative to the structure. .250 (6, W. BRINDLEY AND K. ROBINSON ON In ealeulating the reflected intensities, the f-values of Bragg and West (1928) hhave been used. ‘The third column of table IT gives the calculated values of F4(0), where 4(@) = (1-+003°28)/ain?@ cos @ and @ is the Bragg reflection angle. We agree with Gruner in finding no reflections with (2-2) odd, a result which follows directly from the fact that for the ideal layer structure the e-fuce is centred, Although the triclinic axes could be changed to give a cell of half the volume, it Coreen Oz on es Projection of the kaolinite structure on a plane perpendicular tothe ean ‘Tanti TIL, Atomic co-ordinates in degrees for 2A1,8i0,(OH),. Two equivalent atoms fr ‘each position arising from ecntring of the -fuce. Oxygen... (0,180, 0), (20, 0, 0), (0, 270, 0}, (804, 128, 10H), (20), 248, 110B, OH. 7 4, 3, MOP, (18, 6, 218), (18, 185), 215), (13, 05h, 218). Aluminium” (119, 184, 164), (119, 904, 184) Silicon. (11,121, 30)), (U, 24, 30). seems better to retain the a- and axes at right angles and parallel to the otho- hexagonal axes of the layer itself, for this brings out the peeado-monocine shape of the cell, Tn presenting the reslt, no allowance has been made for absomtion Of the radiation in the specimen, which has the effect of diminishing the lover order refletions as compared with the higher orders. ‘Tho obserced intensities given in table TI are estimated visually from photographs taken with the power outed on thin glass fibres. ‘The measure of the agreement found between the observed and calelted intensities indientes that the layer type of structure suggested by Pauling, com- bined sith the triclinic axes, is essentially correct. ‘The fact that he observed intensities depend to some extent on the preferential onintation of the x3 talltes renders a procise comparison with the calculated valves rather dtc Specimens formed hy coating thin glass fibres show enhancement of (0!) reflections, while specimens prepared by packing the powder into cellpiace tubes give increased intensities from planes making angles approaching 90° with (001).SRC eee eee eee ee eee eee eee et ‘THE STRUCTURE OF KAOLINITE 281 ) Among the lower onder retlectious the following may be specially noted. ‘The |, cay elowe doublet (IIT) and (ITT) at d 4-170 and 120A, is found with all 2 kalnites giving sulliciontly shtcp reflections, and their relative intensities agree = sellwith the ealeulated ratio. ‘The absence of the (111) reflection is particulasly |. _utenarthy, beeanse out of the six possible orientations of the triclinic axes dis- tase above, only twa indieate-& negligible intonsity for this reflection, and one ifthe gives hopelosly incorrect values for many other reflections. ‘There is tierefore no ambiguity ws to which of the six orientations to choose. ‘The (111) fection at 3H5.. has an observed intensity in good agreement with the elated value, ‘That knolinite gives a releetion with this d value is important in mineralogieal analysis because it may easily be mistaken for the strongest «aarte line at 3396. ‘The doublet (110) and (110) is too close to be separated vith our largest eamera, but (110) i# very much stronger than (110) and the observed value lies much nearer the stronger line. The doublets (021), (021), snd (112, (173) show satisfactory agreement between observed and ealeulated itensites, and the very weak line (022) has not been observed. Among the lowerorder reflections the (020) alone is somewhat unsatisfactory, for tie observed intensity is distinctly greater than the Fg(@) value would lead one to expect For the higher-order reflections itis unnecessary to discuss in detail the data set i wt in table I, but it may be remarked that the calculated values explain, for the { nast part, not only the observed intensities but also the widths of the observed composite