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J. THOREZ
Institute of Mineralogy
Lige State University, Belgium

practica! Identification
of clay minerals
A HANDBOOK FOR TEACHERS AND STUDENTS
IN CLAY MINERALOGY

1976
Editions G. LELOTTE
B 4820 DISON (Belgique)
PREFACE
The present author, in designing this short student handbook, had in mind the basic
needs of students and teachers in clay mineralogy and clay geology, who both have
to face routine X-ray diffraction analysis of clay minerals or to have periodic refreshment
of the basic knowledge in this topic.

One of the most mportant problems of application of clay mineralogy to geolgica!


and pedolgica! studies is effectively the obtention of a general key to mark a rapid
clay mineral analysis in a three-fold purpose : the quick and most accurate determination
of a clay mineral; the mineralgica! characterization of complex clay rocks, sediments
and soi/s ; the analysis of mportant series of samp/es which may be composed of
polymineralic mixtures of clay minerals. Henee for this purpose, and for the one of
teaching and studying, a rapid clay mineral analysis is desirable, which gives neither
the best or the poorest results, but can be used as a routine mean until more detailed
data are lateron obtained. This purpose corresponds to the mnimum ABCD in clay
mineralogy designed in this handbook.

The present author has already published a Laboratory Handbook in order to allow and
faciltate the best and accurate determination of phyllosilicates and clay minerals by
X-ray diffraction technique for both the oriented aggregates and the random powder
mounts. (THOREZ, 1975).

In the present handbook, which has to be considered as a companion to the above


quoted one, and which is a part of the practical course given by the author in Lige
State University, a special effort has been made to extract from the explosive and
dispersed literature, as well from the author's experience, all the practical aspeis
encountered during the determination of the clay minerals. In its concept, the present
hanbook appears as a sort of compromise. A mnimum of data is provided which are
related to the crystal/ography and crystallochemistry of the clay minerals : there are
excellent books dealing with these aspeis, and the user is invited to refer to these for
complementary data. It was not the purpose of this handbook to deal again with these
traditional aspeis.
On another hand it was not the author's intention to provide a complete or an exhaustiva
review of the literature. The accent has especially been placed on the analysis of the
oriented aggregates of clay minerals ; but some (hkl) characteristics are provided. The
reader has to refer i. e. to THOREZ (1975) for complementary data. It is hoped that the
presentation and development of this handbook will faciltate the practical point of view
of the X-ray analysis of the clay minerals, just like a kind of ABC of the subject, and
will be attractive and useful for both the teachers and the students.
Altough severa! kinds of methods for Identification of clay minerals are actually used,
the X-ray diffraction technique is always considered to be one of the most rapid proce-
d/res, being most useful to reveal properties of the materials intimetely related to the
crystal structure, composition and other properties (swelling, collapsing). Henee the
accent will be essentially put on the X-ray method.

The clay fraction of sediments, soils and weathering producs is usually composed of
polymineralic associations, where both phyllosilicates and related minerals, and non
phyllosilicates are present (quartz, feldspar, zeolites, carbonates, amorphous etc...). It
is rather difficult and even impossible to seprate the phyllosilicates and clay minerals
from one anofher. For the purpose to identify the different components as in details
as possible without an artificial separation, it is thus desirable firstly to recognize and
confirm the composition of the different components of the mixture, after various treat-
ments, by oriented aggregates (the technique that allows an enhancement of the (001)
reflections), and by random powder mounts. As a consequence the reader will have
to use in simultaneity if necessary the two handbooks, (THOREZ, 1975) and the present
one, following his needs in the accuracy of the determination.

Jacques Thorez
Mineralgica! Instituto
Lige State University.

VI
TABLE OF CONTENTS

PREFACE V IV-E-4 : Distinction between saponite, Fe-sapo-


nite, Fe-montmorillonite, a n d nontronite . . . 25
INTRODUCTION XI
IV-F. VERMICULITES 26
I . TERMINOLOGY O F T H E CLAY MINERALS . . . . 1
IV-F-1 : Generalities 26
II. SAMPLE PREPARATION 1
IV~F2 : Differentiation between vermiculite varieties 26
III. QUANTITATIVE ASPECTS OF THE X-RAY ANALYSIS . 2
IV-G. CHLORITES 30
IV. QUALITATIVE DETERMINARON OF THE SIMPLE CLAY
MINERALS BY X-RAY DIFFRACTION 3 IV-G-1 : Generalities 30

IV-A. DESCRIPTIVE CODE FOR THE d-SPACINGS OF IV-G-2 : Varieties of chlorites 31


CLAY MINERALS 3
IV-G-3 : X-ray diffraction characteristics of chlorites. 33
IV-B. KANDITES 4
IV-G-4 : Chlorites as oriented aggregates . . 33
IV-B-1 : Generalices for dioctahedral minerals . . 4
IV-G-5 : Polytypism in chlorites 34
IV-B-2 : Identification of discrete species. . . 5
IV-H. PALYGORSKITE 36
IV-B-3 : Behaviour of kaolinite with organic and in-
organic compounds 6 IV-I. SEPIOLITE 37

IV-B-4 : Trioctahedral minerals 7 V. SUMMARY OF THE BEHAVIOURS OF THE CLAY MINERALS


TOWARD T H E IDENTIFICATION TREATMENTS . . . 38
I V - B - 5 : Identification of kandites n a clay mixture 8
VI. QUALITATIVE DETERMINARON OF MIXED LAYERS . . 42
IV-B-6 : Differentiation between kaolinite and chlorite 8
VI-A : Generalities 42
IV-B-7 : Crystallinity o f kaolinites . . . . 8
VI-B : Practical determinaron by X-ray diffraction (oriented
IV-C. MICA-LIKE CLAY MINERALS AND ILUTES . . 10 aggregates) 43

IV-C-1 : Generalities 10 VI-C : Regularly interstratified minerals . . . . 44

IV-C-2 : The Hite term 11 VI-C-1 : Generalities 44

IV-C-3 : Polytypism m Hites 11 VI-C-2 : Nomenclature a n d description . . . 44

IV-C-4 '. " Crystallinity and varieties of Hites . . 12 VI C 3 : Behaviour of regularly interstratified mine-
rals upon treatments 45
IV-D. PYROPHYLLITE AND TALC 16
VI-C4 : Gritera for the reoogniton of regularly inter-
Remark : differentiation between pyrophyllite-talc, and stratified minerals 46
brittle micas and paragonite 16
VI-D : Randomly mterstratified structures . . . . 48
IV-E. SMECTITES 16
VI-D-1 : Generalities 48
IV-E-1 : Generalices 16
Vl-D-2 : Criteriaforthe recognition of randomly mter-
I V - E - 2 : Non-smectitic composition of a 1 7 glyco- stratified structures 48
lated material 17
VI-D-3 : Degrees of disorder and consequences . 49
IV-E-3 : Crystallinity of smectites (dioctahedral) 18
VI-D-4 : Proposed notations for randomly nterstrati-
IV-E 4 : Identification o f species . . . . 21 fied structures 51

IV-E-4a : Smectites with high and low charges 21 VI-D-4a : Randomly interstratified structures with
14c and 14y 52
IV-E-4b : Genetic differentiation between smec-
tites : low charge, high charge, authigenic, and mica- V|-D-4b : Randomly interstratified structures with
derived smectites 21 14c and 14|y 52

IV-E-4c : Intermedate smectite-vermiculite mine- VI-D-4c : Randomly in*erstratified structures with


rals 21 14c and 14Q 52

IV-E-4d : The GREENE-KELLY's Li-Test . . 23 VI-D-4d : Randomly interstratified structures with


10 layers a n d 14^ o r 14y interlayers . . . 53
IV-E-4e : Differentiation between beidellite, mont-
morillonite, a n d vermiculite . . . . . 23 Vil. ROUTINE IDENTIFICATION INDEX FOR CLAY MINERALS
AND MIXED LAYERS 62
IV-E-4f : Al-smectites and Al-vermiculites ; Fe-
smectites 24 VIII. DECREASING (001) IN d() OF PHYLLOSILICATES AND
CLAY MINERALS, AND (001) and/or (002) OF REGULAR
IV-E-4g : Wyoming-, Cheto-, and iron-rich smec- MIXED LAYERS (air dried state) 71
tites 24
IX. LIST OF THE ( O O I ) REFLECTIONS -(001) to (006)- FOR
IV E~4h : Distinction between soil-montmorilionite CURRENT CLAY MINERALS INCLUDING MIXED LAYERS
and soil-beidellite 25 (Natural state) 73

Vil
X. ALPHABETICAL LIST OF CURREN! CLAY MINERALS IN- XI. INCREASING (060) OF PHYLLOSILICATES AND CLAY
CLUDING MIXED LAYERS WITH THEIR d(001) VALES IN , MINERALS 79
AND THE CORRESPONDING INTENSITIES OUT TO THE 3
REGIN OF THE DIFFRACTOGRAM (oriented aggregate, na- XII. GLOSSARY OF PHYLLOSILICATES AND CLAY MINERALS 80
tural state) . 76
SELECTED BIBLIOGRAPHICAL REFERENCES 87

INDEX OF TABLES

Table 1. - Classification scheme for layer silicatos . 1 Table 19. - Observed X-ray powder data for sepiolite (after
CAILLERE, n GIESEKING, 1975) : data provided only out
Table 2. - Explanation of the motifs and symbols. . 3-4 to the 3 regin of the X-ray diffractogram 37

Table 3. - Routine differentiation for kaolinite minerals (X-ray Table 20. - Progressive shifting of the 12 sepiolite reflec-
powder pattern) - (data kindly provided to the author by tion towards 10 upon heating treatment from 300 to
Dr SIEFFERMAN) 800"C, with possible simultaneous occurrence of both the
reflections at certam temperatures (after LUCAS. 1963). 37
Table 4. - Comparison between the charactenstic reflections
(peculiar, common, supplementary) of kaolinie, dicktite and Table 21. - Vales of the basal reflection, in d(A), for the cur-
nacnte (after DOUILLET and NICOLS, 1969). . rent clay minerals, after the classical identification essays
(N = natural, untreated sample ; EG = ethylene glycol ;
Table 5. - Reaction types of kaolinite group minerals accordmg 500 = heating to 500C) 38
to heir behaviour towards hydrazine, hydrazine+waer, and
ethylene glycol leachings (after RANGE et a / , 1969) 7 Table 22. - Vales in d() of the charactenstic reflections of
the series (OOI) of curren! clay minerals, after various
Table 6. - Behaviour of kaolinite, and kaolinite types, towards diagnostic treatments (N, EG. 500 and 550"C) ( after
the treatment with K-acetate (ALIETTI, 1966). . 7 LUCAS, 1963) 39

Table 7. - d(001) and d(060) for minerals of the serpentine Table 23. - Vales in d() of the basal (001) reflection of
group (after BROWN, 1971, and THOREZ, 1975). . 7 curren! clay minerals (without, and with cation-saturations
with K+, Ca++, Mg ++) (after QUATERNAAT, 1968) . 40
Table 8. - (hkl) reflections in d(), and corresponding inten-
sities, for polymorph varieties of Hites and hydrous micas Table 24. - Coloured key for the routine identificaron of cur-
(after LEVINSON, 1955) 11 rent clay minerals, based on the behaviour of the basal (001)
reflection after different treatments (after THOREZ, 1975). 41
Table 9. - Charactenstic (hkl) reflections for the polymorph
varieties o f Hites (d-spacngs n ) . . . . . . 12 Table 25. Possible types of intersratification for binary com-
bmations of the various layers of simple clay minerals
Table 10. - Mixture of Hite polymorph varieties : intensities of (after THOREZ, 1975) 42
the specific reflections (after KODAMA, 1962) 12
Table 26. - Classification and combinations of interstratitied
Table 11, - Expansin of synthetic beidellite and montmoril- layers in all the actually known mixed layers (after STOCH,
lonite [(vales of (001) in d()] (after HARWARD and 1971, modified by the present author) 43
BRINDLEY, 1964) 23
Table 27. - Examples of the variability in layer composition for
Table 12. - Differentiation between montmorillomtes, beidel- regularly interstratified minerals (after THOREZ, 1975). . 45
lites and vermiculites on the basis of the saturatmg catin,
moisture conditioning, and solvation method (after HARWARD Table 28. - Position, m d(), and behaviours of the (002) re-
et al., 1969) 23 flection in some of the main types of regularly interstratified
minerals after glycolation and heating (to550C).. . . 46
Table 13. - Distinction between Cheto-, Wyoming-, and iron-
rich montmorillonites after catin saturations (K, Mg) (after Table 29. - Highest d-spacmg m A of the (001) reflection for
GRIM and KULBICKI, 1961). 24 regularly interstratified minerals (after VIVALDI and Mac
EWAN, 1960 ; LUCAS, CAMEZ. and MILLOT, 1959 ; Mac
Table 14. - Classification of Mg-, Al- and Fe-chlorites EWAN and RUIZ-AMIL m GIESEKING, 1975; THOREZ,
(after WARSHAW and ROY, 1961) . 31 1975) 46

Table 15. - Summary of one-layer polytypes in chlorites (after Table 30. - Coloured key for the routine identification of cur-
BAILEY, m GIESEKING, 1975) 35 rent regularly interstratified minerals, based on the behaviour
of the (002) reflection after different treatments. (after
Tablo 16. - Correspondence between chlorite species, and THOREZ, 1975) 64
the vales of the intensities ratio l(002) + (004)/l(003), and
l(003)/l(005) (after POST and PLUMMER, 1972). 36 Tables 31-35. - Routine identification keys (N, EG, 500C)
for current clay minerals, randomly and regularly mixed
Table 1 7. - (OOI) reflections for soil chlorites : Clinochlore, layers, taking into consideration the variations in the shapes
Prochlonte, Corundophilite, Leuchtenbergite, and Thurin- of the basal (001) reflection (simple clay minerals), or of
gite, for the untreated and the heated (to 550C) samples : the (002) reflection of mixed layers 65
positions of the (OOI) reflections n d(), and oorresponding
intensities (after MARTIN, 1955, modified in THOREZ, Table 36. - Classification of phyllosilicates (after BRINDLEY,
1975) 36 1962), and the recommendations of the AIPEA Nomen-
clature Committee, Madrid, 1972). 80
Table 18. - d-spacings and observed intensities of the Atta-
pulgus palygorskite (X-ray pattern out the 3 rea) (after
BRADLEY, 1940) 36

VIII
INDEX OF THE SHORT TABLES - Vermiculite 26

RELATIVE TO THE BEHAVIOUR - Low-charge vermiculite 30

OF CLAY MINERALS - Well-crystallized chiorite, soil chiorite or degradad chiorite


with unstable vermiculite interlayers, soil chiorite . . 31
TOWARDS THE DIAGNOSTIC - Palygorskite 36
TREATMENTS (untreated, glycola- - Sepiolite 37
ted, heated sample)

These tables are generally designed as follows :

Treatments N EG 500C TABLES


(001) n d() FOR THE DIFFERENTIATION
BETWEEN CERTAIN SIMPLE
- Kaolinite . 4 CLAY MINERALS
- Mica-like clay minerals and Hites . 10
- Pyrophyllite 16 - (OOI) reflections o f kaolinite a n d chiorite . . . . .

- Smectites (montmorillonites) . 17 Similarities between WMIemseie,' Paragonite, Margante,


Clintonite, Bityite, Ephesite, relatively to Pyrophillite and Tale,
- Soil montmorillomte . . . . 25 on the basis of their (OOI) and (060) reflections . . 16

- Soil beidellite 25 - Differentiation between vermiculite, smectite and chiorite on


the basis of the behaviour of the (001) reflection upon treat-
Nontronite 25 ments (N, EG, 500C) 26

- Fe-saponite, Fe-montmorillonite, nontronite 25 - Differentiation between chiorite, smectite, Mg-vermiculite, and


desaturated vermiculite (on the basis of the behaviour of the
- Saponte 25 basal reflection upon classical treatments : N, EG, 500"C) . 26

INDEX OFTHE FIGURES

Figure 1. - Crystallinity orders n kaolinite (after MURRAY and Figure 7. Characterization of the Hite Crystallinity" or
LYONS, 1956) 9 sharpness ratio of WEAVER (1960), and DUNOYER de
SEGONZAC, (1969) 14
Figure 2. - Schematic Debye-Scherrer X-ray monogram of well-
crystallized kaolinite, fire-clay and halloysite (hydrokaoli- Figure 8. - Ilute characterization by the acute n d e x and
mte) ( after BRINDLEY and ROBINSON, 1948) . . . 9 the Al2O3/FeO+MgO compositon of the octahedral layer
(after ESQUEVIN, 1969, and DUNOYER de SEGONZAC,
Figure 3. - Crystallinity ndex for kaolmite (after HINCKLEY; 1969). Evolution of the crystallnity and compositon of the
RANGE ef al., 1969) 10 Hite from the diagenetc or weathering zone toward the
epizone . . . . . . . . . . 1 5
Figure 4. - X-ray powder diffraction patterns of monomineralic
kaolin minerals. (A) : well-crystallized, well-formed platy Figure 9. - Diagrammatic representaron of the Hite evoluton
material, enhanced basal reflections (kaolinite) ; (B) : platy during the weathering (after THOREZ, 1973). Vertical axis :
material with b-axis disordered sequence, enhanced basal Al2O3/FeO + MgO ESQUEVIN's ratio n the octahedral
reflections (disordered kaolinite) ; (C) : layer sequence layer based on the ntensities ratio (002)7(001) ; horizontal
partially disordered with respect to both a- and b-axies, axis : subdivisions of the acute ndex la of the ilute, based
little enhancement of basal reflections, rolled form (hal- on the thckness of the 10A reflection at half-height above
loysite) ; (D) : highly disordered layer sequence, no en- background : Hite with acute peak Ip A. with l a -3mrn ;
hancement of basal reflections, tubular form (halloysite) Hite with enlarged foot (lp.|.) with l a =6mm ; open ilute,
(after BRINDLEY and DE SOUZA SANTOS, 1963, repro- with la equal or above 10mm. (A)= domain of ilutes with
duced in DIMANME, RASSEL, TARTE and THOREZ, 1974). 10 a muscovite composiion ; (B)- domain of Hites with a
phengite composition ; (C)= ilute with a muscovite+bo-
Figure 5. - ESQUEVIN's method of fixmg the composition n tite compositon ; (D)= ilutes with a biotite compostion at
Al2O3/FeO+MgO in the octahedral layer of Hites, based the level of the octahedral layer (ESQUEVIN, 1969) . . 15
o n t h e ratio o f t h e ntensities o f (002)7(001) . . . 10
Figure 10. - - opening state of Hite after MELLIERES and
Figure 6. - Schematic representaron of the (001) Hite reflection PEREZ-NIETO (1973), n sedimentary Hites :
at 10 n the case of open varieties : IQ, ly, and IM ST-SI
(LUCAS, 1963). Comparison of the shape after the glyco- E 0 =100^
lation and heating. Minerals related to ilutes (Van der ST= total surface of the 10 reflection above background
MAREL, 1961) 13

IX
S|= surface of the normal reflection of the (well-crystal- Figure 23. - Types of (OOI) sequences of clay minerals (styli-
lized) Hite centered on the 10A: the surface s limited, sed X-ray diffraction patterns, providing the shapes of the
on the high angle side of the diffractogram, by the des- harmonio reflections). a) simple clay mineral, well-crystal-
cending curve of the reflection ; on the low angle side, lized, with symmetrical and intense reflections ; b) mixture of
the shape of the reflection s delimited by drawing the simple clay minerals ; c) regulary interstratified minerals the
symmetrical branch of the high angle side of the reflection. (OOI) reflections of which have d(A) positions intensities
Sample pretreated with C a , a n d glycolated . . . 15 and shapes according tothe same charactersforthe simple
clay minerals the layers of which are interstratified ; d)
Figure 11. - Interference of the (002) of pyrophyllite at 9.1, randomly interstratified structure charactenzed by badly-defined
with the (001) of ilute at 10 during the evaluation of the reflections, with a plateau shape in many cases and an irrational
acute ndex la of the latter mineral by DUNOYER de sequenceof (OOI) reflections ;thesuperlatticestructureisordinarily
SEGONZAC's method of characterization the crystallinity. missing ; e) aspect of a mixture of a simple clay mineral and of a
(A) : case of a mixture where the basal reflection (002) of randomly interstratified structure ; f)degraded mineral (i. e. illite) with
pyrophyllite s not apparent and causes an enlargement of asymmetrical reflections (tailing reflections) . . . . 42
the Hite reflection towards the high angle side ; (B) :
case of a mixture composed of pyrophyllite and ilute ; their Figure 24. - Illustrating the way n which each reflection
basal reflections are very closed, causing an enlargement of migrates and changes shape in randomly interstratified
the low part of the reflections while two distinct peaks struciure. The further apart the mxima for the pur phases
appear in the high part of the reflections respectively at are n reciprocal space, the more the curve of the reflec-
9.1A (pyrophyllite), and at 10A (Hite) 16 tion movement levis out for intermedate compositons, at
the same time as the reflecton becomes diffuse (after
Figure 12. - v/p ratio ( valley >/ peak height ratio) for the Mac EWAN and RUIZ-AMIL n GIESEKING, 1975) . 47
characterization of the crystallinity of smectites (after
BISCAYE, 1965). The measurement s achieved on the 1 7 Figure 25. - Eight types of interstratificaton of A- and B-layers.
peak of the glycolated material. p is measured below Regularly interstratified minerals (alternating ABAB :
the apex of the 1 7 reflection, above the background ; AABBAA : AAABBB ; ABBABB ; AABBBAABBB ; segrega-
" v s measuring the importance of the depression ( val- ted material : alternating AAAABBBB ; randomly interstrati-
ley ) towards the low angle side of the 1 ?A reflection. fied structures ; alternating ABABBAAB, and ABAABBBetc... 47
(A) : well-crystallized smectite ; (B) and (C) badly-crystal-
lized smectites 18 Figure 26. - Schematic representaron of the reflection zones
of an interstratified structure formed of A- and B-types of
Figure 13. - Empirical crystallinity classes of smectitic layers (LUCAS, 1963) 48
materials based on : 1) the shape, symmetry, ntensity of
the 1?A reflection ; 2) on the occurrence/absence and shape Figure 27. - Schematic representaron of the composition of
of the (002) at about 8A, and (003) at about 5.4. (THOREZ). 19 a system consisting of interstratified particles, and possible
X-ray diffraction curve aspect for difieren! mixed layers
Figure 14. - Relationship between the crystallinity ndex v/p composed of A- and B-layers (interlayers). Cl = degree of
of BISCAYE (1965), and the crystallinity classes of interstratification (vales from O to 1 ) ; n = number of
THOREZ (1974, unpublished data), allowng the charac- partiles with a given a (modified after KUBLER, 1961 ;
terzaton of the smectite evolution durng weathering or LUCAS, 1973; in THOREZ, 1975) 49
in a sedimentary nterval of sediments rich in smectites.
This relationship can be provided independently of the Figure 28. - WEAVER's method for the analysis on the X-ray
smectite composition . . . 19 diagram of an nterstratified mineral 50

Figure 15. - Differentiation between smectites (montmoril- Figure 29. Schematic representaron for the reflections of
lonites) vaneties after selective treatments (after THOREZ, mixed layers relatively to the position and intensities of the
1975). 20 pur phases (n this case montmorillonite and muscovite)
(after BYSTRM, 1956) 50
Figure 16. - Effects of amorphous material during the Li-test
of GREENE-KELLY, (1953) for the distinction between mont- Figure 30. - First-order apparent spacings for the three com-
monllonite and beidellite (after MURAVYOV, 1970, and ponent interstratifications that can be formed from 1 O, 1 2.4,
THOREZ, 1975) 22 14, and 15.4 spacings (after JOAS and BROWN, 1959,
also reproduced in GIESEKING, 1975) . . . . 51
Figure 1 7. - Basal reflection (001) n for vermiculite minerals
treated with water or glycerol as affected by the nature Figure 31. - Position in d() of the (001) and (002) reflections
of nterlayer catin and the method of sample preparation for regularly interstratified minrals : (C-V), (C-M), Cg-m),
(after BARSHAD, 1958, i n THOREZ, 1975) . . . 27 (Cg-V) and (M-V) after diagnostic treatments (ethylene
glycol and heating) 55
Figure 18. - Basal reflection (001) in for glycerolated mont-
morillonite minerals as affected by the catin exchange Figure 32. - Behaviour of the " basal " reflecion of random
capacity, the nature of the nterlayer catin, and the method mixed layers (14Q-14v) upon diagnostic treatments (ethy-
of sample preparation (with prevention of drying) (after lene glycol and heating) 56
BARSHAD, 1958, n THOREZ, 1975) 28
Figure 33. - Schematic presentation of the characteristic beha-
Figure 19. - Differentiation between vermiculite varieties -beha- viour and shape of the basal > reflection of random mixed
viour of the d(001) upon treatments (THOREZ, 1975). 29 layers (140-14^) upon diagnostic treatments (ethylene
glycol and heating) 57
Figure 20. - Chiorite species boundaries according to HEY
(1954) for the orthochlorite (A), and oxidized chlorites (B). Figure 34. - Schematic presentation of the characteristic beha-
Abbreviation symbols : pThur ~ pseudothuringie, Corun = viour and shape of the basal reflection of random mixed
corundophilite ; Daph = daphnite ; Ripi = ripidolite ; Sher = layers (14Q-14Q) upon diagnostic treatments (ethylene
sheridanite ; Bruns = brunsvigite ; Pycn = pycnochlorite ; glycol and heating) 58
Cuno clinochlore; Dia diabanite; Penn = penninite;
Talc-Chlo - talc-chlorite ; Thur = thuringite ; Klem = klemen- Figure 35. - Schematic presentation of the characteristic beha-
tite ; Cham = chamosite ; Deles = delessite . . . . 32 viour and shape of the basal reflection of random mixed
layers (10-14^) upon diagnostic treatments (ethylene
Figure 21. - Chiorite species boundaries according to FOSTER glycol and heating) 59
(1962) (U. S. Geol. Surv., Prof. Paper, 414, A-19).
Abbreviation symbols : Thur = thuringite ; Ripi = ripidolite ; Figure 36. - Schematic presentation of the characteristic beha-
Bruns = brunsvigite ; Cham = chamosite ; Diab = diaban- viour and shape of the " basal reflection of random mixed
tite 32 layers (10-14) upon diagnostic treatments (ethylene glycol
and heating) 60
Figure 22. - Schematic X-ray diffraction patterns of four chiorite
polytypes (based on data of BAILEY and BROWN, 1962, Figure 37. - Schematic presentation of the characteristic beha-
p. 839). The indexed, solid black bands are diagnostic for viour and shape of the " basal reflection of random mixed
each structure. The diagnostic (hol) bands of Ib (P=97) layers (10-14v) upon diagnostic treatments (ethylene
a r e broadened. (from HAYES, 1970, p . 288) . . . 35 glycol and heating) 61
INTRODUCTION
The problem of identifying the various existing clay minerals be combined : he (OOI) reflections allow a quick routine
has already been dealt with by several authors (BROWN, 1961 ; idenlificafion of he species or groups of minerals ; he powder
LUCAS, CAMEZ and MILLOT, 1959 ; WARSHAW and ROY, preparalion provides the enlire (hkl) specra for the concerned
1961 ; BRADLEY, 1945; LUCAS, 1963 (1968 in the English clay mineral, and s recommended when one has to deal
translation). Recently two other reference books have been with specific informations such as : the dioclahedral or Irioc-
published on the subjecl. lahedral characler, he polylypes, he crystallinily of the minerals,
the isomorphous subslilulion, etc...
The first one, edited by GIESEKING (1975), deals with the
identification of norganic soil components. Several well-known II is Ihus possible lo derive basic informafion firsl from fhe
scientists have contributed to that work which recalls traditional orientad aggregates of fhe clay minerals. A body of knowledge
data on the clay minerals, but also provides up-to-date and has now been buill up, for some decades and by several
past informations as well, all of them having been published aulhors, which enables he differenl clay mineral groups (and
in several papers since BROWN's book (1961). sub-groups) lo be recognized when he material occurs as
mono-mineralic componenl, or includes differenl componenls
The second one s by THOREZ (1975). Its objeclive is to in a mechanical mixlure.
provide to the clay scientists a series of identification keys
for clay minerals by X-ray diffraction analysis, both for oriented The majorily of clay minerals have layer slrucures consisling
aggregates and random powder preparations. The identification of parallel layers conlaining Si, Al, O and OH, somelimes
s conducted step-by-step on account of the wanted accuracy. combined wilh Mg, Fe and olher elemenls. The layers consisl
Emphasis has also been put on the effects of complementary of parallel sheets of atoms which are firmly bound logelher lo
tests (cation-saturations, glycolation, heating) in order to reach provide a more or less fairly sfable slruclure. Belween layers
a better identification. The work also contains : a series of he forces are usually weaker. So Ihal he sheels of aloms
stylised X-ray diffractogram patterns of oriented aggregates ; are bound logelher lo form layers. The layers are Ihen super-
the (hkl) reflections for about 420 varieties n both clay minerals posed lo form he cryslals. The classif icalion of fhe clay minerals
and phyllosilicates, and a general glossary. is largely based on slruclural consideralions for bofh the
composilional range within mineral groups, and the same order
The aim of the present handbook is to provide and recall to the belween groups.
teachers and students n clay mineralogy some basic X-ray
diffraction characters of clay minerals, including mixed layers, Two main types of layer appear in clay minerals : there are
in oriented aggregates. Some specific data are also presented he 1:1, and he 2:1 lypes. The former is made up by he
for the routine identification according to the X-ray patterns condensalion of one sheel of lelrahedrally coordinaled calions
of random powder preparation. The author recalls some basic wilh one sheel of oclahedrally coordinaled calions. The thickness
data, those usually used when one is concerned with the direct or elemenlary height of a single 1:1 layer is about 7.2 (as for
exploitation of diffractogram patterns. Therefore the conten of kandifes). The 2:1 lype which is he basic layer of micas (and
this handbook is to be beer considerad as a companion of the Hiles), chloriles, vermiculiles and smecliles, is made up by he
former laboraory handbook published by the author in 1975. condensalion of lwo telrahedrally coordinaled sheels of ca-
Its content can be easily combined with the one provided in lions, one on eilher side of oclahedrally coordinaled sheel.
THOREZ (1975). The Ihickness of a single 2:1 layer is aboul 9.3.

