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Historical Development in the Classification of Kaolin Subgroup

Historical Development in the Classification of Kaolin Subgroup

J Pak Mater Soc 2008; 2 (1)

HISTORICAL DEVELOPMENT IN THE CLASSIFICATION OF KAOLIN SUBGROUP

Anwarul Haq*, Yaseen Iqbal, Muhammad Riaz Khan Department of Physics, University of Peshawar ().

Corresponding Author: Anawarul Haq, Department of Physics, University of Peshawar (Pakistan). Tel: 0092 – 91 – 570 4615. E-mail: [email protected]

SUMMARY Kaolin is a subgroup of having polytypes namely , , and and a polymorph called . Kaolinite is of special interest and it constitutes clays like ball-clay, - clay, fire-clay, flint-clay etc. It has diverse industrial applications including , , rubber and pharmaceuticals. In addition, it has been of interest to academics and researchers in the disciplines of geology, agriculture, , engineering, dentistry, crystallography and microscopy. Because each of the above academic disciplines has looked at kaolinite from their own angles and interest, a great confusion has resulted with respect to its name and classification. Thus different organizations arranged conferences, seminars, workshops and lectures to reach a universally accepted classification and names regarding clays and clay minerals. This study reviews the efforts, agreements and recommendations that have been made by international experts in achieving this goal.

INTRODUCTION The name kaolin has originated from Kauling (or sheets, co-axial rolled sheets, and sometimes Gaoling) a clay mine in the Kiangsi province tubes7. The grain orientation and morphologies (China). This mine was first developed in the make the microstructure permeable with 11th century. This mine remained operational individual grains or agglomerates appearing until 1964 before its total depletion1. Kaolin is a sometimes as a collection of open books or sub-group of kaolin-serpentine group of the elongated, loosely bounded books, hydrous planar phyllo- related to clay accompanied by smaller grains and compacts of with a di-octahedral octahedral fine grains, and face-to-face oriented flacks. The characteristic. It has poly-type species namely, book-type grains / agglomerates morphology is kaolinite, dickite, nacrite and a polymorph typical of kaolinite whereas the elongated halloysite2-6. Each of these species has been tubular morphology is considered a described briefly in the next section. The name characteristic morphology of halloysite8. The kaolin is also referred to the clay containing pure microstructure of kaolin comprises stacks or kaolinite mineral. Depending on the origin of book-shaped grains that may be straight or minerals, currently used clays containing curved (Vermicular), plates or flakes floccules or kaolinite include ball-clay, china-clay, fire-clay, non-floccules, tubes, scrolls, prisms, fibers, flint-clay, primary kaolin, secondary kaolin, and spherical to globular shapes etc9. A summary of refractory clay2. historical developments in the classification of kaolin subgroup is given Table 1 and its various The microstructure of kaolin comprises grains characteristics along-with relevant with a number of different morphologies such as crystallographic information is given in Table 2. regular and irregular hexagonal platelets, rolled

Table 1: The name, first locality and structural identification of kaolin group (after Bergaya et al 2) Clay Locality First applier of the name Structural identification Kaolinite Kauling (High ridge) a hill near Jauchau Fu Johanson and Blake, 1867 Ross and Kerr China, Dickite Island of Anglesey , UK Allan Brugh Dick, 1908 Ross and Kerr Nacrite Einigkeit mine, Brand-Erbisdorf, Freiberg in Brongniart, 1807 Ross and Kerr Saxony, Halloysite Liege, Balgium Berthier, 1826 Hofmann et al., Mehmel

Anwarul Haq*, Yaseen Iqbal, Muhammad Riaz Khan: Historical Development in the…….... 44 J Pak Mater Soc 2008; 2 (1)