reflections. Ror example, the broad lines at d 1589, 149, and 1-024. tre sen to arise from a combination of reflections spread over a range of angles. Furthermore, between the lines at d 1-778 and 16824. and again between 41335 and 1-302A., we find particularly clear stretches of background which are [in agreement with the ealeulations | Discussion. {It has been shown by Hendricks (1939) that in dickite and nacrite there is a symmetrical relationship between the oxygen atoms in the hase of one layer and the (OFT) in the adjacent layers the relative displacement of successive layers is such that each (OH) fon is at the same distance, 291A, (Gruner 1932), p. 403), fromite nearest O neighbour in the next layer, In Gruner’sstrueture for kaolinite, two-thirds of the (OH)-O distances are 204. and one-third are 2824. In the sent structure for kaolinite we find a similar result, namely, two-thirds of the {01-0 distances are 290A. and the remaining third 28TA. Our distances ate Aightly greater than Gruner's owing to a small difference in our c-co-ordinates. | Acomparison of our dingram in Sig. 3, with the corresponding diagram for Gruner’s ttructure (see Hendricks, 1999, p. 517), shows that the shorter (O1f}-O distance occurs between different pairs of atoms in the two eases The shape of the triclinic cell suggests a closer relation to monoclinic symmetry | than is rally the ease, for even if the angle « were 90° instead of 91.8%, a single layer structure on the base chosen would not have monoclinic symmetry owing tothe arrangement of the aluminium atoms, Gruner showed thet « single-layer structuro with monoclinic symmetry could only be based on the cell with the dashed outline in fig. 1, corresponding to the space-zroup C? = Cm, A structure ronoelnie symmetry on the base that we have chosen would require tivo22, 6. W, BRINDLEY AND K, ROBINSON ON Jayors per ell with the space-group C! = Co; this in fact was Gruner's solution of the problem. The absence of monoclinic symmetry for a single-layer structure fon this base perhaps indicates why the actual eel is found to be triclinic. © Oxygen @ Si OOF Fie. 8. Projection of adjacent oxygen and (OT) atoms on (01) Acknowledgements—Finally, we wish to record our thanks to Mr. F. A. Bannister of the Mineral Department, British Museum, for placing at out dis posal specimens of kaolinite from many different localities and also to De. A. I. Roberts of the Fuel Department of this University, who supplied a mumber of specimens, We are also indebted to the Department of Scientific and Industrial Research for a grant to one (@.W.B.) of us. Feferonces. Basco (W. I.) end Wasr (J), 1928, A technique for X-ray examination of erystal strwetares ‘vith many parameters, Zeits, Krist, vol. 69, pp. 18-148. [3LA.4-17,] Barvoutx (G. W.) and Rontssox (IC), 1945. The structure of kaolinite, Nature, Londom, ol. 156, p. SL. (EA. 9-232) Favre (J. C. L), 1030.” Zur Method der rontgenographischen Bodenforechung. Zits ‘Krist, ol, 100, pp. 425-490, (MA, 7-121] mm (d, W.), 19928, ‘The exystalatructure of Kuolinite, Zeite, Krist. vol. 88 pp. 5-8. (GHA S187)‘THE STRUCTURE OF KaoLINITE 253 Gacsen{J.W), 19926, ‘The erytal structure of dikite, Zeit, Krist, vol. 88, pp- 381-104, [ola 5-225) lrxpricks (S. 1), 1936. Concerning the crystal structure of kaolinite Al,O,28i0, 21,0, td the compotion of wnauite. Zits. Kee, vol 95, pp. 247-252. (M.A. 6-412.) sii. Gryata structure of nnette AL,0s28i0/211,0, aor polymorphism of the kxolin | inert. Zits: Krist, vol, 100, pp- 500-618. (MLA. 7-422.) Kiontccute (C.), 1031. RUntgenouraplisee Untersuchungen an Tonen. Zeits, Krist, (Nol. 8% pp 180-15. [MLA 6-180) | Prue (a 060. The snore of tho chlorite, Pros. Nat, Acad, Sei, USA. vol 18 pp. 578-382, (MA. 105) | fost (6.5) and Kone (PF), 1981, ‘The kaolin alnerals, Prof. Papor U.S, Geol. Survey, nn. 105-B, pp. 151-176, (M.A. 5-350,)