To define a clay mineral, its composition, and eilher is struc- In a wide sense he 1:1 lype layers are eleclrically neulral.
ture or some other properies tha are closely related to its The 2:1 layers oflen carry a negalive charge due lo isomor-
structure must be known. phous subtitulions. These negalive charges are balanced by
posilively charged aloms or groups of aloms which are silualed
As mostly clay minerals exist as partiles less han 1 micron and inlercalaled belween successive 2:1 layers. As a conse-
in diameer, and oflen occur in mixures, isolalion of pur quence he layer heighl for he 2:1 lype clay minerals depends
minerals is no easy. The slrucures of clay minerals can be on size of fhe posilively charged nlerlayer spaces. As an
sudied n a more or less direc way by X-ray diffracion method, example, in micas, K ions balance he charge on he 2:1 layers
particulary for he deermination of the aomic arrangement in and he elemenlary Ihickness of fhe mica layer is aboul 10.
crystals. The informations obtained from X-ray diffraction specra In vermiculite, moderalely hydraled calions are inlercalaled
can besubdivided inlo a wo-fold purpose : 1)lhe measurement belween lhe=2:1 layers, and he heighl of fhe vermiculite layer
of the geomerical disribution which corresponds tothegeome- s aboul 14. In smecliles, he balancing calions are more
try of atomic planes in the crysal (particularly at the level highly hydraled ; he layer heighl depends bolh on he precise
of he nerplanar spacings and nterplanar angles); 2) the nalure of he calion and on the humidity.
measuremen of he intensities of the reflections (he inensiies
are relaed lo he arrangemenl of aloms in planes). It s on the basis of he differenllhicknesses Ihatthe clay minerals
as single componenl or in mixlure are recognized by X-ray
Because of he nalure, size and cryslallinity grades n clay diffraction analysis. The X-ray pattern, since il allows a measure-
mineral particles, Ihere is a main difficully lo oblain easily he men of he distance between similar planes of atoms, provides
wanled informafions. Therefore I s indicaled to analyse the a direct measure of he heighl of the layers.
samples bolh as random powder preparalions, and as orienled
aggregates. The advanlage of he latter melhod is the enhance- The height of fhe layers, he nalure of he inlerlayered material,
menl of the infensilies of he basal reflecions, he so-called and he degree of hydrafalion in clay minerals can be usefully
integral series of he (OOI) reflecions which are alone repre- checked by fhe X-ray diffraclion in oriented aggregates of he
sentad in the X-ray patlern while he (hk) reflecions are nof clay fraclion (minus lwo-microns fraclion). The unlrealed (nalu-
reproduced. The lwo above quoled analytical melhods are lo ral : N) sample provides already some indicalions aboul he

XI
nature of the clay component(s). These indications can be The second aspect has some links with the first one just
further developed with complementary tests which are intro- presented. It concerns the quantitative (or semi-quanti-
duced n the analysis : effects on the basic spacings by the tative) evaluation of the clay mixture. It is clear that when a
solvation with ethylene glycol (EG) or giycerol (Gl), or by heating certain clay mineral is present n the mixture as a not very
treatments at various temperaturas (usually at about 490-550C). importan! component, there always is a risk not to detect it;
Also cation-saturations with Mg, Na, Ca, K, Li, etc..., combined if there are moreover overlapping effects for some of its
with glycolation (glycerolation) and heating, allow to reach, n reflections used for the evaluation, some misinterpretation
some cases, a better knowledge of the composition and may also occur.
structure of the material. As it will emphasized lateron, also of
interest are other tests which concern intercalations with organc A third aspect to be pointed out is the existence of mixed
and inorganic compounds such as hydrazine, K-acetate, DMSO. layers. There are cases where the combined layers of such
Some clay minerals do not resist to acid attack (HCI in instance). minerals are arranged in a regular way (cf. regular mixed
Thus f one proceeds to a cise examination of the behaviour layers) with respect to each type of layers. But there exists
of the basal reflections of clay minerals after the above cited randomly interstratified structures as well which are not true
tests, it is possible to reach the identificaron of the clay minerals. For the latter the disorder in their stacking of layers
components. But then further indications may sometimes be exists both in the structure and partiles. The interpretation
achieved f, n combination with the oriented aggregates, one of mixed layers, particularly the randomly ones named inter-
analyses a random powder mount of the same sample, and stratified structures, may sometimes be difficult. The difficulty
checks carefully some specific (hko) reflections (in both increases when such structures are engaged in mixture with
positions, and ntensities). other clay components.

In connection with the interpretaron of X-ray diffraction In an effort to reach a better differentiation between regularly
patterns of simple and mono-mineralic clays, there are also and randomly interstratified materials, a specific code has
three other aspects of the determination. been introduced and published by THOREZ (1975). Some of
these informations will be repeated here in the part of the
One concerns the recognition of the clay components into handbook devoted to these types of materials. The proposed
mixtures. In some cases there will be no problem at all method of transcription for mixed layers s not be considered
because the diffraction lines (reflections) of the components as a precise one. It serves the routine identificaron as it
are sufficiently separated one another n d-spacing and emphasizes more fully the characteristic behaviours of the
ntensities, and/or on account of their behaviour after certain combined layers on account of their behaviour upon deter-
dentification tests. mination tests (EG, Gl, heating, saturation, etc...). In fact, as
it will be illustrated in the coloured dentification keys, the
But there often occurs overlapping of reflections in certain aim of the proposed system of codificaron is to obtain first
parts of the X-ray pattern (i. e. the case of a mixture of some basic information about the composition before fur-
kaolinite and chlorite). Or some diagnostic reflections for ther and more precise data can be obtained by a more
a specific mineral are not readily available in the X-ray elaborated method of analysis (Fourier transform) of the real
pattern because of the masking effect by the reflections structure of the material.
(asymmetry, tailing) belonging to the other minerals which
are more or less degraded. Some care has to be taken when
such cases are encountered or suspected, and there is thus
indication to make detailed investigations.

XII
I. - TERMINOLOGY OF THE CLAY MINERALS
Terminology here used for clay minerals is based on the proposal An extensive comment about the content of this table exceeds the
classification for clay minerals and related phyllosilicates as issued scope of this chapter. It is however mportant to point out a decisin
by the Nomenclature Sub-Committee of the A. I. P. E. A. (BRINDLEY taken during the 1976 International Clay Conference, held in
1966, 1967 ; modified after the Madrid Clay Conference in 1972). Mxico ; its concerns the substitution of the group ame mont-
The classification scheme is here presented (table 1). morillonite-saponite by the ame smectites .

Layer type Interlayer Layer charge Group ames Subgroup ames Species
(octahedral layer)

Kaolinite- Di : Kaolinites
Kaolinite, Halloysite,
Serpentine Nacrite, Dicktite
1:1 Without 0 or
Kandites Tri : Serpentines Chrysotile, Lizardite,
Antigorite

Pyrophyllite- Di : Pyrophyllites Pyrophyllite


Without 0 Talc
Tri : Tales Tale

Di : Montmorillonites Montmorillonite, Beidellite


Beidellite
~0.25<x<0.6 Smectites
Saponite, Hectorite,
Tri : Saponites Sauconite

Di : Vermiculites Vermiculite
~0.6<x<0.9 Vermiculites
Tri : Vermiculites Vermiculite
2:1
Dry or Di : Muscovites Muscovite, Paragonite
Hydrated x~1 Micas
Cations Tri : Biotites Biotite, Phlogopite

Di : Margante Margarite
x~2 Brittle Micas
Tri : Clintonite Seybertite, Xanthophyllite

Di : Sudotes Sudotes, Cookeite


Hydroxyde X

Layers variable Chlorites Di-Tri : Donbassite Donbassite

Tri : Chlorites Penninite, Clinochlore

Table 1. - Classification scheme for layer silicates.

II. - SAMPLE PREPARATION


This handbook has not the objective to deal with all problems work will clearly show how drastic may in its effects be the appli-
encountered with the preparation of the clay minerals as well as cation of some traditional methods, and how the procedure modifies
it does not indcate a choice of procedure. the identificaron of the clay components. So that, at this time, each
The important thing to be pointed out is the actual lack of standar- clay scientist may still refer to the method of his choice, until a
dization in the methods of extraction and preparation of (oriented standardizaron s proposed. But some anticipative remarks may
or random powder) material before the X-ray diffraction analysis. already be provided.
Each clay scientist or each generation of clay scientists, uses its Sample preparation must be the simplest as possible. Such tiny
proper preparation method. The danger is that the results obtained and mild materials that are the clay particles are very sensitive to
after different schemes of preparation might well not be easily certain chemical pre-treatements.
compared even for a same material because some sensitive dis-
crepancies may occur when the clay minerals are prepared fol-
lowing different methods. Excepted for some highly organic-rich soil material, it s always
possible to extract and prepare the clay particles with distilled water
by a series of centrifugations and sedimentations as completed n
In order to be able to compare the effects induced by several Lige Laboratory. The use of dispersan! or flocculation agents is
different methods of extraction and preparation published n the also to be avoided. Some of the traditional pre-treatments, beside
literature, THOREZ (n preparation) has started to analyse clays the fact that due to their application the preparation of samples
extracted from soil and sediments by near twenty procedures. The becomes very long, may induce inaccurate determinations or lead to
contradictory results f comparison is made with a material treated in mind that some drastic consequences might occur when the
with distilled water. It s also indicated to use cation-saturations preparation method follows some very elaborated procedures found
only when the set of the classicaltreatments (N, EG, 500C) has n the literature. It is the author's opinin that the clay material has
been recorded in the X-ray pattern, and after a first evaluation of to be analysed when prepared with the less chemical manipula-
the composition has been made. By selecting the post-treatments, tions. The clay minerals have to be analysed as the more n
one can spare time for the essays, especially when a large amount situ as possible, because the clay fraction may then keep these
of samples has to be analysed. The author invites thus the reader fugitive clay partiles that are the random mixed layer structures
to refer to his own and usual method of preparation, and to keep so sensitive to the pre-treatments.

I. - QUANTITATIVE ASPECTS OF THE ANALYSIS


Truly quantitative evaluations are not yet possible n complex clay unjustified assumptions, i. e. the uniform scattering from samples
minerals assemblages. However for simple ones there exists several treated by different methods. Nevertheless, t gives reproducibility
methods published by different authors ; some methods involve the in the treatment of the curves, which n a comparative study is of
artificial (mechanical) separation of the components. It s not also vital mportance . (GJEMS, 1967, p. 338).
ntented here to deal with all the aspects of the quantification of Another procedure interests the measure of the intensities of the
clay mineral mixtures. Some simple semi-quantitative procedures (hkl) reflections for completely unoriented samples. If a high degree
will be recalled. of accuracy can be obtained by this method in pur mixtures
Certain authors use the intensities of the basal reflections of the (MITCHELL, 1960; MACKENZIE, 1961), it s mportant to recall
clay minerals, and compare them after treatments (glycolation, that, in natural clay sample, the (hkl) reflections cannot be referred
cation-saturations, heating). The evaluation has of course to be to those of fixed standard clay minerals. That s the reason t s
combined with the results of the qualitative investigaron, n order better to utilize the basal reflections for a quantitative approach as
to take into consideraron all the possible minerals present n the provided by oriented aggregates X-ray patterns where these reflec-
assemblages. On another hand, t is moreover indicated not to tions are only produced at the cost of the (hk) ones (JOHNS et
deal with too complex procedures of quantification especially n al., 1954 ; GRAF-PETERSEN, 1961).
important series of samples.
A quantitative evaluation of clay minerals s, in any case, very
The intensities of the clay minerals, particulary those related to the uncertain because of the varying degrees of crystallinity eventually
(001) basal reflections, cannot always be used as a measure of the combined with the varying chemical compositions within individual
abundance. mineral groups (GRIM ef al., 1957). Amorphous material that is
Iron-rich chlorites display a very weak basal reflection at 14A which not easily, or not removed by mild pre-treatment may also interfere
becomes enhanced only on heating. Also is the frequent case of with the quantitative estimation. So that great efforts are sometimes
the basal reflection of a specific mineral to become more or less consented for a mathematical approach of the clay assemblages
masked by an accident related to near reflection(s) belonging while, at the first step, one might be not attentive at all to the effects
to other minerals. There are cases of variations n the intensities of the amorphous materials on the final X-ray results.
of the basal reflections due to : sample-mounting and X-ray condi-
tions ; sude thickness ; degree of the prefered orientation ; weaken- For nstance, GJEMS (1967) has used, n the estimation of his series,
ing of the orientation by hydroxydes ; segregation effects during a principie ntroduced by OINUMA and KOBAYASHI (1961) for the
sedimentaron of the clay partiles onto a glass-support. Natural treatment of a system llite-hydrous illite-montmorillonite.
defects also occur in the minerals at the level of the different atomic There are simpler techniques for a semi-quantitative estimation of
planes. Non-uniformization of the preparation may ntervene thanks the clay mineral conten. They involve the measure of the height
to variations in the granulometry. Variations in crystallinity may take of the (001) reflections, above the background. JOHNS era/., (1954)
place particularly n soil clays, according to the sample position provided correction factors : the 1 7A glycolated smectite reflection
in the profile. appears as fpur times (4x) the 10A reflection of the Hite, and twice
Going back to quantitative evaluation methods one has to point (2 x 7) the 7 reflection of kandites (the reflection being for the latter
out again the lack of standardizaron among all the laboratorios taken as the real intensity or as the standard reflection rea).
dealing with this difficult problem. Then the intensities (or the reas) are summed and give the
Ratio of peak reas have been ntroduced. As proposed by JOHNS percentages for each represented clay mineral.
e al. (1954), percentages of each of the major clay mineral WEAVER (1958) has also proposed the following assertations :
components can be calculated when they are based upon their equal amounts of 10A Hite and 14 montmorillonite are equivallent
basal peak reas ; these are then weighted so as to make direct to the ratio : 14 = 3x10. The 7 (of kandite) is two to three (2-3)
comparison. But a main difficulty arises about the way the different more intense than the corresponding 10A of ilute n the same sample.
reas are to be limited (especially when multi-component assem- The present author has always used the method of Strasbourg's
blages occur with possible overlapping of their basal reflections and Clay Laboratory. This semi-quantitative approximation of the conten
about the manner in establishing the background configuration n clay minerals s based on a relative frequence of the minerals ,
beneath the basal reflections). the total association being equal to 10. Heights of the (001)
GJEMS (1967) treated the problem of where to place this back- reflections are measured above the background and taken directly
ground curve : this curve s approximately horizontal at the higher into consideraron. Only, by convention, is the intensity of the 7A
angles n the diagrams, but rises sharply at lower angles towards (kaolinite) divided by a factor 3 (2 o for b o adly-crys o tallzed kaolinite),
029. The simpiest approximation to this theoritical background relativelyto the intensities of the 10, 14Aand 1 7A of the glycolated
curve s a hyperbola with formula x.y=a. A set of different hyper- sample. Of course such a method has weaknesses in particular
bolas with vales o f a equal to 1, 2, 4, 8 and 16 cm, where drawn. when random mixed layer structures ntervene n the clay assem-
They were placed under the diffractometer curves and the hyper- blages and presen t the ir typi cal dif fraction bands (plateau); for these
bola giving the best fit, at both high (greater than 1229), and low there does not exist any discrete reflection or zone where to
angles (2-326) was drawn on the diffractograms and used as the measure the ntensity because of the scattering effect; the relative
background curve. This was first carried out on the untreated ntensity is taken at the half of the band, thus, there exists a risk
sample, and the same background curve then used for the glycol- of underestimation of the relative frequence of the mixed layer
treated sample. As the background often appears diminished n component. The advantage of this method is to be relatively rapid
ignited samples, a second hyperbola was used for these. This which is of great nterest when important series of samples are
technique of estimating the background has its weaknesses, and to be analysed.
Again, as already discussed in the chapter dealing with the sample one is free to use his own method of quantification. The important
preparation (II), there s no rule at all for the quantification of principie, n the publication, isalwaystogive, even briefly.the method
clay assemblages even when a review s made of all the published utilized so that the reader could be able everytime to convert the
literatura. It is the author's feeling and position that, until no general data into his own system of quantification .
agreement has been taken by the international committees, every

IV. - DETERMINATION OF THE CLAY MINERALS BY X-RAY ANALYSIS


The identification of minerals by X-ray diffraction analysis is based chapters. At the end of chapter IV, the reader will n particular find
on the reflection of X-rays by the characteristic atomic lattice planes a set of indication keys for various clay minerals including mixed
within the mineral crystals. layers (regular and random). These different keys provide data on
Thanks to their typical habitu , the clay minerals have the more the behaviours of the basal reflections (001) of the clay minerals,
favorable lattice spacings (when prepared as oriented aggregates) but (002) for regularly interstratified minerals, after the three treat-
for a detailed identification by X-ray diffraction, particularly for a ments providing the X-ray patterns of the untreated (natural N),
routine determinaron . Of course any clay fraction does not neces- the glycolated (EG) and the heated sample (oriented aggregates).
sarily bear only the layer-lattice minerals ; it may also contain other In some of the tables one might find complementary data relative
minerals such as quartz, feldspar, amphiboles, pyroxenes, zeolites, to the effects of cation-saturations etc... For detailed and complete
and various hydroxydes as well amorphous materials. But the topic informations, the reader will refer for nstance to the Laboratory
of this handbook s essentially focused on the determination of the Handbook previously published by the author (THOREZ, 1975).
layer silicates. Different information will be provided n the next

IV - A. - DESCRIPTIVE CODE FOR THE d-SPACINGS OF CLAY MINERALS

In order to provide to the user a guick and simple guiding-mark (glycolation, glycerolation, heating), and to present this objective as
in the search of the position, n d(), and behaviours of the basal a mnemotechnical tool, the d-spacing vales and ranges of the
reflection of clay minerals upon different diagnostic treatments (001) reflections have been represented by colours and symbols.

d-spacing n for the (001) of clay d-spacing in for the (001) of clay
Symbols minerals & (002) of mixed layers Symbols minerals & (002) of mixed layers Symbols Signification

- No reflection
O 13,5-13,8 s~\ Broad reflection

7 ~7 13,9-14,3
r-i Diffraction band

% 9-9,7 *
14,6-15,3 OP Doublet

1 9,8-10,1
e 15,5-15,8
L
Asymmetry towards
low angles

A 10,3-10,5
o 16-16,5
Asymmetry towards
high angles

V 10,6-11
o 16,8-17,2 J
Reflection with
enlarged foot

A 11,2-11,7
17,3-18
. . > ^(*)
(#) Origin, n A, of
the tailing reflection
'

/Q Doublet Possibility of two d-spacings


11,9-12,3 J" for the basal reflection
"/VlH [.e. (10+13)]

B V^ Diffraction band
+
Variation of the d-spacing
^r~1
12,5-13,3
[i.e. (11-14)] for the basal reflection

Table 2. Explanation of the motifs and symbols.

Each colour corresponds to a specific range of d-spacing in . The RED corresponds to intermedate d-spacings (with vales
The YELLOW corresponds to clay minerals whose basal reflections ranging between 11.9and 13.3).
are around 10-11, i. e. micas (these latter are generally white to The BLUE jecalls water, and is reserved for all the d-spacings
slightly yellow n natural samples). above 14.3. In particular it emphasizes the swelling of the basal
The GREEN corresponds to clay minerals with a basal spacing reflection upon solvation (with ethylene glycol and glycerol).
around 14, i. e. chlorites (ordinarily green n nature).
The first subdivisions of the d-spacngs ranges are mmediately This blackening is not chosen at random. It is progressively ob-
marked by a definitiva colour. These coloured ranges are further tained step-by-step n each of the symbols. For nstance, let us take
subdivided n narrower ones by different mnemotechnical symbols. the case pf the circle. The n creas i ng and the range of the d-spacings
In the choice of the latter, special attention has been drawn n in the circle are gradually indicated by : an open circle with a
order to provide a cise correspondence between these secondary central black point, a c/>c/e subdivided by an horizontal black Une,
subdivisions n the d-spacing ranges (limited by their proper colour} a circle subdivided into four sectors, two opposite being blackened,
and the appropriate symbols. In the choice of these symbols, the a solid black circle with a white central point, and finally a solid
number of sides and a gradatory blackening (that ncreases n black circle ; the gradation n the blackening of the circle -symbol
the same symbol) play their role to provide a complete sequence of s thus in relation with the different d-spacings : 14.6-15.3A;
symbols indica:.ing d-spacings increasing from 9.6A to 1 7. 15.5-15.8 ; 16-16.5A ; 16.8-17.2 and 17.3-18.
The selected symbols comprise : a dubbel "-like design , a narrow The most blackening for the different symbols has been managed
but vertically placed rectangle, a triangle, a square, an hexagone, to have spme _ strategic d-spacings emphasized : 10A; 12A;
a star, and a circ/e. 13.5-13.8, 14A, 17-18, because they are related to either specific
There exists a cise relationship between the definite range of clay minerals the (001) of which has a definite d() valu, or to the
d-spacings and the, shape and type of the corresponding symbol. behaviour of the d(001) upon treatments.
For instance, a 10A reflection will be represented by the rectangle All the d-spacings presented n figures and n the tables are ob-
(which has two sides) ; a 11.4, by a triangle (three sides) s. 16, tained for a Cu-anticathode, and a Ni-filter. Another set of mnemo-
by a circle (because of the swelling character, this symbol ndicates technical symbols can be used n parallel way and in association
the occurrence of an infinity of sides). with the just described ones. This complementary set (table 2)
is used n order to provide some further indications relatively to
Gradual blackening of these different symbols, exception for the the shape of the (001) reflection : doublet, broad reflection, dif-
dubbel -like and the rectangle ones, has also been ntroduced. fraction band, asymmetry etc...

EXPLANATION OF THE MOTIFS AND SYMBOLS


"LO
Or doublet narrow but symmetrical reflection

narrow and symmetrical reflection with an increasing


Broad reflection ntensity (.e. heating the sample)

narrow and symmetrical reflection with decreasing


diffraction band or plateau ; ntensity

A large but still well definite reflection contraction of the d-spacing

18 I asymmetrical reflection towards the low angle side of


- A the diffractogram expansin of the basal d-spacing

18 I asymmetrical reflection towards the high angle side of


- K the diffractogram occurrence of two possibilities for the d-spacings

IV - B. - KANDITES (Kaolinite) : symbol K


IV - B - 1. - GENERALITIES FOR DIOCTAHEDRAL MINERALS
Kandites (kaolinite, dicktite, nacrite, halloysite) can and must be The behaviour of the basal reflection (001) upon the classic '
investigated by X-ray diffraction techniques both as oriented ag- treatments can be expressed as follows :
gregates and random powder preparation for their identification.
Treatments N EG 500C
In oriented preparations, kandites are easily recognizable by their
(OOI) sequence of harmonio reflections at : 7 (001), 3.58 (002), (001) n d() 7 7 suppressed
and 2.37 (003).
These (OOI) reflections are stable after glycolation (or glycerolation).
Between 400C and 450C they show a slight decrease of nten- In the case of a hvdrokaolinite (halloysite) which basal reflection s
sity. After having been heated to 500C they are suppressed from situated near 10A, a pre-treatment by heating the sample o at 80 tp
the X-ray pattern providing the preparation has been calcined long 110C irreversibly changes the basal spacing from 10 to 7A.
enough (2 to 4 hours); this characteristic corresponds to a complete Afterwards the mineral behaves tself as another kandite upon treat-
dehydroxylation of the mineral. ments (glycolaton, glycerolation, heating).
IV - B - 2. - IDENTIFICATION OF DISCRETE SPECIES
In oriented aggregate, and in first approximation, a well-ordered Species in the kandites, as well varieties of kaolinite are determined
(well-crystallized) kaolinite can be assumed by the o presence of in the field of order-disorder, from the X-ray patterns of powder
narrow, symmetric and relatively intense 7 and 3.5A reflections. (unoriented) aggregates. Of course there is the problem to obtain
The ntensity of the (001) reflections decreases according to the a perfectly desoriented preparation for this objective. QUAKERNAAT,
degree of desorder ; in a parallel way the reflections become (1968), among others, has discussed the problem and offered some
more or less asymmetric (asymmetry of the 7 reflection towards practical techniques.
the low angle side of the X-ray pattern ; asymmetry of the 3.5 The determinaron of disorder is summarised in the table 3 where
reflection towards the high angle side). Highly disordered kaolinites distinction is readily displayed for : kaolinite sensu stricto, dis-
even display, beside the low-intensity and asymmetric (001) reflections, ordered kaolinite, metahalloysite, hydrated and dehydrated halloysite
a more or less pronounced diffraction effect (as a broad reflection) (data kindly communicated by SIFFERMAN). Tables of (hkl) reflec-
at about 4.4A (corresponding to the (02) band). tions are provided by BRINDLEY in BROWN (1961), and THOREZ
(1975). (See table 4).