Table 2: Comparison of Kaolin group. Property Kaolinite Dickite Nacrite Halloysite Crystal Tri-clinic16 Mono-clinic10 Mono-clinic10 Mono-clinic20 system Unite Cell a(5.1554Å), a(5.1474Å), a(8.906Å), For 10 Å 7 Å data b(8.9448Å), b(8.9386Å), b(5.146Å), a(5.14Å), a(5.14Å) c(7.4048Å) c(14.390Å) c(15.664Å) b(8.90Å), b(8.90Å) α(91.7°) ß(96.483°)12 ß(113.58°)18 c(20.7Å) c(14.9Å) β(104.862°) ß(99.7°) ß(101.9°)20 γ(89.822°)16 General Massive blocks, Transparent, Tabular Pearly luster, fairly Fibrous, Spheroid or appearance Vermiform or Crystals10 transparent, trilled irregular. Fibrous appear granular aggregates tabular crystals, tubular and scroll-like. Some as radiating platelets Wedge shaped time platy morphology.37 or pile of platelets.37 plates.10 10 10 10 36 Composition 2H2O.Al2O3.2SiO2 2H2O.Al2O3.2SiO2 2H2O.Al2O3.2SiO2 2H2O.Al2O3.2SiO2.2H2O Density 2.63g/Cm3 37 2.60g/Cm3 37 2.60g/Cm3 37 2.55g/Cm3 (Dehydrated) to 2.00g/Cm3 (depend on water content) 37 Ross CS & Kerr PF10, Grim A36, Deer WA et al.37,Kohyama N et al.20, Zheng H & Bailey SW18, Bish D & Johnston T12, Bish DL & Dreele RB16

Table 3: Recommended use of kaolin and kaolinite in the classification* of 1:1 layer silicates 24, 25

Layer type Group Sub-group** Species*** 1:1 Kaolin-Serpentine Kaolin Kaolinite, dickite, nacrite 1:1 Kaolin-Serpentine Serpentine lizardite, , berthierine * Refer to Martin et al. (1991) for complete classification scheme ** Octahedral character (di-octahedral or tri-octahedral) may be used also. *** Only a few examples are given

Kaolinte The name ‘kaolinite’ was first used by Johnson techniques were used to determine the exact and Blake. This obviously reflected the original position of H- in dickite mineral and its reference of kauling mine (China) where the first stacking sequence was found to be different clay of this species was discovered2. Ross and from that of kaolinte and nacrite14-15. Its crystal Kerr10 not only introduced different species in structure is monoclinic ( Cc) with kaolin mineral as kaolinite, nacrite and deckite lattice parameters a=5.1474Å, b=8.9386Å, but identified their crystal structures as well. c=14.390Å and β=96.483°. The chemical Initially, the of kaolinite was composition of Dickite is the same as kaolinite identified as monoclinic10-11 but later on using X- and it is a 1:1 layer type mineral but with a ray diffraction data, the crystal structure of different stacking sequence16. kaolinite was found to be triclinic with a=5.1554Å, b=8.9448Å, c=7.4048Å, α=91.7°, Nacrite β=104.862° and γ=89.822° with space group Brongniart introduced the mineral Nacrite C112. Kaolinite has been described as a 1:1 di- (meaning the mother of pearl) in 1807. It was octahedral phyllo- in with chemical obtained from Einigkeit mine (Germany). It was 13 2 composition Al2Si2O5(OH)4 . studied in detail by Des Cloizeaux and Dick . Dick identified this as a different mineral from Dickite kaolinite and later on Mellur, and Ross and Kerr Dickite mineral was first obtained as a kaolin further confirmed Dick’s results2. Using least mineral by Allan Brugh Dick in 1908 from the square method and electron density maps, Island of Anglesey, Wales (UK). Later on, Ross Blount et al.17 determined the crystal symmetry and Kerr distinguished this from kaolinite. They of Nacrite as Cc with a 2-layer structure. Using a determined its crystal structure and gave it the single crystal X-ray Diffractometer, Zheng and name “dickite” after its original discoverer Allan Bailey18 determined the lattice parameters of Brugh Dick2. X-ray and Neutron Diffraction Nacrite as a=8.906Å, b=5.146Å, c=15.664Å and

Anwarul Haq*, Yaseen Iqbal, Muhammad Riaz Khan: Historical Development in the…….... 45 J Pak Mater Soc 2008; 2 (1)