Powder DISORDERED
diffractogram reas KAOLINITE METAHALLOYSITE
HYDRATED DEHYDRATED (80"C)
(d-spacing n A) sensu stricto KAOLINITE HALLOYSITE HALLOYSITE

sharp, but 10, intense, 7.3, asymmetric,


7.15 sharp 7.15-7.5
of lower intensity (mean : 7.2), symmetric or not, as band or reflection,
7 and than for but then extending often extending
very strong often enlarged
kaolinite s. s. towards 7 towards 9
often extending
4-4. 4 diffraction
diffraction band band very asymmetric
distinct reflections, with occurrence 4-4. 4 band 4-4. 4 asymmetric.
4.43 and lowered n as diffraction band
4.35 of lower ntensity of one or two of often asymmetric, ntensity from 4.4 more intense than
versus 7.1 and the three reflections with an ntensity to 4.
4.15
(following the = 7.2 for the hydrated
3.5 reflections Often more intense halloysite
crystallinity) than the 10
Intensity = 7.1

3.5 with 3.6


3.5 of lower intensity an ntensity equal 3.3 with an ntensity
3.5-3.6 3.56 very strong than or lower than equal to the half of less intensity
for Kaolinite s. s. of the 4.4 . than for the 4.4 band
for the 7

3.36 weak
3.13 weak
3.09 weak
2.74 weak

2.56 2.5-2.55 diffraction 2.5-2.55


group 2.50 pair broad reflection,
2.52 band. diffraction band ;
of reflections of reflections often uninter- Intensity equal to 3.3 2.5 often defined
2.49
rupted from 2.56
to 2.30, 2.36 as band 2.40 weak.
2.38 with possible 2.56 2.36-band
group 2.37-2.33 as pair of lower ntensity
2.34 2.50A and 2.32 relatively to 2.5-2.55 more intense
of reflections of reflections reflections
2.29 than for the
hydrated halloysite

4.43, 4.35 4.43-4.12 Same as for the X-ray pattern of powder


and 4.15 4.4-4 band
Oriented of lower ntensity. preparation. When heated to 80-1 10C,
almost disappeared. with ntensity
aggregate 7.1 and 3.56 = 7 and 3.56 the 10 reflection js irreversibly replaced
7.1 and 3.56 ncreased n ntensity by a 7 reflection.
increased n intensity

2ole 3. - Routine differentiation for kaolinite minerals (X-ray powder pattern) (Data kindly provided to the author by SIFFERMAN)

Well-crystallized kao/inite s recognizable in powder preparation by Nacrite resembles dicktite n its X-ray powder pattern, but has
the numerous sharp reflections, the low background, and the generally fewer reflections, and shows perceptible differences both
presence of resolvable doublets and triplets at approximatively : n its d() positions and intensities. A characteristic reflection for
4.15. 3.80, 3.1 O, and 2.50. BRINDLEY (op. c/'.) considers the nacrite occurs at 2.43 (intensity : 6-7).
sharpness of all the (hkl) reflections, and the resolution of the (111) Disordered kaolinites display fewer reflections than the X-ray powder
and (111) reflections, and of the two triplets at 2.46-2.49 and pattern of kaolinite. Halloysite and hydrated halloysite have powder
2.38-2.28, as criteria for a perfect structural layer stacking (see patterns ressembng those of disordered kaolinite, but with broader
also paper by DIMANME e? al., 1974). series of (OOI) reflections, weaker intensities, and higher d-spacings
Dickite resembles kaolinite by its sharp resolvable reflections. than those of any kaolinite.
But there exists several reflections that have no parallel n kaolnite, Fre-clays show a complete set of kaolinite reflections but with a
and other reflections in similar positions to kaolinite but with decrease n intensities. The weakness of intensities reaches a
different intensities (see table 4 providing data from DOUILLET mximum n the case of hydrokaolinite for which the asymmetries of
and NICOLS, 1969). reflections become general, in particular for the (OOI) reflections.
The characteristic triplets of the kaolinite are more or less replaced IV - B - 3. - BEHAVIOUR OF KAOLINITES
by doublets in fire-clays, and by single but broad reflections in some
hydrokaolinite (DOUILLET and NICOLS, 1969 ; DIMANCHE ef al., WITH ORGANIC AND INORGANIC COMPOUNDS
1974).
It is also been proposed, by several authors, a complementary test
in the study of kandites. This test particularly displaces the basoal
(001) reflection at 7 to a position situated at higher vales in d(A).
characteristic KAOLINITE DICKTITE This test concerns the treatment with hydrazine, DMSO or K-acetate,
reflections d() I d() I combined or not with ethylene glycol or glycerol. Such a treatment
can be useful for the differentiation between kaolinite and entorile
4.18 5 4.27 3 in mixture because of the overlapping of the 7 and 3.5A reflections
3.84 4 3.95 2-3 in both the minerals. This overlapping is presented in the following
peculiar 3.74 2 table :
reflections 3.37 4 3.42 3
3.14 3 3.26 2 (OOI) reflections (001) (002) (003) (004)
2.75 3 2.79 2
Kaolinite 7 3.5
common reflec- 4.13 3 4.13 6-7 Chlorite 14 7 4.7 3.5
tions, but with 1.94 4-7 1.94 1-2
different 1.78 4-5 1.78 1-4
intensities 1.62 6-8 1.62 1 Hydrazine displaces the 7 (001) reflection to 10.4. The reaction
is reversible. Practically after 24 hours the treatment with pur
supplementary 2.29 8 2.93 1-2 hydrazine, at the temperatura of 60-65C, causes theoritically the
reflections 1.84 4 complete shift of the 7 to 10.4. But incomplete reaction often
occurs in fire-clays ; the treatment has to be prolonged several days
KAOLINITE DICKTITE NACRITE (up to 15 days sometimes) before the entire 7 reflection becomes
able to move. It has been shown, effectively, that the treatment
d. I d. I d. I works differentially by displacing very quickiy the largest partiles
of kaolinite while the very fine partiles (below 1 micron) are left
7.15 10 7.16 10 7.17 10 at the 7 position.
4.45 4 4.46 0.5 RANGE e a/., (1969) have proposed a classification scheme for
4.44 4 kaolinites which is based on degrees of lattice disorder by using
4.35 6 4.37 4 4.41 7 the effects of the reaction of the partiles with hydrazine water,
4.17 6 4.27 3 ethylene glycol, glyceroj. This sheme is concerned with the variable
4.12 3 4.13 7 4.12 3 displacement of the 7 reflection to 10.4. The behaviour of the
3.84 4 3.95 2 kaolinite after successive replacements and leachings allows a five-
3.734 2 3.795 6 fold classification which s hereafter represented : (table 5).
3.566 10 3.587 10 3.577 10
3.365 4 3.427 3
3.138 2 3.272 2
3,019 2 3.101 2 3.061 1 Other treatments, suoh as the one proposed by WADA (1961),
2.938 2 2.917 0.5 provide data for the recognition of kaolinite in a clay mixture. The
2.748 2 2.794 2 method indicated by WADA (op. c/'.) concerns the grinding of dry
2.553 8 2.560 4 2.576 3 kaolinite with potassium-acetate, which causes = an mtersalation
2.521 4 2.51 5
complex. The 7 reflection o moves towards 14A for an ordered
2.486 9 2.502 : 3 variety, while a doublet at 7 and 14 is characteristic for partially
2.374 7 2.40 1 2.438 i 7 and disordered varieties. In water solution the ammonium nitrate
2.331 10 2.322 9 2.33 2 displaces the potassium actate ; the effect results in the occurrence
2.284 9 of a 11.6A ammonium nitrate-kaolinite complex. But the reaction
2.182 3 2.212 2 2.237 ! 0.5 is not very often entirely quantitative : there can be found some
2.127 2 difficulty in the formation of the kaolinite-KCHsCOO complex with
1.985 7 1.975 5 1.982 0.5 the kaolinite because some natural clay material bears a ciment
1.935 4 1.937 1 1.921 2 richer in AI2O3 than SO2, which binds the kaolinite crystals and
1.892 2 1.898 2 makes difficult the intercalation of the salt (GOMES, 1967).
1.835 4 But by a reduction in the amorphous material conten [following
1.809 2 1.805 1 1.818 2 successive digestions with hot 5% Na2CO3 (MITCHELL and
1.778 5 1.785 1 1.792 3 FARMER, 1962)], a better development of the kaolinite-KCHsCOO
1.682 2 1.686 1 complex can be achieved. According to WADA (1963) the develop-
1.659 8 1 .652 5 1.668 3 ment of the kaolinite-salt complexes depends on the following
1.616 6 1.613 1 1.617 0.6 factors nherent to the kaolinite : 1) thickness, size and crystal-
1.581 4 1.586 1 linity of the partiles ; 2) presence of amorphous alumino-silicates
1.539 5 1.555 4 (allophane), and binding of the crystals by these materials ; 3) ana-
1.486 9 1.489 5 1.488 5 lytical errors.
ALIETTI (1966) provided some data for disordered kaolinites when
Table 4. Comparison between dicktite, kaolinite and nacrite re- the X-ray pattern of the powder preparation is examined n com-
flections (after DOUILLET and NICOLS, 1969). bination with the effects of the potassium actate (table 6).
Treatment Observed basal spacings in d()

Drying at 110C 7.2-7.3

Hydrazine hydrate 10.4 10.4 9.5-9.6 7.2-7.3 10-10.2


at 65C / 7 days

Leaching of hydrazine 7.2 104 10. 2 sharp 9.85


with water + 8 broad

Replacement of water 7.2 10.85 10.85


by ethylene glycol
Replacement of water 7.2 7.2 7.2 11.1
by glycerol

TYPES OF KAOLINITES I II III IV V

no or relatively mdium F , Halloysite


Nttle disorder to strong disorder e-ciay (hydrokaolinite)

Table 5. - Reaction types of kaolinite groups according to their behaviour towards hydrazine hydrated water,ethylene glycol leachings
(after RANGE et al., 1969).

Garnierite shows a basal spacing near 7.2-7.3 and near 10


(001) K-acetate washing with degree of ordering (PHAM THI HANG and BRINDLEY, 1973 ; BRINDLEY and PHAM
in d() H2O NH4CI X-rays intercalaron THI HANG, 1973). In the samples examined by these authors,
method only a mino/ity appears to be dominantly of the one or the other
type. The 7A-type X-ray pattern resembles the one of the serpentine
7.1 14 7.1 10 ordered ordered group minerals, chrysotile and lizardite. The diffraction characters of
the 10-type suggest a talc-like mineral with a high degree of layer
71 14
7.1 ordered or stacking disorder and, in some cases, possible with some swelling
7.1 71
partially partially interlayers. A further accuracy can be achieved by examining both
disordered to the (hkl) X-ray patterns of the garnierite minerals, and the products
*Q ordered or disordered
75 14
7.1 disordered of the heated samples to about 1000C.
71
7.1
Amesife displays a basal spacing of 7.06 (002). Its (060) is at
7 14
7.1 7.1 1.531 A.
7.1
disordered disordered
For all these serpentine and kindred minerals detailed X-ray powder
7 7.1 7.1 7.1 data are presented and contrasted in THOREZ (1975).
Table 6. Behaviour of kaolinite types with K-acetate (ALIETTI, 1966).

IV - B - 4. - TRIOCTAHEDRAL MINERALS Mineral basal spacing in A (060) in A

clino-chrysotile (002) 7.36 1.536


Several mineral species are presented in the serpentine group of
the 1:1 minerals. Generally they show basal spacings larger than cuno
for kaolinite, particularly in the range of 7.2-7.3A. Characteristically (002) 7.36 1.531
+ ortho-chrysotile
is the valu of their d(060) which is also higher than for kaolinite.
The differentiation between kaolinite minerals and the serpentine lizardite (002) 7.36 1.534
group minerals can be achieved by the detailed investigaron
of the X-ray powder mount. Treatment with HCI usually causes lizardite
the serpentine mineral rich n ron to be decomposed, while Mg- (002) 7.35 1.535
+ clino-chrysotile
rich serpentine minerals like the kaolinite minerals are resistant to
the treatment. lizardite (002) 7.36 1.534
For a routine differentiation, table 7 provides some data on the + ortho-chrysotile
d-spacing of the different species.
greenalite (001) 7.21 1.60
Chamos/te has a basal spacing slightly smaller than kaolinite :
(001) at 7.05, but a d(060) at 1.555. Careful X-ray diffraction Ni-serpentine (001) 7.28 1.542
analysis, combined with heat treatment and acid attack, can make
the distinction clear. Co-serpentine (001) 7.53 1.55

Of course, of great interest is the electrn microscope examination antigorite (001) 7.30 1.541
of the trioctahedral 1:1 minerals. For nstance, hollow tubes and
fibers are characteristic for chrysotile while these structures are 6. layer (001) 7.33
also readily differentiated from those of halloysite. Antigorite occurs orthoserpentine 1.535
as plates and laths. Other serpentine minerals may have a X-ray
powder pattern similar to chrysotile, but their electrn micrographs Table 7. - d(001) and d(060) for the serpentine group (from BROWN,
resemble antigorite. 1961, and THOREZ, 1975).
IV - B - 5. - IDENTIFICATION OF KANDITES IN CLAY MIXTURES
The dentification concerns firstly kaolinite-halloysite, kaolinite- Hydrated ha/loysite is detected by a basal spacing of 7.3A or larger,
dicktite, mixture of trioctahedral (serpentina) minerals, and mixtures that shifts to smaller spacings when the sample s heated to 350C
of dioctahedral (kaolinite) and trioctahedral (serpentina) minerals. or less. Glycerol or ethylene glycol can expand the halloysite when
This objective can be achieved by the X-ray analysis of particularly the mineral s hydrated. When halloysite occurs n large amounts
the powder preparation in the regions between 4.4-3.5A, and the X-ray powder pattern shows- prominent broad and asymmetric
2.8-2.0 where the differences are mostly clearly occurring. reflections in the regin 4.6-3.5, and 2.8-2.4. Evaluation by elec-
tronic microscope provides further indications about the shape of
The distinction between kaolinite and haoysite can be obtained the partiles (tubular for halloysite, while platy and more or less
by a combination of different methods : X-ray analysis, DTA, electrn well hexagonal n kaolinite).
microscopy.

IV - B - 6. - DIFFERENTIATION BETWEEN KAOLINITE AND CHLORITE


A second differentiation is focused on the one of kaolinite and limitations and have to be combined :
chlorite in mixtures. 1) at a slow scanning speed the (002) reflection at 3.58A of the
Identification of kaolinite in mixture s not difficult f the mineral kaolinite may become resolved from the corresponding (004) of
occurs with clay minerals other than chlorite. The identificaron of chlorite at 3.53 (BISCAYE, 1965 ; BRADLEY, 1954). This method
kaolinite n the presence of chlorite s delicate because the over- cannot be always strictly applied : many chlorites and kaolinites have
lapping of spme of the (001) reflections. Most chlorites have strong their 3.5 reflection exactly situated at the same 226. The reso-
(001) at 14, and (003) at 4.7, which do not occur n any of the lution of the doublet equally depends on the relative proportion
kaolinite minerals. Particularly s the occurrence of the (004) at of both minerals n the mixture, and also on their crystallinity
4.7. But n iron-rich varieties of chlorite the (001) and (003) (disordered kaolinite and/or chlorite are characterized by the develop-
reflections are generally weak or even are lacking. These reflections ment of a broadening or an asymmetry of the (OOI) reflections
may also be undetectable when the chlorite occurs as a minor in combination with a lowering of the intensities).
component n the mixture. Also to be taken into account is the
natural overlapping of the (001) and (003) by the reflections of 2) the doublet at 3.5 may be enhanced by heating the sample to
more or less degraded minerals (cf. the 5 wide reflection of 400C. The resulting ^effect s sometimes a better resolution of the
degraded Hite ; or the tailing effect of 10 Hite towards the low two reflections at 3.5. When heated to 490 or 500"C / 2 hours the
angle side of the diffractogram with the masking of the 14 (001) kaolinite becomes decomposed ; theoritically the chlorite remains
chlorite reflection) ; or the case of a more or less degraded chlorite unaffected. But the crystallinity of the latter mineral vares, parti-
the (001) of which is shifted on heating towards a lower d-spacing cularly in soils, and the mineral may not be resistant to the heat
than 14A. treatment. On another hand there exist kandites such as nacrite
which are resistant at heat treatment just showing a slight decrease
However the (006) at 2.5 of chlorite s very weak when compared n the intensity of the (001) reflections. After having been heated
to the (003) at 2.5 of kaolinite which s moderately strong. f one to 500C some chlorites (in particular the iron-rich varieties) show
excepts the possibility of the occurrence of dioctahedral chlprite their even orders (002) at 7 and (004) at 3.5 with a sensitive
mixed with kaolinite, the (060) is at 1.49 for kaolinite (1.50 for lowering of their ntensities n comparison to the normal and
dioctahedral chlorite) while at 1.53 or higher for (trioctahedral) untreated sample. These reflections may guickly disappear after
ch lorites. the heating while the basal spacing at 14 is still not detectable
In mixture comprising chlorite and kaolinite, the intensities ratio of n the X-ray pattern.
the 14 and 7A reflections cannot be used since it vares consid- 3) pre-treatment with organic and inorganic compounds should have
erably with the chemical composition of the chlorite. For nstance to be adopted for a routine dentification when chlorite and
the iron-rich chlorite shows a lack of its basal reflection (001) or kaolinite are suspected n mixture. But caution must be taken for
the latter remains unpronouced by being masked by (001) reflections the kaolinite (see above comments about the effects of the hydrazine
related to other clay minerals in the low angle side. treatment).
Thermal treatments also can fail in giving accurate indications 4) n hydrochloric acid (2N to 13N) with concommitent boiling,
because in soils and sediments a poorly-crystallized chlorite occurs chlorite is preferentially dissolved while kaolinite remains intact.
that s already easily transformed into an amorphous material on But some chlorites may offer a variable resistance to the treatment,
heating at 450C. and are only imperfectly decomposed (KODAMA and OINUMA,
1963). Also dioctahedral chlorite s more or less resistant n hydro-
In practice several methods can be used n the determination of chloric acid. There are hghly disordered kaolinite the X-ray pattern
kaolinite and chlorite in mixture. All these methods have their of which becomes confused after the treatment.

IV - B - 7. - CRYSTALLINITY OF KAOLINITE
Crystallinity indexes (or the order-disorder criterion) have been show a first perfectly and well-developed triplet while the other ones
attractive analytical tools and useful techniques for kaolinite, because have been substituted by single and enlarged reflections. These
of the importance of the minerals in ndustry. differences cannot be fully integrated into MURRAY and LYON's
MURRAY and LYON (1956) have proposed a set of 13 stylised classification scheme. It may be that such distorsin in the clas-
diffractogram patterns of random powder preparations, in which sification is in relationship with the genetic conditions of the kaolinite
a progressive decrease in crystallinity s shown (figure 1). Their materials analysed n Belgium.
classification is based on the changes n shapes and ntensities BRINDLEY and ROBINSON (1948) have published a schematic
of the (hkl) reflections, particularly with the enlargement of the chart for distinguishing between crystallized kaolinite, common
reflections, the replacement of triplets by doublet or by a single kaolinite, fire-clay and hydrokaolinite (figure 2).
but wide reflection. From such a gradation t would logically be HINCKLEY (1954) and RANGE [ef al. (1969)] have proposed a
accepted that t s easy to identify the degree of crystallinity. In crystallinity ndex. Their method is based on the ratio vales of
fact, if t s accepted that the decrease n crystallinity s based the intensities of the first triplet reflections (figure 3).
on the common and parallel substitution of the three characteristic
triplets by boublets, and finally by single reflections, the experience Comparison of the entire X-ray powder pattern of the kaolinite
by the present author for Belgian kaolins indcales the method to minerals provides a quick routine evaluation of the crystallinity
be somewhat invalid. For nstance, a monomineralic kaolinite may (figure 4) (data from BRINDLEY and DE SOUZA SANTOS, 1963).
060 igure 1. - Crystallinity orders in kaolinite (after MURRAY and LYONS.
Fig
1956).

Figure 2. - Schematic Debye-Scherrer X-ray monogram of well-crystallized


kaolinite, fire-clay and halloysite (hydrokaolinite) (after BRINDLEY and
ROBINSON,


0 o
Q,O^_
COI *
OJ^^ Ol 0 .
o i o
Well crystallzed
J|? i. 1 ,, , 1 1! i , . i i , , i . i ., 1 11
Common
_l I i I J l l l

Fire-clays
ll ll

Hydrokaolinites

i5
WELL ORYSTALLIZED KAOLINITE 002 001
002 111 110 002

26 25 24 23 22 21 20 19 26 25 24 23 22 21 20 19 26
HINCKLEY CRYSTALLINITY INDEX RANGE AND WEIS CRYSTALLINITY INDEX

Figure 3. - Crystallinity ndex for kaolinite


(after HINCKLEY, RANGE et al.).

Figure 4. - X-ray powder diffraction paterns of monomineralic kaoln r\


minerals. (A) : well-crystallzed, well -formed platy material, enhanced basal
reflections (kaolinite) ; (B) : platy material with b-axis disordered sequence,
enhanced basal reflections (disordered kaolinite) ; (C) : layer sequence
partially disordered with respect to both a- and b-axies, little enhancement
of basal reflections, rolled form (halloysite) ; (D) : highly disordered layer
sequence, no enhancement of basal reflections. tubular form (halloysite)
(after BRINDLEY and DE SOUZA SANTOS, 1963, reproduoed in DIMAN-
CHE, RASSEL, TARTE and THOREZ, 1974). 35 30 25 20 10 28

IV - C. - MICA-LIKE CLAY MINERALS AND ILUTES (symbol : I)

IV- C - 1. - GENERALITIES
The dioctahedral muscovite and its derivative producs (such as (OOI) reflections; n muscovite the 5 s strong ; the ratio 1(001 )/l(002)
ilute) are recognized by their strong first and third order basal s between .7 and 1 ; n Hites, reflections at 4.97 (weak), and
reflections respectively at 10 and 3.3. The latter reflection may 4.47 (strong), occur while the 1(001)71(002) has a valu of 4/9.
coincide with the strongest quartz reflection when this mineral In Mg-rich ilutes, the 1(001)71(002) s weaker than 2 ; in Fe-rich
occurs n the clay fraction. ilutes, the ratio s higher than 3. The same ratio is n relationship
The basal spacing remains unaffected after glycolation (glycerola- with the K content (WHITE, 1962).
tion) and heating. ESQUEVIN (1969) has proposed to use the intensity ratio 1(002)71(001)
to provide, at first approximation, the AlaOs/FeO+MgO content n
This behaviour can be formulated as follows : the octahedral layer. The ratio vales can be correlated with the
AIsOs/FeO + MgO expressed in solid phase compositions as found
Treatments N EG 500C n biotite, phengite, muscovite, or in a mixture of biotite+muscovite
(see figure 5).
d(001) m d() 10 10 10

ratio vales 15 . 2 .3
Generally the ratio of the intensities for the 10 and 5 reflec- corresponding to
tions, hO/l5, s greater n dioctahedral than trioctahedral va- solid compositions biotite biotite phengite mus-
rieties. A high ratio s also associated with high ron conten of n the octahedral
the octahedral layer (GRIM ef al., 1951). layer of
In dioctahedral varieties a (002) reflection occurs at a d-spacing
of 5 while n trioctahedral varieties the 5 reflection s lacking Figure 5. - ESQUEVIN's method of fixing the composition m Al2O3/FeO+MgO
or of very weak mtensity (cf. biotite). n the ocahedral layer of Hites, based on the ratio of the intensities
In dioctahedral Hites the second order reflection at 5 remains of (002)/(001).
intense though weaker than for the muscovite. The latter mineral
usually presents narrow, intense and symmetnc reflections for the

10
I V - C - 2. - THE ILUTE TERM
The term ////fe is to be used as a co/lective ame for all the 10 with normal mica, but without swelling properties. The term hydro-
non-expanding clay material (GAUDETTE et al., 1966). Chemical muscovite, on the other hand, could be reserved for hydromica
analyses of dioctahedral ilutes, first described and named by GRIM formed by the degradation of muscovite ; the hydromica usually
ef al., 1937, show a lower K conten and a higher water conten shows a higher content of Al in the tetrahedral layer and can be
comparatively to muscovite. The lower substitution of Al for Si n assigned to 2M-| polytypic modification. Similarly ames such as
some of the ilutes, n comparison with that of muscovite, has led hydrobiotite and hydrophlogopite pertain the product of partial
GRIM ef al. (1937) to the conclusin that the former are not likely degradation of biotite and phlogopite, the crystalline structure of
to derive from micas. which retains a 10 spacing and does not show any swelling
It must be pointed out that commoner than typical micas as the properties. But one should have to recall that in some literatura
components of clayey rocks and of soils are minerals corresponding the term hydrobiotite is reserved to a regular mixed layer mineral
to i/lites (hydromicas). Apart the deficiency of K+, the electric charge built of biotite and vermiculite layers, and considerad as the product
is compensated by HsO+ introduced n the interlayer spaces ; there of the degradation of a biotite structure.
also occurs additional protons n the nterlayer spaces, and a partial In the mica (Hite) group one has to number glauconite and cela-
oxidation of Fe ++. So that the layer charge in the crystalline donite. However n the crystal lattice of glauconite it s usually
structure of ilutes is usually smaller than that n the structure of found swelling (montmorillonite behaving) interlayers as observed
micas. Normally the Hites do not exhibit any swelling properties. by BURST (1958) and HOWER (1961). As a consequence a sharp
There is however no sharp boundary between micas and hydro- boundary does not exist between glauconite, of the mica type
micas (Hites) as gradual transition between them is observed. structure, and montmonllonite. Celadonite s both structurally and
Detailed chemical composition are sometimes required for their chemically very similar to glauconite. Taking into consideration that
distinstion. For this reason it seems appropriate to include the ilutes the majority of glauconites and celadonites are structurally closer
into the mica group as a subgroup of the dioctahedral varieties. to Hites, these two species have been assigned to the subgroup
of dioctahedral mica too.
To describe hydromicas cise to muscovite, two ames are used :
////fe and hydromuscovite. As recalled by STOCH (1971), some authors In this handbook the term illite is .used for all the clay partiles
consider them as synonyms; other believe that Hite and hydro- that show a 10 layer spacing : the reflection apex s situated at
muscovite are different minerals. After GRIM ef al. (1937), ////fe is 10 while some tailing may occur towards the low angle side of
the ame for fine-grained authigenic micas occurring n clays, that the X-ray pattern, and is developed on the flank of the (001) reflec-
exhibit both a dficit of K+ and an excess of water n comparison tion.

IV - C - 3. - POLYTYPISM IN ILUTES
Dioctahedral illite shows a relatively sharp basal reflection which size, the kind of components with their relative amount, and the
may become slightly sharper after heating. Occurrence of a small the type of mixing (see chapter VI).
amount of expansible layers in the structure results n the development The asymmetry developed, n particular on the side of the (001)
of an asymmetry of the (OOI) reflection towards the low angle side reflection, s to be assigned t'hus to some expansible mterlayers,
for the (001), and towards the high angle side for the (003), while and corresponds to an open or degraded Hite.
the (002) becomes broader (BRADLEY, 1954; LUCAS, 1963;
KUBLER, 1962). The asymmetry is indicative of a transition to The polytypism (1M, 1Md, 2M) of lite is to be evaluated by some
mixed layer systems (REYNOLDS and HOWER, 1970; KODAMA definite (hkl) reflections.
et al., 1969) ; the analysis of such mixed layers involves the particle

3T muscovite 3T Hite 1M Hite 1 M hydromuscovite 1Md fithian illite


9.98 S 9.9 S 10.1 S 10.1 S 10.1 S
4.98 M 4.9 M 4.98 M 4.98 W 4.98 W
4.47 S 4.45 VS 4.50 S 4.48 S 4.48 S
4.29 VW 4.28 W 4.35 VW
4.11 VW 4.10 W 4.10 VW 4.09 VW
3.87 M 3.87 M 3.85 VW 3.87 VW
3.60 M 3.64 MW 3.62 MS 3.65 M
3.34 VS 3.35 VS 3.32 S 3.34 S 3.33 S
3.10 M 3.09 MW 3.08 MS 3.07 M 3.07 VW
2.87 M 2.85 Md 2.89 MW 2.88 VVW 2.85 VW
2.57 VS 2.56 VS 2.67 W 2.67 MW
2.47 Md 2.45 MW 2.57 VS 2.56 S 2.57 VS
2.38 M 2.39 M 2.47 W 2.46 W 2.46 Wd
2.24 W 2.235 MW 2.38 M 2.38 MW 2.38 Wd
2.20 W 2.25 MW 2.35 W 2.25 Wd
2.13 M 2.14 M 2.14 M 2.13 MW 2.L4 Wd
2.05 VW
2.00 MS
1.988 M 1.99 S 2.00 Md 1.99 Wd
1.96 W 1.940 W
1.72 VW 1.71 VW
1.65 M 1.67 Md 1.65 Md 1.64 Wd 1.65 Wd
1.62 VW 1.58 VW
1 .52 VW 1.50 S 1.50 MS 1.50 S
1.50 M 1.497 S

S = strong ; M = mdium ; W = weak ; V = very ; d = diffuse.

Table 8. - (hkl) reflections in d() and corresponding intensities for polymorph varieties among ilutes and hydrous micas (after LEVINSON,
1955).

11
LEVINSON (1955) has published detailed data about the polymor- rassembled in THOREZ (1975).
phism of ilutes and hydrous micas, including the 3T(3-layer trigonal),
2M (2-layer monoclinic), 1M (1-layer monoclinic), and 1 Md (1-layer It often occurs that the polytypes are met in mixture, and in several
monoclinic disordered) (table 8). 2M and 1 Md polymorphs occur relative proportions. The distinction n mixture of 1 M, 1 Md and 2M
n sedimentary rocks ; 3T and 1M belong to non-sedimentary polytypes is not easy and remains a practical difficulty (WARSHAW,
environment, such as hydrothermal weathering. Complementary and 1960 ; VELDE and HOWER, 1963 ; MAXWELL and HOWER, 1967).
much detailed data about the (hkl) positions and intensities of the Each of the polytypes is characterized by a series of reflections
different polymorph varieties published in the literature have been which are presented n table 9.

2M : 4.48 4.29 3.89 3.74 3.66 3.54 3.33 3.21 3.01 2.87
2.08 2.55
1M : 4.48 3.66 3.33 3.07
2.58
1Md : 4.48 3.33
2.58
2M+1M : 2M 3.75 3.50 3.20 2.89
1M 3.66 3.07
Table 9 : characteristic reflections of the polymorph varieties among Hites,
(d spacings n ).

KODAMA (1962) has published the variable intensities of the reflections


specific reflections in the case of a mixture of 2M + 1M (table 10). 2M-I/1M 2:1 1:1 1:2
in d(A)
A semi-quantitative evaluation of polymorphs has been attempted 3.75 2M-| 6 6 6
by DUNOYER de SEGONZAC (1969). Standard mixtures can be 3.66 1M 6 10 12
artificially prepared in order to reach a more accurate figure. The 3.50 2M-| 10 10 6
global conten of jllite is indicated by the height of the composite 3.20 2M-] 12 10 8
reflection at 4.48. The relative percentage of 1M is estimated by 3.09 1M 8 12 16
the height of the 3.3 and 3.74. 2.99 2M-| 14 16 8
The dioctahedral and trioctahedral character of the ilute is provided
by the position of the (060) reflection. _When quartz occurs in the Table 10. Intensities of the common reflections in the case of a
clay fraction, its (211) reflection at 1.54 can be used as an internal mixture of ilute polymorphs (KODAMA, 1962).
standard.

IV - C - 4. - CRYSTALLINITY AND VARIETIES OF ILUTES


The shape of the basal reflection of ilute can be used for an 3) IM : the asymmetry on the lower angle side of the 10 reflection
evaluation of the crystallinity. exhibits an ncreasing background upon glycolation and is repla-
When the material is well-crystallized, the (001) reflection at 10 ced by a narrow but symmetric reflection after heating. There
is relatively narrow and symmetric as in muscovite. When the com- are similarities of behaviour with a montrnori/lonite " specifically
posite layers of Hite are progressively and then intensively stripped for what concerns the 14 foot displacement of the asymmetric
of their original K+, the shape of the (001) becomes asymmetric, reflection : 14(N)^swelling (EG)-*collapse (500UC). The ame
a feature indicating the open character of the Hite . The stripping proposed by LUCAS (1963) s : open illite with montmorillonite-
of K+ determines the progressive djsplacement of some nterlayers, behaviour : l|\/|.
originally at 10, from 10 tp 14. In open ////fe, the apex of the 4) IQ : because some interference effects may occur n the low
reflection still remains at 10,_but the foot of the asymmetry may angle side (due to the (001) of chlorite, smectite or vermiculite),
become situated at about 14. The behaviour of the distended the particular behaviour of the asymmetry upon treatments cannot
spaces (interlayers) in the illite is to be put n parallel during the be related to one of the above quoted varieties ; the material
identification treatments (glycolation, heating) with the modification should be noted : IQ, the O referring only to the open"
in the shape of the basal reflection. LUCAS (1963) has proposed character of the illite.
a classification of open illite into three classes or varieties. (Fi-
gure 6) : As t can be thus noted the development of the asymmetry on the
1) IG : the basal reflection at 10 in the natural (untreated) sample flank of the 10 Hite reflection is indicative of a mixed ayer struc-
shows an asymmetry (tailing) towards the low angle side of. the ture. There s a continuous transition between well-crystallize_d
diffractogram. The asymmetry is developed on the inner side (with narrow 10 reflection) illite, and mixed layers built on illite (10)
of the 10 and remains stable after the treatment, its foot being layers, and 14 interlayers. One may consider the le, IV ar|d IM
situated at 14 after glycolation and heating. The behaviour varieties of open illite as intermedate stages which can be usefully
of this foot is to be compared with the one of a chlorite '. expressed in an evolutionary weathering of a dioctahedral 10
14(N) *14(EG)-14(500C) or Hite with chlorite-behaviour. mica-like material. As t will be shown lateron, open ilutes IM, Iv
LUCAS calis this type of open illite : Ip. It does not mean of and le are parts of a series where other varieties are indicated
course that a true chlorite s intervening n the structure. by the symbols Ip.a.*, and Ipj.* on one side ; clearly interstratified
2) Iv : the asymmetry towards the low angle side and developed structures are indicated, for nstance, by the general formula :
on the flank of the 10 reflection remains unchanged after (10-14^), (10-14y) or (10-140) depending on the nature of the
glycolation, but is replaced by a narrow and more symmetric nterlayered space, on the other side.
reflection (with its apex still at 10A) after heating. Here some
similarities can be proposed with a verm/culite-like behaviour
(stability on glycolation, collapse on heating). The distended
nterlayers of the illite behave themselves as vermiculite, and the
foot of the asymmetric refjection shows a similar instability which
can be formulated : 14(NM4(EG)-10(500C). For these
reasons LUCAS (1963) has proposed the ame of open illite
with vermiculite behaviour, or : \\j. ip.a = Ilute with an acule (a) peak (p) ; Ip | = Illite with a large (I) peak (p).

12
Figure 6. - Schemalic representaron of the (001) Hite reflection at 10A
m the case of open varieties : le, IV, and IM (LUCAS, 1963). Comparison
of the shape after the glycolation and heating. Minerals related to Hites
(Van der MAREL, 1961).

MINERALS RELATED TO ILUTE VARIETIES OF OPEN ILLITE


(AFTER van der MAREL,1961) (AFTER LUCAS, 1963)

O
m m

co
o
oo
O

en
O
Oo
o
O O

EXP(14)I I-MS I-EXP(14)I IM iv ic


m
In a parallel way, van der MAREL (1962) has also ndicated four a property in refering to crystallinity indexes. Ilute partiles
varietes of minerals related to ilute : have generally sizes above 1OOA (0,01 micron) so that the thickness
of the reflections will be related to the regularity n stacking. A
1) hydrated illite with an asymmetric shape, the apex being situated well-crystallized illite will be indicated by narrow reflections ; a
at 10. disordered i/lite, on the contrary will exhibit enlarged and irregular
2) illite-expanded (14) Hite (other ame : degraded i/lite) wich is reflections.
a mixed layer. The second order (002) at 14 oollapses when WEAVER (1960, 1961) has taken into consideraron these crystal-
heated to 350C. The degree of contraction when K-saturated lographical data, and has tried to find out variations in the crys-
depends on the amounts of the 14 non-swelling material. tallinity of ilutes. This author has chosen the (001) reflection
3) expanded 14 illite ; other ames :^open illite, 14A swelling illite): (1 M ndice, 10) and calculated a sharpness ratio A/B (figure?).
the 14 reflection collapses to 10 when K-saturated and heated This method has provided excellent results n an attempt to define
to 350"C. There occurs a slight expansin at 1 7.6A after gly- diagenetic and metamorphic zones or zonation in sedimentary
cerolation. rocks. But WEAVER's sharpness ratio has been abandonned
in the USA because its lack of accuracy. Indeed the A/B ratio
4) swelling illite (or hydrated mica) : the basal spacing s near or becomes badly defined in the case of intense crystallinities where
higher than 14. Heating to 350Coand K-saturation give inter- A s great, and B weak.
mediate vales between 14 and 10; glycerolation expands the
reflection to 17-18A.

In many series studied by the present author (published and un-


published data), t can be demonstrated that when an open illite
of the IM variety occurs, the glycolation produces a particular effect:
the original asymmetric reflection is substitued by a narrow sym-
metric 10 reflection that merges above a tail (or a diffraction band)
extending towards 14 or even to higher d-spacings. It is charac-
teristic to note that the intensity of the remaining 10 s generally
decreased comparatively to the untreated sample.
It s the opinin of the present author that one may still consider
the LUCAS's (1963) varieties of Hite as particular members of the
illite on the way to more pronounced mixed layers (these involving
illite layers and montmorillonite, chlorite or vermiculite interlayers).
There is of course not a firm boundary between the open Hite and
the corresponding mixed layers ; some authors consider already THICKNESS INmm
AT 1/2 HEIGHT
the former material as a typical mixed layer. ABOVE BACKGROUND
Indeed the asymmetry of the (001) in the open illite indicates
that there exists some distended spaces having or not a resistance
to expansin and (or) heating. When the nterlayers in such a material
are further lost, certain partiles of the original illite component
still remain intact, and show a lack of swelling or collapsing pro-
perties. When the weathering ncreases, the illite structure reaches
more clearly the status of a (random) mixed layer composed of these
residual illite layers and of distended interlayers ncreasing in num-
ber; for such a mixed layer structure, in which either the apex of
the basal reflection remains at 10 or s displaced to higher
vales, a specific codificaron has been proposed and ntroduced
by THOREZ (1975) such as : (10-14M) (see chapter VI). For these
latter mixed layers, REYNOLDS and HOWER (1970), and KODAMA
(1969) have established curves allowing an estimation of the expan-
sible interlayers intervening n the mixed layers. ILLITE SHARPNESS RATIO ACUATE INDEX OF THE ILLITE
(WEAVER, 1960) (DUNOYER de SEGONZAC, 1969)
As a conclusin the shape of the basal reflection s that of a illite
characterized by a basal reflection the apex of which is situated at Figure 7. - Characterization of the illite crystallinity or sharpness
10 but with a possible moreorlessdeveloped asymmetryoccurring ratio " of WEAVER (1960), and DUNOYER de SEGONZAC (1969).
on its flank towards the low angle side. Providing that the apex
does not move upon glycolation and/or heating, the material should
be classified as illite. When some changes affect the basal spacing WEAVER's method has been later reconsidered by French authors
upon glycolation and heating (with the d/splacement of the apex at and laboratorios (see KUBLER, DUNOYER de SEGONZAC, op. c/U
higher vales compared to the natural sample), the material should A crystal/inity ndex was reintroduced. It concerns the thickness of
be comprised in the mixed layer material group with illite layers. the 10 reflection, above the background, and is measured at half
This assumption is of course to be considered more as a practical of the height of the reflection in specific X-ray diffraction conditions
mean than as a true crystallochemical or crystallographical (diffractometer Philips 1010, 38kV, 18m, Cu-Ka, Ni-filter; slits :
rule . 2-0.1-2 ; sensibility : 1-102-10 to 1-103-4 (DUNOYER de SEGONZAC,
1969). The advantages of this method are : a quick and easy
These preliminary remarks having been provided for the charac- measurement; the independency toward statistical fluctuations of the
terization of Hite, one can now deal with some methods related to apparatus ; the independency of the eight of the reflection for vales
the crystallinity measurements of the mineral. higher than 3 cm ; the mdependency toward the technique of prepara-
Several authors have been nterested to provide criteria about the tion of the oriented aggregate. The nconvenient s related to the
fact that the ndex s of a absolute valu, and depends on the
crystallinity of illite (WEAVER, 1960, 1961 ; KUBLER, 1964, 1966 experimental conditions, in particular, the registraron ones. This
1967, 1968; DUNOYER de SEGONZAC and KUBLER, 1966
ndex ncreases when the crystallinity of the ilute decreases. As a
DUNOYER de SEGONZAC, PERRERO and KUBLER, 1968 consequence care must be taken relatively to the regstration con-
ESQUEVIN, 1969; TRAUTH, SOMMER and LUCAS, 1968
DUNOYER DE SEGONZAC, 1969; WEBER, 1970, 1972 ditions as fixed by DUNOYER de SEGONZAC (1969) (see above).
Some distorsin may take place n the measure of this ndex when
CHAMLEY, 1967).
the (001) at 10 of the illite is partially overlapped by the (002)
The thickness of the reflections for a crystalline material depends of pyrophyllite at 9.20-9.3 (towards the high angle side) or by the
on the size of the partiles lower than 100 (GUINIER, 1964) (001) of random mixed layers or the (002) of regularly inter-
and the regular stack/ng. The term crystallinity" s often used stratified mineral (towards the low angle side of the diffractogram)
in crystallography, and one is naturally conducted to evalate such n the d-spacing range between 10A and higher vales.

14
Thickness of
the(001)at10 Using this crystallinity parameter DUNOYER de SEGONZAC, in
particular, has succeeded to fix a range of vales related to :
the diagenetic zone, the anchizone (anchimetamorphic zone),
and the epizone. The vales of the ndex can then be combined
10 with those provided by ESQUEVIN (1969) for the AlaOa/FeO+MgO
composition of the octahedral layer of ilute. A graphical presentation
s organized that allows the characterizaton of the Hite toward
and n the three above defined zones (figure 8). Such a presentation
of the crystallochemcal data s useful for nstance for the analysis
DIAGENETIC of a clay illitic-rich material whch has undergone an evoluton from
ZONE the diagenetic conditions toward those existing in the epizone ;
both the crystallinity and the composition of the Hite are taken into
consideraron. Many examples are provided in the work of DUNOYER
de SEGONZAC (1969) n the scope of several evolutions.
TRAUTH, SOMMER and LUCAS (1968) have fixed up some ap-
proaching vales of crystallinity for the ilute. They have proposed
an acuate ndex o based on the measurement (in mm) of the
thickness of the 10A reflection at half-height above the background.
::i ANCHIZONE Three varieties of illite are proposed : ////fe with an acuate peak
4 (Ip.a.) where the ndex has a valu equal or lower than 3 ; illite with
-VT-AM-:* ^.-.V.-.WT- large foot (or large peak) (lp.|.) with a correspondng ndex valu
xl;: ;:x -:'-^: <::: xxix of about 6 ; open illite (le, Iv, M varieties of LUCAS, 1963) where
3.5 the ndex has a valu equal or above 10.
THOREZ in several papers (1970 ; MULLER e al., 1973) has used
TRAUTH ef al. (1968) ndex and the ESQUEVIN's (1969) method
x:l:'.
EPIZONE n an attempt to fill up the evolution of the Hite during the weathering
of a sediment rch in ilute (figure 9). The ntensity of the weathering
can then be followed on account of modifications that take place
both n the octahedral layer, and in the crystallinity of the illite.
Other authors (CHAMLEY, 1967 ; WEBER, 1970, 1972) have also
l(
proposed comparable methods of analysis.
BIOTITE '( BIOTITE + ' i PHENGITE'l 1)
' MUSCOVITE ' ' MUSCOVITE MELLIERES and PEREZ-NIETO (1973) used another parameter for
the estimation of the crystallinity in sedimentary Hites. Their opening
Figure 8. - Illite characterization by the acule n d e x and the
Al2O3/FeO + MgO compostion of the octahedral layer (after ESQUEVIN, status" (figure 10) is measured by the ratio : Eo = 100
1969, and DUNOYER de SEGONZAC, 1969). Evolution of the crystallinty ST
and composition of the Hite from the diagenetic or weathering zone where ST is the total surface of the 10A reflection above the
toward he epizone. background, and S|, the surface of the normal reflection centered
on the 10A apex. The latter surface is measured after having fixed
up the symmetric branch of the reflection towards the low angle
IJ002) side comparatively to ts profile towards the high angle side of the
1(001) diffractogram. The measure is performed after Ca-saturation and
subsequent glycolation.

WEATHERING

.15

10 ACUTE INDEX

ILUTE WITH ILUTE WITH OPEN


ACUTE PEAK LARGE FOOT ILLITE
VARIETIES OF ILLITE
Ip.a. Ip.l lo

Figure 9. - Diagrammatic representaron of the Hite evolution during the Figure 10. - opening state of illite after MELLIERES and PEREZ-NIETO
weathering (after THOREZ, 1973). Vertical axis : Al2O3/FeO + MgO ESQUE- (1973), in sedimentary Hites :
VIN's ratio in the octahedral layer based on the intensities ratio (002)7(001) ; St-S|
horizontal axis : subdvisons of the acuate ndex la of the ilute, based on the EQ=100 ST
thickness of the 10 reflection at half-heght above background : Hite with Sj=total surface of the 10 reflection above background ; S| = surface of the
acute peak Ip.A.) with la3mm ; Hite wth enlarged foot (lp_|_)with Ig 6mm ; normal reflection of the (well-crystallized) illite centered on the 10 ; the
open illite, with la equal or above 10 mm. (A) = domain of Hites with a surface s limited, on the high angle side of the diffractogram, by the
muscovite composition ; (B) = domain of illites with a phengite compositon ; descendng curve of the reflection ; on the low angle side, the shape of the
(C) = ilute with a muscovite + biotte composition ; (D) = Hites with a biotite reflection is delimited by drawing the symmetncal branch of the high angle
compostion at the level of the octahedral layer (ESQUEVIN, 1969). side of the reflection. Sample pretreated with Ca, and glycolated.

15
Of course all these crystallinity ndexes are not to be considerad
as reliable measures with the crystallography of the mineral. But
they are useful when one has to deal with mportant series of
samples wherein sensitive modifications may appear in the shape
of the basal reflection of the ilute component, accordingly to certain
evolutions in the degree of the metamorphism or of the wea-
thering. In practice these measurements whathever the method
selected are easy to perform f the clay mixture comprises the
ilute as the main component. If interference effects ooccur in the
interested X-ray reas (for nstance : presence of the 14of chlorite,
vermiculite, mixed layers etc...) the measure cannot be readily
achieved. There is also the case where pyrophyllite occurs with
illite (figure 11).

-1/2 height

Figure 11. - Interference of the (002) of pyrophyllite at 9.1 A, with the (001)
of illite at 10A during the evaluation of the acule ndex l a of the latter
mineral by DUNOYER de SEGONZAC's method of characterization the
crystallinity. (A) : case of a mixture where the basal reflection (002) of
pyrophyllite is not apparent and causes an enlargement of the illite reflection
towards the high angle side ; (B): case of a mixture composed of pyrophyllite
and illite; their basal reflections are very closed, causing an enlargement
of the low part of the reflections while twq distinct peaks appear in the high
part of the reflections respectively at 9.1 (pyrophyllite), and at 10 (illite). BACKGROUND

IV - D - PYROPHYLLITE (Pyr) AND TALC (Tale)

These minerals are composed of layers structurally similar to the at least 1000C and can still be detected in the X-ray pattern.
micas except that they are electrically neutral, and that there are
no interlayer cations (BROWN, 1961, p. 469). The identification of one of these minerals in a clay fraction should
Pyrophyllite, tale and the allied mineral m/nnesota/te are o readily be verified by the examination of the whole X-ray pattern (oriented
distinguished on the basis of their (002) reflection at 9.16A (pyro- aggregate and powder preparation). These layer silicatos might be
phyllite), at 9.30 (tale) at 9.53-9.6 (minnesotaite)o. The other also easly confused on the basis of their (002) reflection with
reflections of the (OOI) series are situated at : 4.58 (004) and some platy zeo/ites, with britt/e micas (margarite, clintonite, seyber-
3.05 (006) for pyrophyl/ite ; at 4.65 (004) and 3.1 O (006) for tite, xantophyllite) or with paragonite (see table below).
tale ; 4.77 (004) and 3.1 7 (006) for minnesotaite.
These three minerals can be differentiated on the basiso of their ame (002) (004) (006) (060) n d ()
(060) reflection, respectively at 1.49, 1.54 and 1.57 : pyro-
phyllite is dioctahedral, the two others are trioctahedral. The (OOI) Willemseite 9.4 4.68 3.12 1.524
reflections are symmetric, narrow and relatively intense. The basal
reflection (002) s stable upon glycolation (glycerolation), and Paragonite 9.6-9.7 4.82 3.20 1.48
heating.
Margarite 9.56 4.78 3.19 1.48
The behaviour (002) reflection can be expressed as follows :
Clintonite 9.65 4.82 3.29 1.500
Treatments N EG 500C (001) (002) (003)

(002) n d() 9. 9. 9. Bityite 9.46 4.79 3.136 1.45


Ephesite 9.59 4.81 3.20 1.478
The (002) reflection persists on heating up to a high temperature

IV - E - SMECTITES

IV- E - 1. - GENERALITIES

The ame smectite (former montmorillonite-saponite group ame) confirmed during the last 1975 Clay Conference held n Mxico.
s a new group ame forexpanding clay minerals : montmorillonites Smectite will be taken as a group ame while montmorillonite,
(M), beide/lite (Bei), nontronite (Non) (dioctahedral); and saponite beidellite, nontronite as a species ame.
(Sap) (saponite -trioctahedral- group). The use of the ame smec-
tite for minerals of the montmorillonite-saponite group is in ac- The identification of smectites in an oriented aggregate is based
cordance with a suggestion emitted n 1968 by the A. I. P. E. A. on the characteristic expansin of the (001) to about 1 7 (with
Nomenclature Committee. This proposition has been definitively ethylene glycol) orto 18 (with glycerol) ( Mac EWAN, 1944, 1946).