β=113.58° with a monoclinic crystal structure different time who introduced kaolin as a group (space group Cc). Nacrite has the same layer or subgroup in one way or the other. Grim type and chemical composition as kaolinite and proposed kaolinite as a group with equi- dickite but with a different staking sequence. dimensional, 2-layer crystalline materials and halloysite as another group with elongated, 2- Halloysite layer crystalline materials. In 1955, Brindley Halloysite is another having the proposed kaolin type subgroup comprising same chemical composition as kaolinite, nacrite chemical species such as kaolin minerals with and dickite. It was first discovered by Berthier structural varieties including halloysite, kaolinite, and was named “halloysite” after Omalius dickite and nacrite. The same year, Brown d’Halloy, the well-known geologist. Its crystal proposed group name kandites as a structure was determined by Hofmann et al. and dioctahedral, 1:1 family of layer silicates in Mehmel2. Churchman and Carr19 investigated diphormic family with minerals nacrite, dickite, halloysite. They used a number of techniques kaolinite and halloysite. such as X-ray diffraction, electron microscopy, differential thermal analyses, infrared In 1957, Caillere and Henin introduced kaolinite spectrometry, and chemical analyses and as a non-swelling, non-replacement, di- confirmed that it was different from kaolinite. octahedral 7Å (1:1) family of layer silicates with They defined “halloysites” as minerals with a Al2Si2O5(H2O)2 and halloysite kaolin layer structure, which either contains as a swelling, non-replacement, di-octahedral, inter-layer water in their natural state or for 7Å (1:1) family of layer silicates with chemical which there is unequivocal evidence of their formula Al2Si2O5(H2O)2.H2O. Furthermore, formation by dehydration from kaolin minerals kaolinite has crystallographic and textural containing inter-layer water. The chemical varieties as a) kaolinite (Triclinic), b) nacrite composition of halloysite varies from (monoclinicK., β = 90.3º), c) dickite 19 Al2Si2O5(OH)4 to Al2Si2O5(OH)4.2H2O . The (monoclinicK., β = 96.8º), d) fireclay hydrated tubular halloysite (10Å) has 2-layer (pseudomonoclinicK.), e) Metahalloysite monoclinic crystal structure (space group Cc) (pseudomonoclinicK.), whereas halloysite has with a=5.15Å, b=8.90Å, c=20.7Å, and β=99.7°. no crystallographic and textural varieties. The The dehydration of halloysite does not affect its same year, Strunz introduced kaolin-type sheets morphology and . However, it table of kaolinite-serpentine, halloysite (H2O- changes the lattice parameter c from 20.7Å to expanded kaolinite) and OH-expanded kaolinite 14.9Å and the angle β from 99.7° to 101.9°. The groups. These groups have subgroups as dehydrated halloysite is referred to as halloysite kaolinite series di-octahedral having Al:Si=0.4 (7Å). This variation occurs due to the removal of kolinite, and Halloysite series subgroups with 50-100Å thick inter-layer domains of water along Al:Si=0.4 halloysite. The group OH-expanded the c-axis upon dehydration20. kaolinite has di-octahedral hydrargillite-kaolinite. However, Mackenzie proposed Kandites as a NOMENCLATURE OF CLASSIFICATION OF group of di-octahedral, diphormic (or 1:1) layer- THE KAOLIN SUB-GROUP lattice types and comprised i) Nacrite, The first national conference on clays and clay Al2Si2O5(OH)4, ii) Dickite, Al2Si2O5(OH)4, iii) Tc- technology in USA suggested halloysite to be a Kaolinite, Al2Si2O5(OH)4, iv) ψM-kaolinite, group name, but there was no discussion on the Al2Si2O5(OH)4, v) Metahalloysite, Al2Si2O5(OH)4, 21 classification of clays . Until 1953, there was no vi) Halloysite, Al2Si2O5(OH)4.H2O, and vii) proper classification of clays or clay minerals. Anauxite, Al2Si3O7(OH)4. Generally, clay minerals were considered as crystalline silicates of, a) chain lattices with two In 1958, Frank-Kamenetsky proposed Kaolinite clay minerals and and, b) (non-swelling) and Halloysite (both non-swelling 1:1 (Diphormic), 2:1 (Triphormic) and 2:2 and swelling) as di-octahedral layer silicates. (Tetraphormic) layer lattices. Mackenzie22 The kaolinite group has minerals Kaolinite, reported the decisions of the meeting under the dickite and nacrite while halloysite has meta- umbrella of Committee Internationale Pour halloysite and hydro-halloysite (endellite). The I’Etude des Argiles (CIPEA) at Brussels, and suggestions of Konta have also been reported mentioned different schemes of classification of who described the Kaolinite group, as a group clay minerals discussed. A total of eight having kaolinite as abundant mineral. proposals were forwarded by different experts at

Anwarul Haq*, Yaseen Iqbal, Muhammad Riaz Khan: Historical Development in the…….... 46 J Pak Mater Soc 2008; 2 (1)