16
A differentiation between montmorillonite and vermicu/ite can be reflection since osome smectites do not provide a distinct narrow
achieved by pretreated Mg-saturated and then glycerolated sam- reflection al 10, after Ihe Irealmenl but a broad reflection with
ples ; montmorillonite is still expandable after the treatment while a lower intensity compared lo Ihe basal refleclion in Ihe unlreated
vermiculite remains stable at 14. sample.
The X-ray patterns of smectite are generally of poor quality and The behaviour of the basal reflection upon trealments can be
the harmonio reflections other than the basal one are usually more formulated as follows :
or less diffuse. The most intense reflection, corresponding to the
basal one, occurs n the d-spacing range of 12-15. Some
varieties exhibit in the natural sample a prominent 14-15 Treatments N EG Gl 500"C
reflection with a diffuse range (tail) down to 10. This is probably
(001) n d() 12-15 17 18 9.6-10
n relation with the degree of the hydratation, or corresponds to
some random mixed layering involving smectite layers as well.
It is often written that a 12-montmorllonite corresponds to a Na- Generally speaking if the X-ray pattern of Ihe orienled smeclite
montmorillonite with one H2O molecule, while a 14-montmorillonite s relalively poor in refleclions n the untreatedsample, the distensin
belongs to the Ca-varieties with two H2O molecules ; but the of the lallice by polyalcools causes somelimes Ihe appearance of
hydration degrees range influences greatly the (001) basal spac- Ihe other harmonio reflections at 8.5 (002), 5.7 (003), 4.2 (004),
ing, and the chemical analysis must then be performed before one 3.4 (005). Moreover n the natural (untrealed) sample Ihere often
may decide if the mineral s a Na- or a Ca-rich one. occurs a 4.7 reflection which must not be confused with the (003)
The heating provokes a collapse of the first order, the mineral of a chlorite al the same d-spacing. In many varieties of smectites,
becoming anhydrous with a valu of the d-spacng o equal to 9.6-10. the X-ray pattern of oriented aggregate exhibits an intense 14-15
In a parallel way a reflection occurs near 3.1 7. In sedimentary (001 \ reflection while other reflections of very low intensity occur
smectites the d-spacng after heating s generally situated at 10. at 5A and 3.05. Dioctahedral smectites have a (060) between
When smectite is engaged into a mixture with ilute, it is not ndicated 1.49-1.52, while trioctahedral smectites have Iheir (060) between
to try after heating a semi-quantitative evaluation of the smectite 1.53-1.54.
conten on the basis of Ihe increased common 10A (Ilite+smectite)

IV - E -2. - NON-SMECTITIC COMPOSITION OF 1 7 GLYCOLATED MATERIAL


Emphasis must be put on the fac that all clay material or mineral K-, Na- and Ca-salurated samples while 10 layers are absent
that swells to 1 7A when glycolated is not necessarily related to or present in very low concenlralions n Ihe natural fraction.
a smectite. This shows Ihat some of the expanding silicato layers of the un-
Mg-desaturated vermiculite may behave as a smectite upon ethylene treated fractions have been rendered non-expanding when
glycol or glycerol. exchanged with K+, Na+ or Ca++ ;
On another hand there exist several varieties of random mixed 2) The intensities of the 1 7 reflection show that the amount of
layers composed of a majority of montmorillonite (or beidellite) expanding material has been reduced considerably in the K-satu-
layers, and of a minority of illilic layers that similarly expand to rated sample, somewhat less n the Na+-clay, and even less n
1 7 too. The problem, and its different aspects will be dealt with n the Ca++-clay. Presumably all the layers that do not diffract
chapter VI devoted to the mixed layer materials. at 1 7 after the treatmenl have been converted tp non-expanded
An mportant paper by ROBERSON and JOAS (1965) has esta- 10 diffracling layers. The intensily of Ihe 1 7 reflection may
blished the occurrence of clay minerals that are intermedale belween be a more sensitive indicalion of Ihe amounl of conversin than
Hile and monlmorillonite. Different resulls of this paper are sum- s the height of the 10 refleclion ;
marized here. The paper evokes the presence and properties of 3) When the s Na+-clay s saturated with Ca++, there s a reduction
three-layer clay minerals obtained as a series of size fractions of n the 10 reflection indicating Ihat the Ca++ exchanges for
a montmorillonite. With the naturalexchange cations,the 2-4microns some of the Na+.
fraction of the clay expands when solvated with ethylene glycol.
After exchanging the natural interlayer cations for either Na+ or 4) there s a more intense 10 reflection for the K+-trealed and
K+ or Ca+ + , a portion of the fraction collapses to a 10 d-spacing Na+-lrealed clay at 60%RH than there is afler glycolation indi-
even when soaked with ethylene glycol. II appears, as shown by cating thal fewer of the layers will expand at 60%RH than will
ROBERSON and JOAS, Ihat this material represents a missing expand when solvated with ethylene glycol ;
iink in the series between montmorillonite and Hite. Montmoril- 5) discrete phases of 10 and 17 predomnate; there is litlle
lonite s recognized by nterlayer expansin Ihal can be caused by indication of random mixed-layering ;
the relatively weak absorption of water as well as the stronger 6) fewer 10 layers are formed when finer fractions (than 2-4
absorption of elhylene glycol regardless of the type of on occu- microns) are saturated with Na+ or K+. Ca-saturation of the
pying the interlayer position. These ions are fully exchangeable finer fractions produces no layers that diffract at 10.
with ions from sal Solutions of modrate concentraron, ////fe, on
the other hand, resisls to expansin with eilher waler or ethylene glycol, The indications provided by ROBERSON and JOAS (op. cit.) are
and the interlayer cations are not exchangeable except under long- imporlanl because, as t will be shown later, the differentiation
term treatments with concentrated solutions. A portion of the between smectite species s partly based on their behaviour upon
material described by the two above authors, afler exchange wilh cation-saturations. The important point _lo recall here s Ihat all
Na+ or K+ or Ca++, resembles ////fe in that it does not expand, clay material thal expands thus to 17 after glycolation s not
but the interlayer ions are exchangeable like those in montmorillonite. readily to be related to a true smectile mineral : there are several
(it must be indicated that the material is n fact a bentonitic clay). types of random mixed layers (thal behave similarly with glycol),
Examination of the X-ray diffraction palterns by ROBERSON and and there are thus Ihe intermedate mineral sludied by ROBERSON
JOAS (op. cit.) has shown Ihe following facts : and JOAS (op. cit.).
1) after glycol solvation, some of the layers diffract at 10 n the

17
IV - E - 3. - CRYSTALLINITY OF SMECTITES (dioctahedral species)
An evaluation and characterzation of the crystallinity of smecttes t s probably not entirely independen! of smectite abundance in
can be brought about n two complementary ways. When one deals the sample. This ratio is thus not a true measure of crystallinity, but
with important series of smectitic clays in sedimentary or strati- a good first approximation .
graphical problems, t is of nterest to fix up the trends of the (001)
as exh'ibited n the X-ray diffractogram patterns of glycolated The present author has uses this parameter n analyses of several
samples. Such an objective can be achieved ndependently of the hundreds of samples where smectite was a dominant componen!
real composition of the mineral f nodetailed analyses are completed. of the mixture ; he has obtained good correlations of this ratio with
In particular two methods enable the characterization of the crys- the stratigraphical position and depth of the samples as well with
tallinity (BISCAYE, 1965; THOREZ, 1974 and unpublished data). the diagenetic effects affecting these samples. BISCAYE's para-
meter can be combined with crystallinity classes developed by
A measure of the crystallinity of the smectite has been proposed THOREZ (1974 ; unpublished data).
by BISCAYE (op. cit.) as an additional and useful parameter n
routine even if empirical. It is an observation fact that the 1 7 (001) The five "crystallinity" classes developed by the present author are
reflection of an expanded smectite s often broad, and may exhibit schematized in figure 13. They are based on the shape of the 1 7 A
several patterns (or shapes). BISCAYE's parameter consists to reflection, and on the occurrence/lack, shapes and intensities of the
measure both the height of the 17A reflection above the background other (OOI) reflections for glycolated smectite. Emphasis s put
(the valu is indicated by the letter p , p for peak), and the depth on the manner the (002) is developed as well-shaped (class A),
of the val ley ( v ); the latter is shown moreor less well-developed badly-shaped reflection (class C), as shoulder (class B) or as foot
on the low angle side of the 17 reflection. (class D) ; the same gradation occurs n a parallel way with the (003)
A ratio v/p s then measured on the X-ray diffractogram pattern of of smectite. To reinforce through these classes the modification
the oriented aggregate. BISCAYE's comments are following : affecting the shape of the (002) and (003), figure 13 compares the
Because of the low angle position of the expanded smectite re- diffraction effects with those of the (OOI) -1001) and (002)- reflec-
flection (5.2 26), the depth of the valley (v) depends upon where tions of illite (figured as blackened reflections) and taken as nternal
the low-angle side of the reflection ntercepts and contributes to standard. This s shown on account of the ubiquitous character
the general background radiation which rises exponentially at low of illite n many mixtures where smectite also occurs. In a parallel
angles. The broadest the reflection is, the highest s the 29 angle way the v/p ratio by BISCAYE (op. cit.) s also represented.
at which t will contribute to the background trace, and the shal- Figure 14 shows the way these two parameters, v/p and crystal-
lowest s the valley between the reflection (at or near 1 7) and linity classes, may be used graphically. There appears a good
background. As a consequence a perfectly crystallized smectite correlation for the disposition of the representative points when
will have a v/p ratio approaching the unity (value = 1). Poor-crystal- important series of samples are analysed providing the smectites
lzed materials will correspond to small fraction of the ratio until show some variability both n the v/p and crystallinity classes.
v/p=^0 because there does not exist any valley and the reflection The method has been apphed to several problems by the present
at 5.2 26 is appearing just as a shoulder. author; it has been possible to reach a better presentaron and
For very poorly crystallinities, the ratio v/p will be represented by differentiation between the different samples, series, stratigraphical
increasingly large negativa fractions (see figure 12). As the ratio positions, weathering evolution etc...
v/p is based upon measurements of vertical reflection parameters,

V/p =0.7 V/p = 0.1

A B

5.2 26 5.2 26 5.2 29

Figure 12. - v/p rallo (< valley / peak height ratio) for the characterization of the c r y s t a l l i n i t y of smectites
(after BISCAYE, 1965). The measurement s achieved on the 1 7 peak of the glycolated material, p is measured
below the apex of the 1 7 reflection, above the background: v is measuring the importance of the depression
(valley) towards the low angle side of the 1 7 reflection. (A) : well-crystallized smectite; (B) and (C) : badly-
crystallized smectites.

18
WELL-CRYSTALLIZED
17 (001)
CLASS A CLASS B CLASS C
v/p>0 v/p>0
Positive Positive
I
10

I (003)
5 M
ENLARGED
FOOT
\

BADLY CRYSTALLIZED

CLASS E
ILUTE
v/p<0 REFLECTIONS
Negativa
I
5 M
MONTMORILLONITE
REFLECTIONS

CRYSTALLINITY CLASSES OF MONTMORILLONITES

Figure 13. - Empincal crystallinity classes of smectitic materials based Wp RATIO (BISCAVE, 1965)

on : 1) the shape, symmetry, ntensity of the 1 7 reflection ; 2) on the


occurrence/absence and shape of the (002) at about 8, and (003) at SMECTITES (MONTMORILLONITES)
about 5.4. (THOREZ). CRYSTALLINITY

Figure 14. - Relationship between the crystallinity ndex v/p of BISCAYE


(1965), and the crystallinity classes of THOREZ ( 1 9 7 4 ; unpublished
data), allowing the characterization of the smectite evolution during weathe-
ring or n a sedimentary interval of sediments rich in smectites. This C CD D E
relationship can be provided independently of the smectite composition. CRYSTALLINITY CLASSES (THOREZ)

19
Figure 15. - Differentiation between smectites (montmonllonites) varieties after selective treatments
(after THOREZ, 1975).

If diffraction band extends from 14 to 17 A = mixing of smectite with high charge


and of vermiculite.
K saturation + glycerol (KGI) with reflection at 14 : high charge smectite.
The collapse was that t had a high net of umbalanced negative charges wch resulted
m Stron
* D/^DCDT P D A DOLJ A r\ 9 bonding with K saturation, the bonding being strong enough to prevent the 2
RBLRT & BARSHAD (1972) molecule layers of glycerol from entering between sheets.

20
IV - E - 4. - IDENTIFICATION OF SPECIES
There s a possibility to reach an accurate Identification of the VEEN (1970) considers it likely that authigenic smectite is concer-
different species represented n the smectite group : montmon- ned when the basal spacing contrais to 9.5 after heat treatment.
lonite, beidellite, low charge and high charge montmorillonites, When the basal spacing only collapses to about 10, this might
nontronite, montmorillonite with Al- or Fe-inter/ayers, etc... This point out to a mica-derived smectite, the larger contraction being
objective can be achieved by complementary tests involving cation- probably produced by the presence of K-ions located in the smec-
saturations, solvation by ethylene glycol and glycerol, heating tite layers as an inheritance effect from the parental mica structure.
treatments, variability n the RH conditions.
Figure 15, taken from THOREZ's (1975) Laboratory Handbook,
provides the necessary data for such a differentiation. These data IV - E - 4c. - INTERMEDATE SMECTITE-VERMICULITE
result from a synthesls of the available ones n the literatura. MINERALS
To allow a quick check of the variability of the behaviour of the
minerals upon the different tests, the d(001) n has been repre- In relationship with the considerations emitted above about the
sented by a mnemotechnic code (see table 2). The reader is in a authigenic or mica-derived character of smectites, ROBERT and
BARSHAD (1972) have pointed out the occurrence of expandmg
right position to reach a step-by-step differentiation and recognition
of the different and possible varieties n the smectite group (dioc- minerals intermedate between smectites and vermiculites (see fig-
tahedral species only). ure 15, separated column on the right hand). Referring to the
behaviour of these minerals after cation-saturations (with Ca"1""1",
Mg ++, L+, Na+, K + ), solvation (with ethylene glycol, glycerol,
IV - E - 4a. - SMECTITES WITH HIGH AND LOW CHARGES and water), and heating (to 110C), ROBERT and BARSHAD
(op. cit.) have demonstrated these minerals to show :
A significant difference between low-charge and high-charge smec- 1) smectite properties thanks to their expansin with ethylene glycol
tites can be obtained on the basis of the contraction of the mineral (with Mg and Na), or with glycerol (with Mg);
after K-saturation (WEAVER, 1958).
BARSHAD (1954) has stated that saturation causes an expanded 2) vermiculite properties (see detailed data for the vermiculite in
lattice with a high negative charge to contract to d(001)=10.4, the next chapter) because of the one layer swelling effect with
while a lattice with a low negative charge contrais tod(001) = 1 2.4. Na ; the mineral has also a vermiculite behaviour on account
Also HARWARD ef al. (1969) stated that at 45% RH, d(001)=12 of its irreversible contraction when K-saturated and heated to
for a K-saturated montmorillonite, and d(001)=11.6 for a K-satura- 110C.
ted beidellite with a relative high tetrahedrally located charge. 3) intermedate characters between smectite and vermiculite be-
cause of the swelling with water for the Mg- and Na-saturated
samp/es, or the lack of contraction for the K-saturated sample
IV - E - 4b. - GENETIC DIFFERENTIATION BETWEEN SMECTITES : treated with water or glycerol.
LOW-CHARGE AND HIGH-CHARGE SMECTITES, AU- The results obtained by ROBERT and BARSHAD (op. cit.) lead
THIGENIC AND MICA-DERIVED SMECTITES. to some important conclusions about the identification of such an
intermedate material, n particular if one refers only in practice
Interpretation of the occurrence of smectites has also to be based to a selected cation-saturation and to a single method of solvation.
on the difference between authigenic smectites and those originated Indeed, as demonstrated by these authors :
by the transformaron from other minerals and phyllosilicates. Often
this differentiation is by mostly difficult because two categories of 1) with ethylene glycol and Na- or Ca- or Mg-saturation, the mineral
smectite can only be differentiated after further and detailed inves- corres ponds to a smectite that different ates itself from low-charge
tigations (WIERSMA, 1970). This genetic differentiation has been vermiculite ;
too often disregarded (WEAVER, 1958 ; SCHWERTMANN, 1962). 2) with glycerol treatment, the mineral s a smectite when only
Smectites derived from Hite though transformaron might be indicated Mg-saturated, or a vermiculite f only Na-saturated ;
by high-charge minerals whereas a large part of the authigenic smec-
tites are of the type with a low-charge. SCHWERTMANN (1962) 3) the heating to 110C, and the air dried specimen show a
considers also that low-charge smectites may not only have been a variation within the expansin when the mineral is saturated
formed by the breakdown products of volcanic material, but also with monovallent cations. The Li-saturation cannot be used for
from the weathering of augite, hornblende, and feldspars, and from the identification of the beidellite composition. (see paragraph
hydrothermal solutions. IV-E-d).
WEAyER (1958) considered mica-derived smectite to collapse with As an immediate consequence the above authors recommend two
K-satration to a d(001) = 10.0-10.4, while authigenic smectite determination tests at least, which offer several possible results
(volcanic derived smectite, weathered augite, hydrothermal smectite) a) Na- then Mg-saturation, with subsequent glycerolation : vermicu-
has a d(001)= 10.4-1 2.4 after the same treatment. If this treatment lite will always give a single interlayer complex, while smectite
does not result into a contraction, WEAVER (op. cit.) has considered will always largely expand (two-layers complex). But smectites
the mineral to possess a low octahedrally located charge. generated by the transformation of previous minerals (cf. smectite
For authigenic smectite, GALLITELLI (1962) indicated a K-contrac- of transformation ) will only fix one layer with Na, and two layers
tion to d(001)=11.6-12; GORBUNOV and GRADUSOV (1966) with Mg during the glycerolation treatment;
indicated a valu of d(001)=12.5A for authigenic smectites, and b) if there exists a double layer swelling with glycerol after Mg-
d(001)=10-11 for a mica-derived smectite after a K-saturation saturation, there s an indication for a further investigaron : K-satu-
treatment. ration, and heating to 110C.
The smectites originated by the weathering of dioctahedral micas
It thus appears from those data (also those presented in figure will contract to 70/4 and maintain their contraction to 10 when
15) that high-charge smectites show a stronger K-contraction tp solvated with water, glycerol and ethylene glycol. True (neo-
a d(001)=10-11 than low-charge smectites where d(001)=12. formed, authigenic) smectites will swell after the K-saturation with
K-saturated mica-derived smectites treated with glycerol have, on water, glycerol, ethylene glycol.
the other hand, a d(001 ) = 10-14 while authigenic smectites expand
to 18A. For low-charge K-saturated smectites QUAKERNAAT The intermedate character of these materials have already been
(1968) stated o an expansin to d(001) = 1 7 with ethylene glycol, and shown by SCHWERTMANN (1962) by a comparison of the pro-
d(001) = 17.8 with glycerol. For high-charge K-smectites the same perties between standard (Wyoming-type) montmorillonite and
author stated a d(001 )=1 2.4-1 2.7A after glycolation, and d(001)= almost pur montmorillonite extracted from soil. The latter mineral
12.4-14A after glycerolation. has shown a greater contraction after K-saturation in spite of its
lower catin exchange capacity. WEAVER (1958) has suggested
But the degree of K-contraction can be sensibly affected by the that the K-fixation is related to an excess of negative charges
possible occurrence of nterlayer materials and ntergrades (RICH associated with tetrahedral layers.
and OBERSHAIN, 1955; WALKER, 1957; RICH, 1968), or by
organic materials, or by other factors (GEBHARDT et al., 1966).

21
Figure 16. - Effects o amorphous material during the Li-test of GREENE-KELLY (1953), for the
distinction between montmonllonite and beidelte (after MURAVYOV, 1970, m THOREZ, 1975).

How amorphous collodal substance in natural montmorillonite can affect the sorption
properties.
Li-test may fail to give conclusive results without prior removal of amorphous material.

1 octahedraly substitued montmorillonite.


2 tetrahedraly substitued montrnorillonite.
* amorphous SiO2 extraction with 10 % Na3CO3 at T = 90-95 C ; extracted amount
= 18,3 %.
" % SiO2<2 + Fe (OH).
IV - E - 4d. - THE GREENE-KELLY's LI-TEST At 55%RH prior to the glycerol (vapor) treatment, Mg-saturation
again results in a differentiation between montmorillonite and bei-
Distinction between beidellite and montmorillonite can be reached dellite. However on Ca-saturation the beidellite shows some
with the GREENE-KELLY's test. It concerns the L-saturaton of the expansin to 16A that leads to a less clear differentiation.
sample, with subsequent heating to 250C, and the solvation with
glycerol. K-saturated montmorillonite and beidellite show little difference with
Tetrahedrally substitued montmorillonites swell to 17-18, while respect to humid atmosphere (O to 80%RH), but at 100%RH
beidellites remain stable at the original d-spacing. But caution must K-montmorillonite expands toward a two-layer complex with a
been paid when amorphous matarais are occurring n the sample. d(001)=15, while the K-beidellite expands only toward a one-layer
MURAVYOV (1970 ; figure 16) has demonstrated how amorphous complex with d(001)=13.7A. K-montmorillonites also show a greater
collodal substances can affect the absorption properties, with the tendency than K-beidellites toward rehydratation after heating at
consequence that the Li-test can fail to provide conclusive results 400-500C.
if one does not remove prior to the test the contaminant material. These results are reported n table 11, and n figure 15.
SCHULTZ (1969) has published a careful study of more than eighty
samples to try a distinction, upon L- and K-saturations, between Treatments
Wyoming, Tatatilla, Otay, Chambers, and non-ideal types of mont- solvation Beidellite Montmorillonite
morillonites, as well between ideal and non-ideal types of beidellite. saturating moisture Bei M
Detailed data are provided in SCHULTZ's paper, but t has been catin conditioning
of some interest to record here some of the results n the scope
of a routine dentification of smectites. Mg 55% RH 14.8-15.0 15.0-15.2
As shown by SCHULTZ (op. c/f.), the GREENE-KELLY's test with Mg dried at 105 C EG vapor 16.8-17.0 16.9-17.0
Li-saturation discriminates between beidellite and montmorillonite. Mg dried at 105C Gl vapor 14.2-14.5 16.7-17.8
An estimation of the expanding bejdellite-like layers is based on Mg 55% RH Gl vapor 14.2-14.5 16.1-17.6
the relative intensities of the 9.6 (collapsed layers) and 18 Mg dried at 105C Gl liquid 17.8-17.9 17.9
expanding layers) before and afterthe treatment with liquid glycerol.
On the other hand, K-saturation, heating to 300C/'/2hour, and EG = ethylene glycol ; Gl = glycerol ; Bei = beidellite ; M = mont-
the degree of re-expansion after glycerolation appear to be n morillonite.
relationship with the total net layer charge of Al-smectites (a later
paragraph will deal with Al-smectites and vermiculites). Wyoming- Table 11. Expansin of synthetic beidellite and montmorillonite
type montmorillonites have a low net layer charge and re-expand [vales of (001) in d()](after HARWARD and BRINDLEY, 1964).
to 17. The different types quoted by SCHULTZ show a high net
layer charge, and re-expand only to 13-16A. SCHULTZ (op. c/f.)
points out that the same relationship of net layer charge and re- HARWARD ef al. (1969) have mproved the basis for differentiating
expansion seems to mtervene with the same mportance in the case criteria for the identification of smectites and vermiculites (table 12 ;
of the examination of beidellites. see also figures 15 and 19).

IV - E - 4e. - DIFFERENTIATION BETWEEN BEIDELLITE, Some comments by HARWARD ef al. (op. c/f.) can be provided
MONTMORILLONITE AND VERMICULITE about table 1 2 content.
The montmorillonite expands to the equivalent two-layer complex
upon solvation by condensaron of ethylene glycol or glycerol
Montmorillonite is characterized by a lower charge compared to
vermiculite, and substitution of Mg for Al in the octahedral layer vapour. Beidellite exhibits the one-layer complex with glycerol
while vermiculite has a higher charge arising from substitution of vapour, and the two-layer complex with ethylene glycol. The vermi-
Al for Si n tetrahedral layer. HARWARD and BRINDLEY (1964) culite does not yield regular two-layer complexes regardness of
have provided conclusive data for the differentiation of beidellite saturating catin, prior to the moisture or the solvating agent
from montmorillonite on account of the results of experimental action. A number of different complexes of vermiculite are obtained
wo;ks conducted n synthetic materials with exchange capacities depending on conditions of solvation (spacings at 13.6A, 14.OA,
in the range 0.95-1.35 meq/gr. These two authors have shown that 14.3, 15A and 15.3).
oeidellite is intermedate between montmorillonite and vermiculite. K-saturated vermiculite and K-saturated smectites (montmorillonites
with respect to the expansin upon solvation (see figure 15). and beidellites) both exhibit collapsed layers n a dry atmosphere.
From HARWARD and BRINDLEY's (op. c/f.) experiments it is Hydratation of smectites occurs at humidities above 20%, and
clearly established that a distinction can be achieved between results n poorly ordered diffraction mxima of 11-12. The K-
montmorillonite and beidellite on the basis of the swelling behaviour saturated vermiculite tends to retain the collapsed lattice, and
.."en certain definite conditions are imposed. Solvation with ethy- exhibits diffraction mxima of 10-10.6, with integral higher orders.
"e glycol or with glycerol (liquid) offers no olear differentiation. Some hydratation occurs as evidenced by the reflection asymmetnc
3 _ t with glycerol vapours, and Mg- and Ca-saturation with drying shapes, or by the appearance of a small 14.3 reflection at higher
at 105C. before solvation, montmorillonite expands to about humidities, although the collapsed spacing predominates. The ten-
16.7-17.7, while beidellite expands only or remains at about dency of vermiculite to hydrate decreases as the exchange capacity
14.2-1 4.6. increases.

Treatments
M M Bei V
saturation moisture solvation d(001) m A d(001) n A d(001) in A
catin conditioning

Mg 54% RH 15.3 14.7 14.3


Mg Gl vapor 17.4 14.4 14.1
Mg EG vapor 16.9 16.8 14.2
K air dried 10.3 10.3 10.3
K 54% RH 12.1 11.6 10.4

Table 12. Differentiation between montmorillonites, beidellites, and vermiculites on


the basis of the saturating catin, moisture conditioning, and solvation method
(after HARWARD ef al., 1969).
Remark : Mg-saturation gives more consistent results than Ca-saturation for solva-
tion of vermiculite. The reverse s true for montmorillonite.

23
IV - E - 4f. - AI-SMECTITES AND AI-VERMICULITES ; adsorbed into the interlayer surfaces of the montmorillonite formed
Fe-SMECTITES in situ, and in part translocated from the A horizon. By these
interlayering and subsequent altrnate dessication and wetting
RICH (1968) has emphasized the occurrence of smectites and processes, the silicate layers in the B horizon will become so
vermiculites in soils and sediments that are frequently and partially firmly constricted that the glycerol molecules cannot enter; an
inter/ayered o r chloritized. Dioctahedral expansible layer silicates agressive agent as 4M HCI must then be used to dissolve the Al
are those most frequently interlayered, and hydroxy-AI appears to and Fe compounds and allow a subsequent expansin upon gly-
be the principal componen! of the non exchangeable interlayer cerolation.
material. But the main problem which we were dealing with is to unable
Vermiculites with such nterlayers do not collapse readily after a distinction between a partially interlayered vermiculite or smectite
K-saturation. The basal spacings of smectites show a collapse on from a randomly interstratified vermiculite-chlorite (cf. the (14c~14v)
their side, after having been K-saturated ; this collapse depends following THOREZ's (1975) codificaron ; see chapter VI), or smec-
on the charge density, humidity conditions (SAYEGH et al., 1965), tite-chlorite mixed layer structure (14M-14c). Partial collapse should
and presence of nterlayer material. reveal non-integral higher orders of the nterstratified material,
As reported by RICH (1968), low-charge smectites placed in a but higher orders of the nterstratified material, may also not
moist atmosphere do not easily collapse on K-saturation even if been distinct n the preparation as well. For the ntergrade
nterlayers are absent. Interlayered expansible layer silicates may not material, there is an increase n central scattering (Mac EWAN,
expand with glycerol solvation (JAMURA, 1957, 1958), but mont- 1950), and a broadening of the 10 reflection on K-saturation
morillonite expands when nterlayers are first removed and the and subsequent 550C heating (JACKSON, 1963).
clay is then Mg-saturated and glycerolated. The relative intensities of the (001) and (002) reflections are also
Some parallel and interesting features have been published by indicative of interlayering ; as the interlayering ncreases in the
WIKLANDER and ALEKSANDROVIC (1969) about what they cali a structure, the intensities ratio (002)7(001) (cf. I7/I14) of the
crypto-montmorillonite found in Swedish Earths and Podzols. mixed layers increases as well. But caution must be taken n the
The behaviour of this particuliar mineral has also been recorded evaluation of this above ratio when kaolinite occurs n the clay
in the stylised diffractogram patterns by THOREZ (1975). In the fraction ; then the 1(003)71(001) may sometimes be more useful.
B horizon of the examined podzols no true montmorillonite occurs On another hand chloritization may not be uniform n all the
after glycerolation. On heating at 450 and 600C, the 14.2 s nterlayers.
replaced by a broad reflection at 11,3. If the clay s prepared
with 4M HCI, a distinct and large montmorillonite reflection appears
that expands to 18. The authors have demonstrated that the ap- IV - E - 4g. - WYOMING-, CHETO, AND IRON-RICH
pearance of the 18 reflection is not caused by swelling vermiculite MONTMORILLONITES
and/or chlorite as these minerals are normally dissolved in 4M HCI.
GRIM and KULBICKI (1961) have published some routine Gritera
By acid treatment, thus, hydroxy aluminum and ron adsorbed on for a X-ray diffraction distinguishing between Cheto- and Wyoming-
and oriented between the interplanar surfaces are dissolved. This type smectites, for a mixture of these two types, and a iron-rich
makes it possible the entrance and adsorption of glycerol molecules montmorillonite. It is of nterest to recall here the importan! works
on the inner surfaces. The montmorillonite has thereby been trans- completed by GRIM and KULBICKI (op. c/f.), and in Strasbourg's
formad from a non-expanding material with d(001) at 14 into Laboratory of Profs. MILLOT and LUCAS about the possibility of
an expanding one with d(001) at 18. WIKLANDER ef al. (1969) differentiation between the different smectites by the DTA method,
have also found that treatments with TAMM's oxalate solution and combined with TGA. But those methods are only accurate if the
ditionite solution do not induce expansin of the d-spacings n analysed material s made of a rather pur smectite. Otherwise
glycerol while the HCI does it. interferences are taking place in the DTA curves, and lead to some
TAMURA (1958) has made similar observations of expansin from discrepancies as well misinterpretations. The thermal accidents
14 to 16-18 with glycerol and Ca-saturation after treatment with may occur at least with 10% of another clay mineral present n the
Na-citrate at 100C for a clay from certain acid soils. This author mixture.
has concluded the unknown mineral to be of montmorillonite type, The Cheto-type montmorillonite is characterized by intense and
modified by weathering. About the mechanism involved in the sharp (001), but the higher orders are always of about uniform
formation of the crypto-montmorillonite WIKLANDER ef al. (op. low intensities (in both cases without and with solvation). The
c/r.) evoked the possible leaching of hydroxy -Al and -Fe from the Wyoming-type montmorillonite has a sharp (001) reflection, and
A horizon to the B horizon. These hydroxy -Al and -Fe are then intense and sharp higher orders too, up to about the (006) reflection.

Montmorillonite Treatments d(001) n R ema rk


types
Wyoming-type + KCL 11.17 (air dried)
+MgCL2 17.4 (air dried, and oven dried at 100C72 hours after glycolation).
There s no permanent collapse of the structure or retardation of expansin related
to the low charge character of the mineral.
Cheto-type + KCI or MgCl2 11.9 or 12.1 (air dried).
15.5 or 14.7 after glycolation
15.5 or 14.7 after having dried the mineral n the oven at 100C/2 hours.
The behaviours are related to the high charge character of the mineral.
Iron-rich + KCI 12.5 (air dried).
montmorillonite
13.6 when K-saturated, then air dried, and glycolated.
11.6 when K-saturated, dried at 100C72 hours n the oven, then glycolated.
The behaviours correspond to a layer substitution within the octahedral position.
Table 13. Distinction between Cheto-, Wyoming-, and ron-rich montmorillonites after cation-saturations (K, Mg) (after GRIM and KULBICKI.
1961).

24
These higher orders are mainly developed after glycerolation. MATSUIand YATSU (1969) have published some Identification data
When a mixture of the two types does occur, the X-ray pattern allowing a quick differentiation between Fe-saponite (trioctahedral),
presents sharp higher orders reflections as for the Wyoming-type, Fe-montmorillonite and nontronite (both dioctahedral). The three
but somewhat less intense reflections : the (004) and (006) are minerals yield of course a high amount of Fe (Fe2O3 + FeO) the
relatively weaker than the (002), (003) and (005). Such a character total of which reaching 13% n the iron-saponite, 15% n the Fe-
is more pronounced in the mixture of the two types than in the pur montmorillonite, and more than 30% n the nontronite.
Wyoming-type mineral. The dioctahedral and trioctahedral characters are established on
Further distnction can been achieved after K- and Mg-saturations the basis of the d(060) : 1.53 for the Fe-saponite, while near
as shown in table 13. 1.50 for the two dioctahedral species. The diagnostic behaviours
of the minerals upon treatments can be formulated as follows:
IV - E - 4h. - DISTNCTION BETWEEN SOIL MONTMORILLONITE,
MS, AND SOIL BEIDELLITE, BeS Treatments
d(001) n N EG 500C MH4NO30 HCl(")
So/7 montmorillonite MQ exhibits a broad 14.5 (001) reflection in
the untreated sample. The glyce/ol solvation provokes the expansin Fe-saponite 15.2 17.0 10.0 12.4 collapses
of the basal reflection to 1 7.9 (the resulting reflection remaining
as broad as n the untreated sample), while a clear reflection, of Fe-montmorillonite 12 g tends to
low ntensity, occurs at 8.9. K-saturation causes a collapse to and nontronite
16 6
' (w?thGI) 99
' collapse
12.4. The heating treatment is also indicative : at 350C there
occurs a diffraction band between 10 and 14.1, with two distinct (*) : 1N NH4NO3, boiled 10 min.; (**) : 6N HCI, 30 min.
reflections, at the above d-spacings and with a more or less well-
developed v a l l e y between them ; at 550C, the basal reflection
has its apex at 9.7 with a clear asymmetry (tail) towards the low MATSUI and YATSU (1969) indicated also that the Fe-saponite
angle side of the X-ray diffractogram pattern. heated to 200C shows a doublet at 10 (asymmetric towards the
These behaviour can be formulated as follows : low angle side, and intense), and at 14.7 (weak and relatively
symmetric). In comparison with the Fe-saponite behaviour upon
diagnostic treatments, it seems of interest to complete the data by
Treatments N Gl K 350C 550C providing those related to a normal" saponite. VENALE and van
der MAREL (1969) have published their observations on saponite.
d(001) n 14.5 b 17.9 b 12.4 b 10+14.1 d 9.7 as At the natural (untreated) state, the d(001) is situated at 14.4;
the reflection being particularly intense and well-defined. Upon
b = broad ; d = diffraction band ; as = asymmetric reflection. glycerolation, the (001) shifts to 1 7.4 (intense and narrow), while
a weak (002) reflection occurs at 8.8f\. K-saturation provokes a
Upon glycerolation, and after Mg-saturation, so;7 beidellite BeiQ collapse of the basal reflection to 11.9A. Heating to 350C does
such as the one described by ROSS and MORTLAND (1966), has not affect the basal reflection neither n position (still at 14.4)
a well-defined and intense reflection at 14.8, with a lower intense or in intensity; but the heating to 550C collapses the basal
reflection at 9.1 [cf. the d(002)]. K-saturation causes a contraction reflection to 9.6. These behaviours are formulated as follows :
of the lattice which shifts to give a d(001)=10.1. The same beha-
viour occurs with a K-saturated sample when heated to 500C.
Of interest is the expansin of the basal reflection to 17.7 with Treatments N Gl K 350 550
the GREENE-KELLY's test; but the basal reflection then becomes
broader, and the (002) reflection appears n the X-ray pattern as d(001) n
a diffraction band with its limits between 8.85 and 9.5A. saponite 14.4 17.4 11.9 14.4 9.6
These behaviour are formulated as follows :

Other uncommon smectites are : volkonskoite, pimelite, sauconite.


Treatments Mg + GI K K+500 U/250C/GI
In the subgroup of dioctahedral smectites the chromium montmoril-
d(001) n 17.8 s 10.1 10.1 17.7 b lonite volkonskoite has been confirmed by ROSS (1960). Chemical
analysis provides the diagnostic character of the mineral with a
s = symmetric, sharp ; b = broad. relatively high conten n Cr. A high conten n Zn, occurs is sauco-
nite. Medmontite, the copper montmorillonite, has been shown to
be n fact a mixture of chryscolle and dioctahedral mica. Some
IV - E - 4. - DISTNCTION BETWEEN SAPONITE, Fe-SAPONITE, controversy and discrepancies still persist about the validity of the
Fe-MONTMORILLONITE AND NONTRONITE nickel-rich montmorillonites named pimelite. For some authors the
mineral appears to be true Ni-saponite, while others consider the
Several data are provided separately n the literature regarding the material to be a talc-like mineral containing nickel. But the ame
characteristic X-ray patterns of these minerals when analysed as pimelite has been however accepted as a ame for a nickel smectite.
oriented aggregates, and identified by routine treatments. For all the varieties of smectites which have been dealt with n this
chapter, THOREZ (1975) has synthetized several data from the
As published /. e. by ROSS and MORTLAND (1966) nontronite literatura both for the characteristic X-ray diffraction patterns of
exhibits a sharp well defined 1 7.7 (001) reflection when Mg-satura- oriented aggregates and random powder mounts.
ted and treated with glycerol. K-saturation and heating to 550 C
provoke a collapse to 10.1; the (001) reflection still remains
intense but less narrow than n the glycolated sample. The GREENE-
KELLY's Li-test provides an X-ray diffractogram pattern with a high
but largely broader 1 7.7 and with a sharp but narrow 8.85 cor-
responding to the d(001) and d(002) reflections respectively. These
behaviour can be formulated as follows :

Treatments Mg+GI K K+550C Li/250C/GI

d(001) in 17.7 n 10.1 10.1 17.7 b

n = narrow ; b = broad.

25
IV - F. - VERMICULITE : V

IV- F- 1. - GENERALITIES
The Identification of vermiculite is often a rather difficult problem new intensity of the 10 ref/ection. The collapse after and upon
because of its variable behaviours upon treatments. The term heating must be checked very carefully because the mineral
vermiculite has been used for numerous minarais which, underX-ray rehydrates very quickly even at room temperatures, and this pro-
diffraction examination, exhibit different properties. vokes heterogeneity of the X-ray diffraction pattern during the
collapsing phenomenon, or a misinterpretation of the real clay
An important character of the mineral, in particular at the level of
its (001)around 14A, is its dependence on the degree of hydratation. composition.
As a consequence it is indlcated for an accurate identificaron to On another hand, the collapse upon heating s not completely achie-
work under uniform and definite relative humidities. ved when the mineral incorporates some hydroxy nterlayered
WALKER (1957, 1958) has shown thatthe most reliable Information material. Particularly in soil clays, vermiculite may be engaged into
can be obtalned wlth Mg-saturated sample prior to the X-ray dif- mixtures with other clay components. As a consequence it often
fractiqn analysis as oriented aggregate. Then, the basal reflection occurs that the d-spacing of the basal reflection remains higher
at 14A in the natural sample remains stable over a wide range of than 10 after the heating. This effect is due to the interlayered
contaminan! which has not been removed by the treatment. It s
relative humldities at room temperature (BROWN, 1961). Mg-verm-
culite resists to expansin with glycerol (WALKER, 1950 ; BARSHAD, thus indicated to Mg-saturate the material, and then to proceed to
1950). However f Mg-saturated vermiculites are not expanding a step-by-step heating : t^ie 14 reflection s replaced by a 11.6
during solvation, certain natural and partially desaturated vermicu- one at 100C, and by a 10A at 300C. But these latter d-spacings
lites may incorprate two nterlayered sheets of glycerol or of must be absolutely measured before the complete cooling of the
ethylene glycol and, as a consequence, expand to 1 7A. That s sample which has to be kept in the oven as long as possible. This
the reason to have a Mg-saturation when vermicullte clay mineral is necessary because the vermiculite is very sensitive within a few
is suspected in a mixture. seconds or minutes to moisture n the laboratory atmosphere. If
these cautions are not taken the vermiculite might well be inter-
Magnesium vermiculite is defined by its sequence of (001) at (001) preted as a faulse chlorite.
14, (002) 7.1, (003) 4.7, and (004) 3.5. The first (or basal
reflection) s characterized by an intense and more or less broad
reflection, while the other (OOI) reflections are of very low ntensity
or even are lacking in the X-ray diffraction pattern. The intensities Treatments
N EG 500
of the (OOI) reflections are thus n contrast with those of a chlorite d(001) n
(see chapter IV-G).
normal, naturally
Heat treatment causes a shift of the 14 spacing to 9-1O. In so/7 or artificially 14 14 9.6-10
clay vermiculites this shifting is often accompagnied by a net Mg-saturated vermiculite
decrease of intensity ; the new reflection s usually broader relatively
to the 14 for the untreated sample. In many examples analysed desaturated vermiculite 14 expansin 1 0 broad
by the present author, t has been significant that the 10 reflection vermiculite with hydroxy
obtained after heating was of very low ntensity, the collapse being 14 variable 12-14
nterlayered matarais
not restricted to the d-spacing alone bul marking particular/y the

IV - F - 2. - DIFFERENTIATION BETWEEN VERMICULITE VARIETS


A normal vermiculite, with no clay-size characters, s thus readily capacity. Mximum expansin and hydratation occur with Ca and Mg
distinguished from smectites and chlorites on the basis of the n interlayer positions, the basal spacing being at 14-15.
effect of the diagnostic r o u t i n e treatments, as recapitulated as TAMURA (1956, 1958) has ndicated that numerous minerals which,
follows : after the normal procedure of identification, have been taken as
dioctahedral vermiculite might well be in fact smectites with Al-
d(001) in hydroxy interlayers that prevent normal expansin upon glycolation.
Mineral (See chapter IV-E-4f.)
N EG 500C
It is also mportant to recall the crypto-montmorillonite described
vermiculite 14 14 10 by WICKLANDER et al. (1969) (see p. 24). As a consequence of
the presence of nterlayered materials, the contraction of the basal
smectite 12-15 17 10 spacing by heating, or by K-saturation, might well be reduced because
chlorite 14 14 14 the occurrence of gibbsitic or brucitic islands " between the layers
(RICH and OBENSHAIN, 1955).
As already pointed out, the basal spacing of vermiculites is depend-
But in clay fractions, or as clay-s/zed vermiculite, the mineral does ing on the degree of hydratation. Microscopio allegedly vermi-
not present the properties of well-crystallized macrovermiculite. culite s able to incorprate polyalcools, with the consequence
The latter is ordinanly trioctahedral with a d(060) at 1.528-1.54, of becoming expansable (Mac EWAN, 1944; BRADLEY, 1945).
while both tri-and dioctahedral types occurs in clay-vermiculites (WALKER, Misleadmg results n the dentification might thus occur. BARSHAD
1950; BROWN, 1953). In clay fraction, the vermicullte behaves (1952) has ntroduced and proposed a salted method n the pre-
as a structure often corresponding to the clay-size minerals ; these paration of vermiculites (and also of smectites) n order to reach a
are probably intermedate and poorly defined materials with better distinction between vermiculites exhibiting various exchange
three sheets. The bonds between the layers seem not to be firmly capacities, and their diagnostic characters n comparison with
attached. Clay-vermiculite can be characterized as a mica-like smectites treated n the same conditions. The results obtained by
mineral with an expanded lattice, and with a high catin exchange BARSHAD (1958) are llustrated n figures 1 7 and 18.

26
= Strong
= Medium
W=Weak
Figure 1 7. - Basal refleclion (001) n lor vermiculite mmerals treated with water or glyoerol as
affected by the nature of nterlayer catin and the method of sample preparation (after BARSHAD, 1 958.
m THOREZ. 1975).
CATIN: Na
GLYCERAT/Q/V

Figure 18. - Basal reflection (001) in A for glycerolated tnontmorillonite minerals as affected by tho
catin exchange capacity, tho nature of the interlayer catin, and Ihe rnethod of sample preparation
(with prevention of drymg) (after BARSHAD, 1958. m THOREZ, 1975).
Figure 19. - Differentiation between vermiculite varieties -behaviour of the d(001) upon treatments
(after THOREZ, 1975).

With K : 14 ; with Mg + 350 C : 10-14 band = chloritized vermiculite.


(2) WALKER (1958) : reaction of expanding lattioe of clay minerals with glycerol and
ethylene glycol :

Mg + EG : d (001) at 16,3 = Vermiculite with charge of 150 meq/100 g.


d (001) at 14 to 15 = Vermiculite with charge > 163 meq/100 g.
Ca + Gl : d (001) at 17,6 = Vermiculite with charge ^ 175 meq/100 g.
Mg + Gl : normally no expansin expected.

29
In particular n the clay-sized vermiculites, but also n the well- In the high-charge varieties a Mg-saturated sample remains stable
crystallized (macro)vermiculite, replacement of the Mg + + by K+ upon either glycolation or glycerolation. The data of WALKER
causes a sensitiva contraction of the c-dimension of the lattice. (1958) are to be compared with those provided by BARSHAD
When K-saturated, and subsequently dried at room temperature, (1958) (figure 19).
the basal spacing originally at about 14 n the untreated sample
s reduced to about 10-11. Many glycolated verrniculites give X-ray patterns with irregular
WEAVER (1958) considers that clay vermiculite derived from the layer sequences and with a d-spacing of 15.4. Such.a d-spacing
mica weathering has a relatively high charge character, and s is intermedate between the ones of a low-charge and of a high-
contracting to about 10A after the K-saturation. On the contrary, charge vermiculite. As a consequence this variety of vermiculite
clay vermiculites generated by the weathering of non phyllosilicates probably corresponds to a random nterlayering of 14.9 and 16.2
(such amphiboles) or from volcanic material, have a low charge, d-spacings.
and show a limited contraction after the same treatment. These
non-mica derived vermiculites show a basal spacing, n the K-satu- Other behaviours characterize verrniculites. Mg-saturated sample
rated sample, which ranges between 11 and 12.4, probably does not expand normally; But low-charge vermiculites (when Ca-
because of the interlayered materials and contaminants. The ubi- saturated) swell to 17.6 with glycerol (or to 15.5-15.8 with
quitous character of the nterlayer contaminants n the expanding ethylene glycol). On another hand, high-charge vermiculites (when
lattice of some clay soil minerals and of mixed layer structures Ca saturated) remain at 14.4 with glycerol, while expand to
has now been clearly established. For nstance Al-interlayers occur 16-16.5 with ethylene glycol. As a consequence, if care is not
as positively charged hydroxy-AI polymers. Gibbsitic or o brucitic taken, some confusin may arise in the identification between a
nterlayers tend to decrease the relative intensity of the 14 reflec- low-charge Ca-saturated vermiculite solvated with glycerol, and
tion too ; on the other hand, they enhance that of the subsequent smectites with both low-andhigh-charges treatedin the same conditions.
low-ordered reflections of the (OOI) series. Also a Al-smectite which becomes Ca-saturated and then solvated
Another consequence of the latter evoked situation is a deviation of with ethylene glycerol provides a basa/ spacing of 14.6-15.3,
the vermiculite interpretation to one of chlorite, because of the more a behaviour which can be easily confused with a high-charge and
or less stability of the 14 reflection upon heating. a low-charge Ca-vermiculite that have been glycero/ated.
Figure 19 displays detailed data to attempt an accurate differen- It s nteresting to notice the behaviour of what can be named a
tiation between the varieties of vermiculite. The elaboration of the ch/oritized vermiculite. The normal or other varieties of vermi;
figure and its informations are based on a review from the literature, culite have their first order reflection collapsed to about 10-11
These data concern : the vermiculite in general ; the low-charge upon K-saturation. A similar range of d-spacing occurs when the
(V<0), and high-charge (V>c) vermiculites, vermiculites with Al- and K-saturated samples have been heated to 100, 300 and 550C.
Fe-interlayers. Also provided for comparison are the characteristic In a chloritized vermiculite, the K-saturation maintains the d-spacing
behaviours of Al-interlayers and of a smectitic mineral with Al- of the (001) at about 14. The Mg-saturation, followed by a heating
interlayers. treatment at 350C, provokes, on the other Jiand, a partial collapse
with a diffraction band between 10 and 1 4.
Upon glycolation low-charg^e vermiculites may exhibit a rather large
d-spacings from 14 to 1 7A ; some have typically a d(001) = 16.2.
Mg-saturation induces ad(001)=14-15 in the untreated (N) sample
that remains at 14, or ranges between 14 and 15.5 upon gly-
colation (14 or 15.5 upon glycerolation). WALKER (1958) indicated
some reactions of the vermiculites upon Mg- and Ca-saturation
(with subsequent solvation) that can be recapituled as follows :

Treatments d(001) in vermiculite composition

16.3 vermiculite
with a charge of 150 meq/100g.
Mg+EG
14 to 15 vermiculite
with a charge above 163 meq/100g.

17.6 vermiculite with a charge


Ca+GI equal or less than 175 meq/100g.

Mg+GI normally no expansin expected

IV - G. - CHLORITES : C

V - G - 1. - GENERALITIES

Well-crystallized chlorites exhibit an integral series of basal reflec- already be entirely decomposed at a temperature of 450C (GRIM
tions at : 14(001), 7(002), 4.7(003), 3.5(004) and 2.8(005). and JHNS, 1954). This latter situation s somewhat embarrassing
But the precise position and intensity of these (OOI) reflections are because one of the proposed identification and differentiation test
deeply depending of the kind of cations occupying both the between chlorite and kaolinite s effectively based on the result of
octahedral and tetrahedral positions (see further the discussion on the heating which, in the range of 450 to 500C, decomposes the
this problem). kaolinite.
The d-spacings are not affected by glycolation or glycerolation. Another characteristic behaviour of the chlorite upon heating to
Upon heating to 500C, the intensities of the (001) reflection are 500-550C is the more_or less complete disappearance of the even
enhanced o while its position s slightly shifted to a lower valu orders at 7 and 3.5, while the uneven ones, n particular the
(13.6-13.8) relatively to the original position in the untreated basal reflection near 14, remain more or less stable (excepted
sample. After the heating treatment, the other (OOI) reflections the slight shift towards the high angle side), and might moreover
decrease in intensity as the brucitic layer decomposes. But poorly be enhanced in intensity.
crystallized chlorites such as found n recent sediments, n soils, Chlorites occurring in the clay fraction (cf. clay-chlorte) are naturally
and in products of the weathering of chlorite-containing rocks, may and easily altered by weathering. As a consequence, defects occur

30
in the lattice that influence the relative ntensities of the (001) reflec- will deal with these peculiar mixed layers derived from the partial
tions. When the brucite layer becomes partly replaced by hydrated weathering of a chlorite structure.
cations during the weathering, the (001) reflection becomes dis-
placed towards the high angle side of the dffractogram after heating, The behaviour of a chlorite upon solvation and heating, can be
it may even not appear after heating because of the low thermal stability expressed as follows :
of the mineral. The easy collapse of the basal reflection might be
then confused with the one of vermiculite. Treatments N EG 550
More or less degraded chiorites, which show a 14 reflection n d(001) n A
the natural sample, that is not affected after solvation, may also
after the heating treatmentexhibit, n place of a single 14 reflection, well-crystallized
various scattering effects such as diffraction band (with ranges 14 14 13.8-14
chlorite
between 10 and 14), doublets, single but broad reflection at about
11, 12A, or 13. This behaviour indicates the occurrence n the soil-chlorite or
degraded chlorite various forms of collapse
chlorite lattice of unstable interlayer spaces which are similar to 14 14 that maintain the (001)
vermiculite. These unstable soil-chlorites are to be considerad, on with (vermiculite)
unstable nterlayers between 10 and 13
the basis of the heating treatment, more as random mixed layers
with residual chlorite layers (14c), and vermiculite inter/ayers (14v) ; collapsed (or decompo-
the representativo formula for such a random mixed layer can be soil-chlorite 14 14 sed at 450C)
shematized by : (14c~14v). Chapter V relative to the mixed layers

IV - G - 2. - VARIETS OF CHLORITE

According to the actual knowledge, chiorites group comprises Dioctahedral chlorite has been named sudofte by MLJLLER (1963) ;
trioctahedral, dioctahedral and di-trioctahedral minerals. After the the subgroup comprises also cookefte, wich is a Li-AI-rich chlorite.
recommendations of the A.I.P.E.A. Nomenclature Committee (Madrid Donbassite is considered as a di-trioctahedral chlorite.
1972), the layer of chiorites has to be considerad as one of the
2:1 type, but with hydroxyde layers in the nterlayer position. Usually the identificaron of the various species in the chlorite group
Representativo of the trioctahedral chiorites are Penninite, C/ino- is a difficult problem. There s a large variety of chiorites because
chlore. The nomenclature of trioctahedral chiorites is still characteri- of the wide possible range of ionic substitutions. Because of
zed by some arbitrariness. FOSTER (1962) has proposed a classi- extensivo solid solutions that occur n the group, there exist no
fication based on the crvstallochemical criteria. Other trioctahedral sharp boundaries between varieties even if some ames have been
chiorites comprise : Sheridanite, Ripidolite, Brunsvigite, Thuringite, used to define some of the species.
Chamosite, Kochubeite, Kmmererite, N imite. The classification of An effort to systematize the classification of chiorites has been
Cr-chlorites has been proposed by LAPHAM (1958); this author attempted by several authors (HEY, 1954; NELSON and ROY,
defines Kmmererite as a chlorite containing Cr3+ exclusively in 1958, and many others). Significant data have been provided by
the octahedral layer ; Kochubeite s considered as a chlorite in NELSON and ROY (1958) toward a systematization of chiorites
which Cr3+ s also localized in the tetrahedral layer. Ni-chlorite the results of which have also been published by WARSHAW and
has been named nimite (WAAL, 1970). ROY (1961).

SEPTECHLORITES NORMAL CHLORITES


Idealized formula Increasing
R" = Mg R'" = AI R" = Fe"R'" = Fe'", Al R" = MgR'" = AI Fe" and Fe1" Oxidized Fe

R"6S4Oio(OH)8 Chrysotile Greenalite (orthochlorites) (leptochloritos)


Antigorite
Lizardite

Penninite Diadantite Delessite

R"5R'"S3R"'O10(OH)8 Clinochlore Chamosite Clinochlore Pycnochlorite


Brunsvigite

Sheridanite Prochlorite
Daphnite

Ripidolite

Corundophyllite

Pseudo- Thuringite
thuringite
Amesite Amesite

Table 14. Classification of Mg-, Al-, and Fe-chlorites (after WARSHAW and ROY, 1961).
Rernark : classification based on studies by NELSON and ROY (1954, 1958), and HEY (1954).
Shuchardite is a nickeliferous normal chlorite ; Grovesite is a manganeso chlorite which may be either the 7 or 14 polymorph
Kmmererite s the Cr-chlorite where Cr substitutos for Al only n the octahedral positions.

31
It is difficult to achieve a comprehensive classification sheme for an excellent synthesis of all the available data. In 1972, BAILEY
chiorites because of the variety of chemical substitutions that are has published an importan! paper on the determinaron of chlorite
possible. Classifications are subject to change with advances in compositions by X-ray spacings and intensities. In particular this
our knowledge of the compositions, properties, and structures of author underlined the fact that the use of the (001) and (060) X-ray
chiorites noted BAILEY in GIESEKING (1975). Since TSCHERMAK's spacings, a method mentionned in the literature as empirical mea-
(1890) classification of chiorites there have been several other ones, sureof the tetrahedral and octahedral catin populations of chiorites,
the most used being, among the modern classifications, those by can show some pitfalls altough useful quantitative informations
HEY (1954) and by FOSTER (1962). (Figures 20 and 21.) obtained. On the other hand, relative (OOI) intensities yield, as
Several authors have also been dealt with the crystallochemical shown by BAILEY (1972), less reliable results that the spacing
aspects of the chiorites. BAILEY in GIESEKING (1975) provided method for octahedral compositions.