Brindley23 reported the recommendations of the which were considered as settled issues in the Nomenclature and Liaison Committee of the Meeting in 197528. Clay Minerals Society, having Type, Group, Sub-Group, and Species as column heading in Bailey29 reported the meeting of IMA-IUCr joint classification. The Committee also committee on poly-typism of layered structure recommended a classification having 1:1 layer and recommended the Kaolinite-Aabc type Kaolin-serpentine (x~0) as a group with (Kaolinite), kaolinite-Mab2c (dickite) and sub-group kaolinite and serpentine. The kaolinite kaolinite-Mba2c (nacrite) as poly-types of subgroup has species kaolinite-1Tc and kaolinite. kaolinite-D. The committee also discussed the species name of kaolinite as a) well crystallized Summarizing the proceedings of the meetings of kaolinite (kaolinite-1Tc), b) disordered layer nomenclature committee, Bailey formed a table sequence (kaolinite-D), c) dickite (kaolinite-2M1) namely “classification scheme for phyllosilicates and d) nacrite (kaolinite-2M2). The names related to clay minerals”, that included 1:1 layer endellite and halloysite were recommended for type kaolinite-serpentine group (x~0) comprising discussion in CIPEA to resolve confusion23. kaolinite and serpentine subgroups. The subgroup kaolinite comprised species namely The CIPEA first agreed on kaolinite-serpentine kaolinite, dickite and halloysite30-32. group, di-octahedral and tri-octahedral sub- groups in the case of a single word group name, Martin et al.5 reported the revised classification the kaolinite-1Tc, kaolinite-2M1 and kaolinite– of clay minerals, having planer and non-planer 2M2 in light of the new research work and hydrous phyllosilicates. The classification of forwarded a memorandum to International hydrous phyllo-silicates includes serpentine- Mineral Association (IMA) to drop the name of kaolin group with octahedral characters as tri- endelite and adapted the name ‘halloysite’, the octahedral, di-octahedral and di-tri-octahedral. classification scheme, structural verities of Kaolin has di-octahedral with species kaolinite, kaolinite as such, along with the other issues dickite, nacrite and halloysite (planar). Non- where the mentioned issues were voted by 15- planar hydrous phyllo-silicates include di- members of IMA. The committee recommended octahedral kaolin of a species halloysite (non- the classification scheme by 13 votes, halloysite- planar). metahalloysite and re-naming the structural verities of kaolinite by 9 votes24. Guggenheim33-34 reported the discussion of AIPEA meeting on “poly-typism, polymorphism Brindley25 summarized the recommendations of and the kaolin group”. AIPEA agreed upon the the Clay Mineral Society, where IMA endorsed name Kaolin-Serpentine with two sub-groups the layer sequence notation for kaolinite, dickite kaolin and serpentine. They dropped all the and nacrite. However, the Committee other names like kaolinite-serpentine, kandite Internationale Pour l’Etude des Argiles (CIPEA) etc. Kaolin with species Kaolinite, dickite and put observations on these names and excluded nacrite are poly-types as these are close in dickite and nacrite at that time. They referred the structure and layer types. Kaolin clay contains issues for further discussion in the next meeting. pure kaolinite or related clay minerals with white, Briley26 reported the revised classification which nearly white colour, and is natural and used in included 1:1 layer type kaolinite-serpentine with white-ware, paper, rubber, and etc33-34. a charge per unit cell x~0 and further sub-groups They recommended the classification given in of kaolinite and serpentine. Thus the kaolinite Table 3. Guggenheim35 also summarized the sub-group contained two species kaolinite and reports of the AIPEA Nomenclature Committee halloysite with a modification of excluding dickite and formed a Table for clay related phyllo- and nacrite. silicates as planar and non-planar phyllo- silicates as previously given by Martin et al.5. The AIPEA discredited the name anauxite and the renaming of kaolinite, dickite and nacrite In conclusion, this overview of historical were left open for further discussion. This development of the Kaolin sub-group indicates Committee also published the same groups as that kaolin is an important clay mineral and has reported by Bailey27. AIPEA recommended the been a subject of continuous research and species halloysite (7Å) and halloysite (10Å), discussion. Obviously, further research and discussions are needed to explore and

Anwarul Haq*, Yaseen Iqbal, Muhammad Riaz Khan: Historical Development in the…….... 47 J Pak Mater Soc 2008; 2 (1)

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