6.0

4.0

0.67 -

2.0

2.0 2.5 2.8 3.1 3.5 4.0


Figure 20. - Chlorite species boundaries according to HEY (1954) fot the orthochlonte (A), and oxidized chiorites (B). Abbreviatlon symbols : pThur =
pseudothuringite ; Corun = corundophilite ; Daph daphnite ; Ripi = ripidolite ; Sher = sheridanie ; Bruns brunsvigite : Pyc = pycnochlorite :
Clino = clmochlore ; Penn = pennmite ; Talc-Chlo = talc-chlorite ; Thur = thunngite ; Klem = klementite ; Cham = chamosite ; Deles = delessite.

1.00
I
Th ur
Cham
0.8

Ripi Bruns Di ab
0.6

<M
o:
0.4

0.2
Sher Clino R;nn

2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 4.0
Formula positions occupied by Si
Figure 21. - Chlorite species boundaries according to FOSTER (1962) (U. S. Geol. Surv., Prof Paper, 414, A-19).
Abbreviaion symbols : Thur - thunngite ; Ripi = ripidolite : Bruns = brunsvigite ; Cham = chamosite : Diab = diabantme.
Sher = sheridanite ; Clino = clinochlore ; Penn penmnite.

32
IV - G - 3. - X-RAY DIFFRACTION CHARACTERISTICS OF CHLORITES
The small sze of the partiles and their rather irregular crystal- 2) chiorites with two dioctahedral sheets : d(060)=1.49-1.50A ;
linity in c/ay-ch/or/tes provoke some diffuseness of the reflections, 3) less-crystallized layer silicates, compared to (1) and (2), with
and the absence of some ordinarily weak ones. Chiorites in which ncompletely developed nterlayer material.
the number of octahedral positions occupied by Fe-ions s not
exceeding 30% show mdium to strong intensities for the first A dioctahedral chlorite has been reported by HAYASHI and
five orders of the (001) series (BROWN, 1961). OINUMA (1964), with a d(060) at 1.509, and a d(001) at 14.18
Substitution of Fe for Mg in the octahedral layers provokes a which s table on heating and solvation ; the intensity of the basal
modification of the absolute as well of the relative intensities of the reflection is increased by a factor 5 to 6 on heating at 600C.
basal reflections (BROWN, 1955 ; BRINDLEY and GILLERY, 1956). the di-tri-chlorite category s represented by donbassite, but also
In a parallel way, increasing substitution of Al for Si displaces the by other types wherein the (060) is still at 1.49-1.50, and the d(001)
(001) reflection of macrocrystalline chlorite towards a higher angle. s stable upon solvation and heating. On heating this basal reflection
The (001) and (003) reflections are relatively weak in iron-rich increases in intensity, and s stable to temperatures of 550-600C.
chiorites as compared to the intensities n the magnesium-rich
chiorites. The even orders (002) and (004) are stronger. As pointed out by BAILEY ( n GIESEKING, 1975), during the past
In iron-rich chiorites the (001) reflection may lack because of its ten years, a large number of occurrences have been reported in
very low intensity. It also occurs n clay mixture that this basal sediments and soils of fine-grained, imperfectly crystallized diocta-
reflection s masked by the adjacent ones belonging to other clay hedral layer silicates that give a 14 basal spacing. These materials
components (as the asymmetric shape of an open Hite which is have been called : dioctahedral chlorite, dioctahedral vermiculite,
predominan! n the mixture relatively to the chlorite ; the occurrence swelling chiorites, intergradient chlorite-vermiculite, chlorite-like
of vermiculite, smectite, mixed layers the basal reflections of which mineral or 14-minerals, depending on their reactions to various
overlap the (001) of chlorite etc...). diagnostic tests. A majority among these materials appears to
On the other hand, Mg-rich chiorites have relatively equal intensities result from the precipitation of gibbsite-like or brucite-like sheets
n their (OOI) series of reflections. n the nterlayer spaces of preexisting degraded micas, or n
vermiculites, montmorillonites, or in' other mixed layers. The inter-
Sedimentar/ chiorites, as well those occurring n weakly metamor- layered material is often ncompletely developed as t is attested
phosed rocks, are ordinarily trioctahedral : with their d(060) at by their variable behaviour on heating, solvation and relative dis-
1.53-1.57. But dioctahedral chiorites have also been observed n solution. It s of nterest to note that such a 14 material may also
the nature, usually as^products of the hydrothermal weathering or be produced by reaction of a degraded mineral with organic matter
n some sedimentary environments and soils ; these dioctahedral when both present n the soil.
chiorites have their d(060) situated near 1.50, EGGLETON and
BAILEY (1967) have grouped the dioctahedral chiorites into three Two methods of study by X-ray diffraction can be used n order
different categones : to reach an accurate or possible identification. One s concerned with
1) chiorites with one dioctahedral sheet and one trioctahedral sheet: the oriented aggregates, the other, with random powder mounts.
d(060)= 1.49-1.51;

IV - G - 4. - CHLORITES AS ORIENTED AGGREGATES


It has already been dealt with the general X-ray pattern of oriented a low d(). In mixture of clay components when such a partially
aggregates at the beginning of the chapter. degraded chlorite occurs, it may become rather difficult to interpret
The peculiar character that allows a differentiation between chlorite the displacement of the basal reflection on heating. Confusin
and other layer silicates (vermiculite, smectites, mixed layers that might indeed be easy with a vermiculite f the degree of hydra-
also may exhibit a d(001) at about the same d-spacing of 14), tation s high.
concerns their various behaviours on heating and solvation, as Some useful diagnostic data for the identification of chiorites and
expressed in the following table : related minerals in sediments have been published by van der
MAREL (1964). These indications concern a practical appreciation
Treatments d(001) n N EG 500C of the basal reflection upon treatments (untreated (natural), heated
(to 350C), K-saturated, and glycerolated samples). In a parallel way,
Well-crysta!lized chlorite this author provides an excellent review about the several synonyms
(normal)
14 14 14 (more intense) used sometimes for the same species. He also emphasizes the fac
that an accurate identification of chlorite n sediments may become
smectite 12-15 expansin collapse or remains problematic because of the composition of the clay
mixture, and the overlapping of some reflections. Some of van der
Mg-vermiculite 14 14 collapse MAREL's criteria for the determination of chiorites are reproduced
desaturated vermiculite 14 expansin collapse here. These data have been completed with those provided by
LUCAS (1963).
1) Normal chlorite (CN) : STEPHEN and Mac EWAN, 1951 ; BRINDLEY
Beside we/l-crystallized chiorites that are completely insensible to and ROBINSON, 1951 ; DALTON et al., 1958 ; WARSHAW et al.,
solvation and heating, there exists species which expand when 1960, also named true chlorite (NELSON, 1960). Trioctahedral and
glycolated (or glycerolated) while not showing n a parallel way dioctahedral. Basal reflection at 14-15A (depending on the strength
an appreciable collapse on heating. These chiorites have been of nterlayer bonding and chemical composition).
named swelling chiorites (symbol n this handbook : Cg). The intensity of the basal spacing s enhanced (by a factor 2-5)
MARTIN VIVALDI and Mac EWAN (1969) interprete them as chiorites by heating at 550C/2 hours, while the (002) at 7 s weakened.
with mperfect interlayer sheets. STEPHEN and Mac EWAN (1951) No change on glycerol solvation and K-saturation.
have demonstrated that, while the on-attraction between the brucite This normal chlorite can be further characterized into species by
and tale layers prevens expansin in normal chiorites, in swelling X-ray diffraction of random powder mounts, or by other rnethods
chiorites there occurs a discontinuous brucite layer n the form of of study (infra red, chemical analysis, etc...).
islands beiween the tale layers. As a consequence a two-layer
complex with glycerol may fill the natural openings in the defect 2) Hydrated chlorite (CHsO) or exfoliated chlorite : same characters
as for 1), but in the untreated (natural) sample the (001) reflection
brucite layer, and thus produces a partial expansin in the
c-direction. shows a shoulder on the side of the 14, towards the high angle
side. This shoulder has its apex at about 12.6. This accident
There also occurs chiorites wherein the brucite layer is partly replaced persists or s slightly enhanced on K-saturation, or glycerolation and
by hydrated cations ; their d(001) is displaced on heating towards heating (at 350 and 550C).

33
3) Sedimentary chiorite : found m sediments and of clay-sizes. The d(060) spacing at 1.49-1.50 is an important character of
It behaves rather as the two above described varieties. these dioctahedral chiorites.
4) Swelling chiorite (Cg) : the 14 reflection tends to become Dioctahedral chiorites exhibit an integral series of basal reflections
flatter and less pronounced than in normal chiorite.This isapparently of the (OOI) series such as the normal trioctahedral chiorites. Of
due to the fact that the layer tends to collapse somewhat between mterest is the fact that most of these dioctahedral chiorites have
the brucite columns. These swelling chiorites maintain a d-spacng a (003) reflection at 4.7 which s typically more intense that the
at about 14 but are slightly buckled, the reflections of these other reflections. The basal spacing remains stable upon glycolatio o n.
uneven planes being broader and weakened. Heating over 300C causes a gradual collapse of the 14.0A;
The basal reflection at 14 exhibits a broad base followed by a at 700C the d-spacing remains at 13.10. At an intermedate
small nflection near 1 2A. After glycolation, this reflection s replaced temperature of 500C it is noticed a marked increase in the intensity
by a large asymmetric reflection which culminates at 16.5 and of the basal reflection, and a reproduction in amplitude of the (002)
shows a gentle slope towards the high angle side. A clear defined reflection at 7/4. This behaviour is different than the one ordinarily
12 reflection may emerge from the background. On heating at observed for normal chiorites where occurs an increase in intensity
550C or after K-saturation,othe 1 4 reflection may be displaced of the 14A reflection accompagnied by a decrease in intensity for
to a lower valu (13.7-13.8) and exhibits a slightly asymmetric both the 7 (002), and 3.5A (004) reflections.
towards the high angle side as well. While trioctahedral chiorite s soluble in warm diluted HCI, diocta-
The asymmetry after the treatments s ndicative of the presence of hedral chiorite and kandites are relatively insoluble. GOMES (1967)
interstratified layers, some of them being more resistan! than the for a dioctahedral chloritegenerated bythe weathering of alepidolite,
others. Bucite islands remain in the interlayer spaces, and prevent has observed the extraordinary resistance of the mineral to HCI
a complete displacement of the basal spacing on heating ; this gives attack, even f the treatments were done with 1N, 6N and 12N HCI
rise to the slope towards the high angle side. solutions in a boiling water bath for varying periods of time.
The displacement of the reflection at 14 upon glycerolation (or PATTERSON and HOSTERMAN (1962) have also reported a highly
glycolation) proves the presence of some swelling layers. However aluminous chiorite that was not destroyed with 3N HCI. GOMES
the degree of swelling s less than for a fully swelling mineral (op. c/f.) has demonstrated that a Al-chlorite may be resistant to
such as a smectite. H u m p s observed between 10A and 7 treatment with 1N NaOH.
indcate a certain interstratification. The latter s more pronounced 9) Chamosites.
in true interstratified structures (regular, and random) mvolving Two types of chamosite have been recognized : a 2:1 chiorite,
chiorite and swelling chiorite layers (see chapter VI). and a 1:1 type (which should be called berthierine ) (BRINDLEY
5) So/7 chiorite (Cs) : such a mineral s characterized by a basal et al., 1968). BRINDLEY (1961) has discussed the structure of
reflection at 13.8-14 that remains stable upon glycerolation. After chamosite. BRINDLEY and YOUELL (1953) described ferrous and
K-saturation no change does occur, or only a slight decrease may ferric chamosites.
affect the basal reflection which collapse at about 13.4. On In nature there may occur mixtures of ferrous and ferric varieties,
heating there occurs a diffraction band between 10 and 13.8 as well of chlorite-type chamosite.
(350C), and a doublet 11+13.8A (550C). In the X-ray pattern only the basal (OOI) reflection usually shows
6) Swelling so/7 chiorite (Csg) : the basal reflection at about 13.2 rather diffuse shapes. But in rand_om powder mounts, a triplet of
becomes a doublet upon glycolation : a more intense reflection mdium intensity occurring at 2.40, 2.1 5 and 2.67A is diagnostic,
occurs at 1 7.8 with a hump or shoulder at 14. After K-satu- while a diffraction band is displayed at 4.5 that corresponds to
ration, or on heating an ill-defined reflection at about 12.8. the (02) une n disordered kaolinites.
Sometimes a remaining reflection occurs at 14A. After heat Chamosite s often associated with siderite, some of the d-spacings
treatment at 550C, the broad reflection is situated at 11.4 with of which coinciding with those of chamosite.
a remaining and less intense reflection at 13.8. Chamosite, an authigenic mineral (generally of the Ib chiorite poly-
type, see further in this chapter) exhibits a green colour (due to the
7) Chiorite with the behaviour of montmorillonite (C|\/|) (LUCAS, occurrence of the Fe ++)which is maintained n reducing conditions
1963) : in the natural (untreated) sample, the 14 reflection is very and in the presence of decomposed organic matter. On oxydation,
symmetric or slightly asymmetric towards the high angle side. Fe++ changes in Fe + + + : the diffractogram res m bles then that of a
The glycolation modifies the shape of the reflection while its apex disordered kaolinite. Chamosite has generally a rather poor crystal-
remains at the original d-spacing : the reflection becomes indeed line structure which is shown by only a 7 (001) reflection. The Ib
asymmetric, and broadens towards the small angle side. After chiorite polytype, n which Fe++ s found n appreciable amounts
heating, the asymmetry s reversed, the broadening being developed can be identified as either a disordered kaolinite or as a Ib chiorite.
towards the high angle side. The occurrence of an asymmetry, in In oriented X-ray pattern chamosite shows reflections at 7.07 and
this variety of chiorite, s related to the presence of certain inter- at 3.54A, as for a kaolinite. If one takes an X-ray pattern of a powder
layer spaces that are less stable, swell slightly upon glycolation, and mount, there occurs reflections at 4.54 (cf. (110) reflection), and
collapse in the same manner on heating. at 2.60 [cf. (130)] that distinguish the chamosite from the chiorite.
8) Dioctahedral chiorite (Co) the existence of dioctahedral chiorites If there also occur reflections at 2.60 and 2.44, the chamosite
has been comproved by several authors (BRYDON e al., 1961 ; can be mterpreted as of a ferric composition (BRINDLEY, n
MLLER, 1961; ENGELHARDT e a/., 1962; MLLER and BROWN, 1961).
KROMER, 1962 ; CAILLERE e al., 1962 ; HAYASHI and OINUMA, The d(060)=1.56 for ferrous chamosite, while =1.54 for ferric
1964; KOIZUMI and ROY, 1959; SUDO and HAYASHI, 1956; chamosite.
SUDO, 1963). AN the dioctahedral chiorites have been described The kaolin-type chamosite, on the other hand, gives an X-ray pattern
as Al-rich chiorites. The structural model of such silicates consists on natural and heated sample similar to kaolinite. The chlorite-type
of alternating pyrophyllite and gibbsite layers. MLLER (1963) has chamosite exhibits an X-ray pattern of a chiorite. That will say
proposed the ame sudoi'te for the dioctahedral chiorites. But there the kaolin-type structure of chamosite collapses at about 550C,
are also other chlorite-types, such as cookeite, which show struc- and becomes amorphous, while the chlorite-type structure shows an
tural characters between true dioctahedral members and true trioc- intensified 14 reflection, and does not collapse on heating.
tahedral members of the chiorite group.

IV - G - 5. - POLYTYPISM IN CHLORITES

It is not the topic of this handbook to deal with all the crystal- Asrecalled by BAILEY (n GIESEKING, 1975), there are 24 resultmg
lographic aspects of the chiorite group. The reader who whishes regular one-layer polytypes, designated la-1 through la-6,lb-1
to be nformed. in details on the subject should refer to several through lb-6, and so forth, depending on the type of nterlayer sheet
papers by BAILEY and BROWN (1962), BROWN and BAILEY (I or II), the position (a or b) of the nterlayer sheet on the initial 2:1
(1963), SHIROZU and BAILEY (1965, 1966), EGGLETON and layer, and the poston (1 through 6) of the repeatmg 2:1 layer on
BAILEY(1967), LISTER and BAILEY(1967), BAILEY (in GESIEKING. the interlayer sheet. Only 12 of these 24 structures prove to be
1975). truly different; the others are either enantiomorphic or equivalen!

34
by 180 rotation about Y. Two of the 12 unique polytypes are based 060
on a triclinic-shaped unit cell w t h a = 1 0 2 , and have triclinic 203 |+201
symmetry. Two are based on an orthorhombic-shaped unit cell with Si Hb
O - P - Y = 90, and have monoclinc symmetry. The remaining eight
polytypes are based on a monoclinic-shaped unit cell with P=97, 202
& 202
and include monoclinic symmetry and one triclinic symmetry repre-
sentative of each of the four structural unit types. Table 15 sum-
marizes details provided by BAILEY (m GIESEKING, 1975) for
S 204 005

II i Jl \, ,l
regular one-layer polytypes.

Equivallent Enantiomorphic
Symbol Space group Unique angle
structure structure

la-1 Cm P=97 lb-2 - i 1 1 1 | I I I I i I I I I I


la-2 C2/m P=97 - -
la-3 C1 P=97 lb-6 la-5
la-4 C1 P=97 la-6 - +060 202*
la
la-5 C1
el
p=97 lb-4 la-3
2.39
200

I
la-6 P = 97 la-4 - i 005
- -
lb-1
lb-2
lb-3
C2/m
Cm
C
P=90
P=97
a = 192
la-1
lb-5
-
-
! S |
lb-4
lb-5
C1
C
P=97
a=102
la-5
lb-3
lb-6
- ! 5 i S i, S i
lb-6 C1 P=97 la-3 lb-4 2.0 A 3.0A

lla-1 C2/m P=97 - - k060 203*|


lla-2 Cm P=90 llb-1 - I Ib ((3 = 97) 2.44+ I
lla-3 C P=97 lla-5 -
lla-4 C1 a = 102 llb-5 lla-6
i 2os I 005
lla-5
lla-6
C
C1
p=97
0=102
lla-3
llb-3
-
lla-4
i > J 5*
llb-1
llb-2
lb-3
Cm
C2/m
C
P=90
P = 97
0-102
lla-2
-
lla-6
-
-

llb-5
S i ii! * ; 1J I i "H
I lb-4 C P=97 llb-6 -
I lb-5 C 0 = 102 lla-4 llb-3
202
llb-6 C1 p=97 I lb-4 - 2.50
Ib (3=90)

i.
Table 15. Summary of one-layer polytypes in chlorites (after BAILEY
in GIESEKING, 1975).

Only six unique semi-random one-layer stacking polytypes are


possible, but only four of them have been recognized in natural S+060
chlorites by BAILEY and BROWN (1962) who have examined some
303 different chlorite specimens (see table below), and by HAYES ! 206 204
(1970). 008

J, ;H
Occurrence of structural units in natural chlorites (303 specimens
005
analysed by BAILEY and BROWN, 1962) :

Structure
llb-evon,
Ib-odd ,
p=97
p=90
Number of specimens observed
243
37 i
1.6
I
J I I I
2.0
I I I I i i i i |
3.0
Ib-even , p-97" 13
la-even , p-97 10 Figure 22. - Shematic X-ray diffraction paterns of four chlorite polytypes
lla-even, p=90" O (based on data of BAILEY and BROWN, 1962, p. 839). The mdexed, soid
lla-odd , P=97 O black bands are diagnostic for each structure. The diagnostic hoi bands
of Ib ( P=97) are broadened. (from HAYES, 1970, p. 288).
These polytypes are distinguishable by their (hOl) reflections in
the X-ray powder pattern. The differentiation between chlorite species can be achieved with
HAYES (1970) provides a sheme of diagnostic (hOl) reflections for DTA, and chemical analysis, both combined with X-ray diffraction
the four naturally occurring semi-random polytypes in sedimentary analysis (POST and PLUMMER, 1972). Each chlorite (Ripidolite,
rocks. As recalled by the latter author, the d-spacings and the Sheridanite, Clinochlore, Penninite) has a more or less distingui-
relativo intensities depend somewhat on the composition. It s rather shable set of reflections with definite intensities. POST and
easy to recognize polytypes by a visual examination and comparison PLUMMER (1972) have shown some good routme correlation
of the X-ray pattern given in figure 22 which has been based on between the above cited species on account of the 1(002)
data by BAILEY and BROWN (1962). HAYES (op. cit.) also empha- + 1(004)71(003) ratio, and the l(003)/l(005) (detailed data are given
sizes the difficulty of Identification of clay-size chlorites when they n the paper by POST and PLUMMER, op. cit.). As an example
become mixed with or are subordnate to other clay minerals, hereon, some of the results found by POST and PLUMMER (op.
principally micas and Hites, in a clay mixture. cit.) are here reproduced (table 16).

35
MARTIN (1955) has provided some data about chlorites identifi-
l(002)+l(004) 1(003) cation (Clinochlore, Proch/orite, Corundophilite, Leuchtenbergite,
Chiorite species 003] 1(005) Thuringite) found in soils. THOREZ (1975) has summarized
d n lowest highest lowest highest MARTIN's data and reproduced the positions and intensities of the
vales vales vales vales (001) reflections only both for the natural and the heated (550C/30
min.) samples (see table 1 7).
Ripidolite 4.79 6.53 2.23 3.20
Sheridanite 2.63 3.89 3.13 4.06
Clinochlore 2.15 3.16 3.10 5.43
Penninite 2.26 4.70
Cr-chlorte 2.25 6.66
Table 16. Correspondence between chiorite species, and the vales
of intensities ratio (after POST and PLUMMER, 1972).

N 550C/30min.
Chiorite species
d() I d() I

Clinochlore (001) 14.5 W 14 VS


(002) 7.2 S 7 (almost disappeared)
(003) 4.75 W 4.64 W-VW
(004) 3.55 M 3.53 VW
Proch/orite (001) 14.3 W 14.3 VS
(002) 7.1 M 7 (almost disappeared)
(003) 4.72 M broad 4.7 (almost disappeared)
(004) 3.56 M 3.52 VW
Corundophilite (001) 14.5 W 14 VS
(002) 7.16 M 7 VW broad
(003) 4.75 W 4.7 VW broad
(004) 3.52 W

Leuchtenbergite (001) 14.3 S 14 VS


(002) 7.16 S 7.16 W
(003) 4.74 S 4.7 W
(004) 3.54 S 3.53 W

Thuringite (001) 14.7 w-vw 13.9-14.3 S


(002) 7.5 W 6.9 VW
(003) 4.61 w-vw 4.7 (almost disappeared)
(004) 3.53 W 3.5 (almost disappeared)

Table 17. (001) reflections : (positions in d(A) and intensities) of untreated and heated (to 550C)soil chlorites
[data after MARTIN (1955), modified by THOREZ, (1975)].

IV - H. - PALYGORSKITE (ATTAPULGITE) : PAL (Att)


In oriented aggregate, palygorskite (Attapulgite)js readily identified
by its characteristic reflections at 10.4-10.5, while the other (hkl) d() I obs.
reflections are situated at 6.44, 5.42, 4.49, 4.18 and 3.69.
Apart the first reflection, the others are not systematically well- 110 10.50 10
indicated in the X-ray pattern. No change takes place in the X-ray 200 6.44 6
pattern after solvation with ither ethylene glycol or glycerol. 130 5.42 5
On heating at 500C, the 10.4-10.5 reflection is replaced by one 040 4.49 8
at 10, while the others, when occurring in the untreated sample, 310 4.18 3
have disappeared or weakened.
240 3.69 5
The behaviour of the mineral upon treatments can be expressed 330 I
as follows for the first characteristic reflection : 3.50 3
150 I
400 3.23 10
first reflection N EG 500C 420 3,03 1
n d() 10.4 10.4 10
Table 18. d-spacings and observed intensities of the Attapulgus
palygorskite (after BRADLEY, 1940), X-ray pattern out to the 3
The 6.4 reflection is not reliable indicator unless the analysed rea.
sample s exceedingly high in palygorskite. On a pract'cal point of view in clay mixture comprising palygorskite
Table 18 presents the X-ray data of the palygorskite from Attapulgus and ilute, there s a problem n distinguishing readily the occurrence
(BRADLEY, 1940). of the former mineral. Its 10.4-10.5 reflection falls within the

36
ascending section of the illite (001) reflection at 10A. It s conse- palygorskite ; 4) the same as 3) when mixed layers occur.
quently recognized with some difficulties when : 1) the amount But in these above problems there s always the possibility to
of palygorskite s small in the mixture ; 2) the other reflections of refer to an e/ectronic microscope examination which provides a
the mineral are not sufficiently pronounced to be observed, or are useful distinction between the fibrous and laths patterns of the
masked by those related to the associa;ed clay minerals ; 3) f palygorskite as compared with the usual irregular flakes of the
the 10A of a degraded Hite, with its asymmetric reflection towards illite.
the low angle side, nterferes with the reflection at 10.5 of the

IV - I. - SEPIOLITE : SEP
Sepiolte has a diagnostic reflection at 12 (cf.(110) reflection). Table 19 provides the d-spacings and corresponding intensities
Others reflections may be more or less pronounced at : 7.6, 5, of the X-ray pattern out to the 3 rea (data provided by HENIN
4.60, and 3.82. and CAILLERE, in GIESEKING, 1975) ; and CAILLERE and HENIN
The 12 reflection s stable after glycolation (or glycerolation), m BROWN, 1961).
with/without Ca- and K-saturation, and subsequent heating at 250C.
When the unsaturated sample is heated to 550C the 12A reflection
shifts to 10.
The behaviour of sepiolite upon diagnostic treatments can be
expressed as follows :

first reflection N EG 500C


in d() 12 12 10

(hkl) d() I d(A) I d() I d(A) I

110 12.05 100 12.1 100 12.1 100 12.3 60


130 7.47 10 7.5 7 7.7 5b 7.6 5
200 I
6.73 5 6.7 4b 6.7 5b
040 I
150 5.01 7 5.04 3b 5.0 5b 4.9 6b
060 4.498 25 4.49 25 4.47 18 4.5 _
20
131 4.306 40 4.29 35 4.31 25 4.3
330 4.022 7 4.02 7
260 3.750 30 3.738 25 3.738 20 3.746 20b
241 3.533 12 3.506 5 3.49 5
080 3.366 30 3.339 45 3.339 35 3.34 20b
331 3.196 35 3.181 15b 3.187 12
261 3.050 12 3.048 5

Table 19. Observed X-ray powder data for sepiolitejafter CAILLERE and HENIN, m BROWN (1961), and HENIN and CAILLERE in
GIESEKING, 1975) ; data are provided out to the 3 rea of the X-ray diffraction pattern.

Other X-ray data for powder mounts are presented m THOREZ


(1975). Temperature
Behaviour of the 12 reflection
in C
The sepiolte 12 reflection may be mistaken both for smectite
300 single reflection at 12; no transformation.
and/or mixed layers in the natural untreated sample. Treatment with
glycol or glycerol brings out the clear difference between non- 350 doubletat 12and 10, theoccurrenceof the latter
swelling sepiolite, and montmorillonite. The heat treatment at 550C being due to the loss of a part of the zeolitic water,
s not conclusive at all because sepiolite, and certain mixed layers 350-450 weakening ofthe12, andstrengtheningofthe 10.
give both a 1 O reflection. 500 single 10 reflection.
800 disappearance of all the reflections.

LUCAS (1963) has indicated how to reach the identification of Table 20. Progressive shifting of the 12 sepiolite reflection to 10,
sepiolite when the heating treatment is proceeded step-by-step with possible simultaneous presence of both the two reflections at 12
(table 20). and 10A during the heating (LUCAS, 1963).

37
V. - SUMMARY OF BEHAVIOURS OF THE CLAY MINERALS
TOWARD IDENTIFICATION TREATMENTS
The results obtained by X-ray analysis after the three classical (glycolation or glycerolation, heating), may be relatively decisive for
determination tests for the basal reflections (001) of the current a gross identificaron. But it is indicated to proceed to a further
clay minerals are schematically presented n table 21. investigaron about the position in d() of the other (OOI) reflections.
Some data are summarized n table 22.

The hereon routine identificaron key can be directly used for


the current clay minerals. But the data must be precised n the Table 23 presents certain indicatve behaviours of the basal reflec-
case of mixture of clay minerals because of the overlapping of the tions (001) of the current clay mineral after subsequent saturations
basal reflections that may occur n some cases. The position of (with K+, Ca++, Mg + + ), with subsequent glycolation or glycero-
the basal reflection, and its behaviour u pon thediagnostictreatments lation, and heating (after QUAKERNAAT, 1968).

d-spacing in A
MINERAL SYMBOL 10 11 12 13 14 15 16 17

Kaolinite K N
EG

Chlorite C N
EG
500

Swelling Chlorite Cg N EG
500

Ilute I N
EG
500

Smectites M 500 EG
(Montmonllomtes)

Vermiculite 500 N
EG

Palygorskite PAL N
EG
500

Sepiolite SEP 500 N


EG

Table 21. Vales of the basal reflection, n d(), for the current clay minerals, after the classical identification essays (N = natural,
untreated sample ; EG = ethylene glycol ; 500 = heating to 500C).

38
Vales (n ) of the characteristic reflections of simple clay minerals after
different treatments.

MINERAL TREATMENTS (001) (002) (003) (004) (005)

K N 7,1 3,58 2,33


EG no changes
500 disappearance of all the reflections

1 N 10 5 3,3 2,5
EG no changes
500

M N 15,4 5,1 3,05


EG 17 8,5 5,7 4,2 3,4
500 10 5 3,3

C N 14 7 4,7 3,5 2,83


EG no changes
500 no changes or slight changes in the even orders
550 14 4,7 2,83
(disappearance of the even orders)

C
9 N 14 7-7,2 4,7 3,5 2,83
EG 17 8,85 5,85
500
550
same reactions as for normal chlorites

V N 14
(Mg-satured) EG 14 no changes
500 10

Table 22. Vales in d() of the characteristic reflections of the series (OOI) of current clay minerals, after various diagnostic treat-
ments (after LUCAS, 1963). (N = natural, untreated sample ; EG = ethylene glycol ; 500 and 550 = heating treatments).

39
UNTREATED SAMPLE d-spacing (in ) of the (001)
MINERAL COMPARED WITH
(Symbol) SATURATED SAMPLE 10 11 12 13 14 15 16 17 18

Untreated N
EG
500
I nr IWIi1)

Saturated with K or Mg N
EG
Gl
500

Untreated N
EG
500

Saturated with K or Mg N
EG
Gl
500

Untreated N EG
500
f~n
'-'Q
Saturated with K or Mg N EG
500

Untreated 500 -* M > re.

Saturated with K 500 N EG Gl

(low charge) Saturated with Mg 500 -* N v EG Gl

M .. r-f~\ p,|
Saturated with Ca 500

Untreated 500 < N * EG Gl

Saturated with K
500

500 M ta. r~r\ r\\


(high charge) Saturated with Mg

Saturated with Ca 500 * M re"1 r* i

500 N
Untreated
EG
\/<?v
(low charge) Saturated with K 500 N

Saturated with Mg 500 N

Gl

Untreated 500 N
EG
\/-*>~

(high charge) Saturated with K N >

Saturated with Mg 500 N


EG
Gl

Table 23. Vales in d() of the basal (001) reflection of curren! clay minerals after treatments (without and with cation-saturations
with K + , Ca++ , Mg++ ) ( after QUAKERNAAT, 1968).

40
NATURAL-WITHOUT PRETREATMENTS Mg-SATURATION K-SATURATION

COMPOSITION GL 300 550 GL 300 500

Ca-SATURATION

N EG GL 300
Vermcute
(high charge)
,,^
e
Vermiculite
(low charge)
^^
o *

Smectite c .
blT
(high charge)
M r
Smectite
(low charge)
Q
brT
,

^ L *j$
Table 24. - Coloured key for the routine Identification of current clay minerals, based
Beidelte BEI 1 on the behaviour of the basal (001) reflection after different treatments (after THOREZ,
1975).
*
VI. - QUALITATIVE DETERMINATION OF MIXED LAYERS
VI - A. - GENERALITIES
Simple clay minerals are composed of layers of one type. The Besides monomineralic clay samples (and mixtures of discreet clay
structure of a layer is the critenon for ts classification and iden- minerals) that exhibit their own series of (OOI) reflections (see figure
tification. The latter s generally concerned with the position of the 23), another type of mixture exists. It concerns the interstratification
basal reflections, and with ts possible alteration after various of clay minerals and corresponds to the interstratified or mixed layer
teatments. minerals and structures.
001 Mixed layers are usually built up by layers of two mineral types,
but some of them are characterized by the combination and inter-
004 003 002 stratification of three different types of layers as well. They have
MMBRALA
basically the same crystal structure as for simple clay minerals,
but they differ from these by amount and nature of the (inter)layer
populations.
Theoritically and practically the number of combinations (or possible
modes of interstratifications) in the mixed layers materials is very
large since any of the simple clay minerals (i////fe : I ; vermiculite :
V ; chlorite : C ; montmorillonite : M ; beidellite : Bei etc...) may
002 001 become interstratratified in binary systems of interstratification. It
MINERALS
B& C s less frequently encountered mixed layers nvolving more than two
components. Besides the nature and number of clay minerals
intervening in the interstratified clay minerals, one must take other
factors into account : the fypes of ordering, the proportions of
different layers, the degree of crystallization and the partile size
distribution of the components.
Mixed layers have occurrence and abundance that have not to be
003
recalled. They have been mostly recognized in soils, but also in
REGULARLY 02 sediments and as producs of the weathering (deuteric and hydro-
005 004
INTERSTRA-
TIFIED
thermal). They may be more or less easily produced artificially
MINERAL d u ring laboratory experiments through the weathering of well-cristal-
(B-C) lized simple clay minerals.
As reported by Mac EWAN (1949), three types of interstratification
occur n the nature : 1) regular (ordered) ; 2) random ; 3) with
segregation.
RANDOMLY Any nvestigator of an interstratified material hinges on the ability
INTERSTRA- to dentify it with the more accuracy as possible. But his ability
TIFIED is often limited thanks to an inadequate knowledge about the manner
"003"
,10Q2,,STRUCTURE
002
, the determination must be conducted, or because of the very large
(XB-YC) 01 range of combinations that exists n the mixed layers. In addition
to these two factors, there also occur structures the components
of which have a more or less distinct zonal distribution (GJEMS,
1967). As recalled by this authorthe layers ofmicrocrystals forming
the individual zones may be insufficient in number to give X-ray
MIXTURE reflections and will thus appear amorphous (JACKSON et al., 1952),
OF while phases similar to those in a mechanical mixture are shown
MINERAL (XB-YC)+C from the individual mineral components when the zones are very
C pronounced >>.
If one takes into account the nature of the components (layers)
that can become two by two nvolved in an interstratifieation, at least
13 main types are possible and found n the nature. Table 25
provides all the cases within a short formulation based on the
DEGRADED symbol of the mineral (see further the meaning of these formula).
MINERAL

Basal layer M(=Sm)


symbols 7(=K) I C V Cg

Possible 7-M I-M M-C C-V V-Cg

high angle sde low angle sde - compositions K-Bio l-Bei M-V C-Cg
of thve mixed I-C M-Cg
Figure 23. - Types of (OOI) sequences of clay minerals (stylised X-ray
layers I-V
diffraction patterns, providing the shapes of the harmonio reflections). (binary combinations) l-Vg
a) simple clay mineral, well-crystallized, with symmetric and intense reflec-
tions ; b) mixture of simple clay minerals ; c) regulary interstratified minerals K = kaolinite ; I = Hite (micas) ; M = montmorillonite ; Bei = bei
the (OOI) reflections of which have d() positions intensities and shapes dellite ; Sm = smectite ; C = chlorite ; V = vermiculite ; Cg =
according to the same characters for the simple clay minerals the layers swelling chlorite ; Bio = biotite.
of which are interstratified ; d) randomly interstratified structure charac-
terized by badly-defined reflections, with a plateau shapes n many Table 25. Possible types of interstratification for binary combina-
cases and an irrational sequence of (OOI) reflections ; the superlattice tions of the various layers of simple clay minerals (after THOREZ,
structure is ordmarily missing ; e) aspect of a mixture of a simple clay
1975).
mineral and of a randomly interstratified structure ; f) degraded mineral
(i. e. Hite) with asymmetrical reflections (tailing reflecions).

42
The table 25 does not indcate of course the regular or random Data n table 26 are based on STOCH (1972), and are slightly
stacking, types for the degree of interstratification, or the law of modified after recent results provided by the literature. STOCH
repetition. In fac the above symbolism has been mtroduced here in (op. c/.) has attempted to represent all the combinations of two
place of long descriptions : kaolinite-montmorillonite ; kaolinite- different layers. The subdivisin considers the stacking character
biotite ; llite-montmorillonite, etc... Further in the text t will be (regular, random), and the di- or trioctahedral character of the
emphasized howan accurate descriptive notation of the mixed layers material. On the right-hand along the oblique line limiting the
can be presented for these of regular and random types of mixed diagram, are represented the layer structures composed of homo-
layers. topic layers with different interlayer cations. The latter selectively
fill the nterlayer spaces (interlayers); the homotopic layers may
STOCH (1971) has published a table (26) displaying a more comprise different amounts of water molecules between the layers
complete subdivisin of the known nterstratified clay minerals. themselves with the consequence that different vales n d-spacings
may also occur n the mixed layers. Interlayer spaces are either
occupied by simple cations only (micas), or by fairly hydrated cations
(smectites and vermiculites), or by a brucite-type layer (chlorites).
The character of the occupying cations determines the size of the
nterlayer space, while the binding forces between the layers
determine whether interlayer are more or less resistant to various
determinaron agents such as ethylene glycol, qlycerol, or heat.
As t has been recalled n the case of simple clay minerals, the
nterlayers alone unable the determination of the valu of the d-spac-
ing ; this valu s measured directly on the X-ray diffraction pattern
at the level of the reflections. The variations in the d-spacings are
taken into account for the determination of the mineral groups.
Such a procedure permits a rather quick distinction between
families of clay minerals, but not necessary between and among
the species being grouped into a specific family.
This brief review s represented here to show that there are no basic
a = crysalline structures
differences between simple and nterstratified minerals. The main
built up of heterotopic differences are in the mode of stacking ofstructura/ly identical layers,
layers. and in the nature of the cations occupying the various possib/e sites.
=
"~" b crystalne structures X-ray diffraction analysis makes it possible the determination of the
built upof homotopic
layers but with iner-
stacking of the layers within simple clay minerals, regularly nter-
layers filled n a dif- stratified minerals, and randomly nterstratfed structures :
ferent manner.
1) In simple clay minerals the stackmg s made of dentical layers
separated by identical interlayers ;
+ = structures confirmed but little studied 2) n regularly interstratified minerals, the stacking s made of
* = polymorphic or polytypic modiflcation
R = regular ordering dentical layers separated by nterlayer spaces of two types which
D - random ordering / altrnate regularly ;
? = posslble mixed layers 3) n randomly interstratified structures, the stackmg s made of
1 = corrensie ; 2 = montmorillomte-chlorlte mixed
layers including tosudite ; 3 = allevardlte (rectorite): identical or different layers separated by different interlayers
4 = tarasovlte (LAZARENKO and KOROLEV, 1970); which show no repetition in the period following the c axis (see
5 ' THIRY (1973). further).
LUCAS (1963) recalls that the differences between the clay minerals
Table 26. Classification and combinations of nterstratified layers can be explained by ionio substitution within a fixed framework.
n all the actually known mixed layers (after STOCH, 1971, modified This author compares the 2:1 clay minerals to houses the archi-
by the present author). tecture of which remains fixed but the tenants of which change.

VI - B. - PRACTICAL DETERMINATION BY X-RAY DIFFRACTION


(ORIENTED AGGREGATES)

The identification of the mixed layers has often to face theoritical ingly to the method the sample has been prepared in particular
and practical difficulties due to : with or without pretreatments, some discrepancies are observed
1)the search for an accurate defnition (description) of the nter- n the description of the material because crystallochemical modi-
stratified clay minerals with a simple notation system : after fications may have been induced in the analysed material.
having proceeded to the identification tests (so/vation, cation- 3) the large range of combinaisons in the mixed layers built on one or
saturations, heating), it often occurs that several notations exist two (sometimes three) components. These components are made
for the description of the same material n the literature ; that of different clay minerals (I, C, V, M, Bei, etc...) nterstratified n
leads to some confusions about the notation to take into consid- a regularly or n a randomly manner, with different degrees of
eration. There s thus a lack of the standardizaron for the interstratification of one component with the other.
description of the mixed layers. THOREZ (1975) has attempted One must also take into consideraron the variable degrees of
to offer a system of notations that unables this objective. It also crystallinity, the size distributions of the partiles, the relative
occurs that different descriptions are given fot the same material proportons of the components. All these factors may induce a
[(see Mac EWAN and RUIZ-AMIL, n GIESEKING, 1975 ; and van variability in the shapes, intensities and positions of the ref/ec-
der MAREL (1964)] i.e. for the synonyms in mixed layers built up tions belonging to the various interstratified clay minerals, n parti-
of chlorite layers). cular f moreover the effects of solvation, heating and cation-
2) the lack of uniformization during the sample preparation. Accord- saturations are considered as well.

43
4) an incompleta set ofdiagnost/c determination ofthe nterstratified exist presently several books and papers dealing with this subject,
materials. Classic tests as solvat/on and heating are not necessary and discussing the problem of the recognition and nomenclature
sufficient to unable an accurate Identification. It is often indicated (among the main authors to be cited are Mac EWAN and BROWN,
tooto perform complementary tests in particular cation-saturations 1949, 1950; Mac EWAN et al., 1961 ; WEAVER (1955, 1956),
(with subsequent so/vation and heating), acid attack etc... to reach LUCAS (1963). The bibliography in THOREZ (1975) provides
a better evaluation of the composition, mode of stacking, quan- a detailed list of references on the subject.
titative and reciproca! participations ofthe components. The d(060) The identification of mixed layers presents difficulties f one does
is also to be checked. not pay sufficiently attention to a series of criteria or aspects related
to them during the X-ray diffraction analysis.
The nterstratified clay minerals state genetic and nomenclature
problems similar or more difficult to solve relatively to those in The mixed ayer provides X-ray patterns of oriented aggregates, with
simple clay minerals. The complexity, variability and nomenclature definite series of (OOI) harmonio reflections that do not correspond to
of nterstratified clay minerals and structures have given rise to any simple clay minerals. The recognition of the nterstratified clay
numerous dscussions. The abundance of these materials in minerals is consequently based on :
different environments (soils, sediments, weathering) imposes to 1) the number of layers : a factor that ntervenes in the unit-cell,
the mineralogists, geologists, soil mechanicians and others, to and nfluences the basal spacing by displaying vales of the
achieve the most perfectly the practical and complete characteri- basal (001) reflection higher than 24 ;
zation. 2) the nature ofthe components (layers and interlayers) ;
It is however out of the scope of this chapter to provide the reader 3) the repartition of the layers (1:1, 2:1) which can be provided with
an exhaustive statement about the mixed layers structures. There more accuracy by the Fourier's transform method for nstance.

VI - C. - REGULARLY INTERSTRATIFIED MINERALS

VI- C - 1. - GENERALITIES

The minerals are formed by the stacking of generally two layers The number of layers per un it ce 11 is given by the g reate r thickness
types. Each layer is characterized by the structure of a simple clay which s obtained by multiplying each of the d(A) valu of the (OOI)
mineral such as Hite (mica), chlorite, vermiculite, montmorillonite, reflections of the mineral by the serial number, i. e. f the (001) s
beidellite, swelling chlorite, thus moreover involving di- and/or equal to 28A, the series of harmonio reflections will be : (002) = 28/2
trioctahedral varieties. = 14, (003)=28/3 = 9.3, (004)=28/4 = 7, etc... . In practice the
The stacking is perfectly ordered, and gives rise in the X-ray numbering of the dfferent (OOI) reflections s achieved n this
diffractogram pattern of an oriented aggregate to a regular period manner. In a parallel way, the verification may be achieved by
perpendicular to the (OOI) plae (along the c axis). The period is multiplying the d(A) of the corresponding order (as measured in the
equal to the sum of the period of the composing layers that form X-ray pattern) by the serial number in order to check also f the
the theme of repetition. This can be expressed by: result of the multiplication s equal or near the d(A) of the (001)
reflection. The more regular nterstratified mineral the more identical
d(OOI)AB = d(OOI) A +d(OOI)B are the results of the multiplications for all the (OOI) reflections.
A and B designating the two layer components. When the thickness of the theme s established, it becomes easy
to calclate the number of composing layers having a defined thick-
The basal reflection (001) of the nterstratified clay minerals occurs ness of 10, 12, 14. However the calculation must be repeated
as a superlattice reflection with a d-spacing equal to the sum for solvated and heated samples at least, n order to get the most
of the d(001) of the A and B components as expressed in the accurate dentification of the layers. Stability, swelling and/or col-
formula: lapse of the (001) (superlattice reflection) and of (002) reflections
d(001 )AB = d(001 )A+d(001 )B are importan! both for the diagnose of the mineral and the measure
and verification of the X-ray pattern (where the other (OOI) reflec-
The regularity in the stacking is also indicated by the presence tions are exhibited). Complementary data about the composition
of a rational series of (OOI) reflections up to the 10th order in some of the mineral are sometimos indicated by reference to the results
cases. Each of the (OOI) reflections of the minerals corresponds, of complementary tests (cation-saturation).
for its d-spacing, to a d(A) position related to the submltiplos of It is also more or less difficult to assign only and firmly the
the basal (001) reflection, in other words, to 1/2, 1/3, 1/4, etc... of distribution of the different sheets and layers of the mineral on the
the thickness of the repetitivo motif as expressed m the formula : basis of a simple X-ray diffraction analysis ofthe oriented aggregate.
It s indicatd to refer to the calculated curves (Fourier transform)
d(002)AB=d(002)A+d(002)e ; d(003)AB = d(003)A+d(003)e ; etc...
by Mac EWAN ef al. (1 961)

VI - C - 2. - NOMENCLATURE AND DESCRIPTION


An important aspect in the determination of the nterstratified and randomly nterstratified materials (the former being named
minerals concerns their nomenclature. BROWN (1955) has pre- minerals , the latter having been called structures -or di-
sented a resolution : If the interstratification is regular, and the fices in French- because their lack or regular stacking) (LUCAS.
nature of the layers is established, a specific ame should be given 1963).
to the material, i. e. rectorite, stilpnomelane. If the interstratification In the case of regular mixed layers, besides certain definite ames
is not regular the material should be descripted in terms of the already given to some of them (corrensite, allevardite, etc...), the
componen? layers, i. e. for a material composed of a small proportion determination of the occurrence of a regularly nterstratified mineral,
of chlorite layer, randomly interstratified with a mayor proportion of and their accurate description on account of the nature of the
mica layers, the ame proposed is ch/oritic-mica. For more near composing layers, ar achieved by the combined use of capital
equal proportions of two types of layers, randomly interstratified, letters, hyphen and parentheses. The capital letters correspond to
the ame chlorite-mica is proposed (note the use of hyphen). More the symbols of the clay minerals : I (Hite), Mi (micas), M (mont-
comp/ex type of interstratification would have to be described fully. morillonite), Bei (beidellite), V (vermiculite), C (chlorite), Ser(sericite),
Sap (saponite), Cg (swelling chlorite), Su (sudote) etc...
A descriptivo proposition has been offered by THOREZ (1975) to The proposed formulation will expressed by putting the capital letters
reach a better characterizaton and differentiation between regularly (corresponding to the layer components nature) in parentheses ;

44
the two appropriate letters are linked by a hyphen : (I-C) will thus being similar of a smectite. Differentiation between montmorillonite
mean a regular mixed /ayer llite-ch/orite. If t s need, species and beidel/ite can be achieved by complementary and appropriate
can be also described, such as (Ser-Su) for a regular mixed /ayer treatments such as those indicated n thechapter IV-E. By convention
composed of sericite and sudo/te /ayers. A further descripton may in the proposed notation system, the capital letter M will indcate
be completed by 1:1 designating the proportion of the component a smectite (group ame) or a montmorillonite (species ame) if the
layers. A letter D can be added to the formula : composition (beidellite, montmorillonite) is fixed. If the d(060)
(C-M)o desgnales a dioctahedral regular mixed ayer chlorite- indicates a trioctahedral or a dioctahedral smectite, the capital letter
montmorillonite. A peculiar chemical character will be designated will be respectively designated by : Sap and M.
in the formula by placing ts chemical symbol in front of the formula : V : the layer spacing of 14A is unaffected after glycolation (glyce-
Al (C-M) will desgnate the aluminous character of the mixed layer rolation) n the natural sample or after a preliminary Mg-saturation ;
mineral. By convention, f no D s added at the end of the formula, the layer spacing collapses to 10A on heating, being similar to a
t will signify that the mixed layer mineral is naturally trioctahedral, vermicu/ite.
all the composed layers being trioctahedral. However the fact the
proposed notations can be concise by the use of capital letters The nature of the layer components can be implicity referred to the
instead of a complete description [(I-M) referring to a regularly geological (or pedological) background . For nstance, if there are
interstratified llite-montmorillonite clay mineral] presents of course, indications that the parental rocks (or soils) contain a peculiar
at this step of determination, a lack about the relative proportion of mineral such as sappnite (Sap), biotite (Bio), sudote (Su), etc..-there
the two components ; i. e. a mica-chlorite interstratified mineral can might be some probabilities that the layer components engaged, in
be expressed either by (Mi-C) or (C-Mi) until the real proportion of the mixed layers, in the vicinity of the unweathered rocks have some
layers has been calculated. As far this complementary data s not composition similar. In this case, a formula such as (I-C) or (C-M)
provided, the descriptive notation as here designed for the shorten- can then be better differentiated and specified : (I-C) s replaced
ng of the description, does not preclude at all about the real by (Ser-Su); (I-V), by i. e. (Bio-V) ; (C-M), by (C-Sap); etc...
proport/ons of one component relatively to the other.
Pair combinations of these layer types provide different regularly
In the case of regular mixed layers minerals, f one excepts the interstratified minerals.
descriptive formula such as (Ser-Su) where the symbols refer to
definite layers of clay minerals (i. e. sericite = Ser; biotite = Bio ;
saponite = Sap ; montmorllonite = M ; beidellite = Be ; sudote = Su) d(A) of layer M
for the other representative formula, the symbols (I, M, Bei, etc...)
refer, on their side, to layers having the same or similar behav/ours minerals (I-C) (l-Cg) (I-M) (l-Bei) (I-V) (Mi-C) (Mi-Be)
(upon diagnostic treatments) as the corresponding simple clay (Mi-M) (M-V) (Phlog-V) (Ser-Su) (Bio-C) (Bio-V)
minerals. (C-Cg) (C-M) (C-M)o Al (C-M)o (C-V)
(Cg-M) (Talc-Sap) (Mi-ALL)
I : the layer spacing has a valu of 10A n the natural sample, and (Bei-hydrous Mi) (Bei-V) (C-Sap)
is not affected by either glycolation ( glycerolation) or heating. It
behaves as an ////fe (with not marked sweiling character). Table 27. Examples of the variability in layer composition for re-
Mi : the layer component has the behaviour of a mica (Mi), the 10 gularly interstratified minerals (after THOREZ, 1975).
basal spacing of which s stable upon treatments. I = Hite ; Mi = mica ; C = chiorite, Cg = sweiling chiorite ; M =
C : the layer spacing of 14 s stable upon glycolation (glycerolation) smectite (undifferentiated) or montmorillonite ; Bei = beidellite ;
and heating, being similar to a c/7/or/fe. The d(060) provides moreover V = vermiculite ; Phlog = phlogopite ; Ser = sericite ; Su = sudote ;
the dioctahedral or trioctahedral character. Bio = biotite ; Sap = saponite ; All = allevardite ; Hydrous Mi =
hydrous mica; D = dioctahedral.
Cg : the spacing of 14 in the natural sample increases to 16-1 7
upon glycolation (1 7-18 after glycerolation), but remains unaffected
on heating, being similar to a sweiling chiorite. If an interstratified mineral such as (I-C) is combined with simple clay
M or Bei : the layer spacing of 12-15 (generally ndicated by a minerals in a mixture, i. e. with ilute and chiorite, the notation ot the
d-spacing of 14Aforthe commodity of the notation) i n creases to 1 7 A association will be expressed by : I, C, (I-C). The comma separates
upon glycolation (glycerolation), and decreases to 10 on heating, the different components of the clay association.

VI - C - 3. - BEHAVIOUR OF REGULARLY INTERSTRATIFIED MINERALS UPON TREATMENTS


Table 28 and figure 25 present schematically the position of the of (C-V). Glycolation will shift the d(002) from 14 to about 16
d(002) of regularly interstratified minerals, and its behaviour upon upon glycolation in the case of (C-Cg). The movements of the d(002)
the identificaron treatments. -and of the corresponding d(001) and other d(OOI)- s an indication
At first approximation, t is indicated to check the behaviour of the of the interstratification because of the rational ordering developed
(002) reflection -situated between 10 and 1 7 n the low angles after the treatments.
range- because its position and ts movements (stability, sweiling,
shifting, ncrease ordecrease of ntensity) are there better expressed However, in the case of (C-V), if this interstratified mineral is well
than the (001) which may be not very clearly allocated because of developed, there occurs a more or less clearly definite superlat-
of the background influence. tice reflection -the d(001)- in the regin of 28. The position
of the latter corresponds to the sum of the basal spacing of the two
Certain types of interlayering can only be readily recognized with component layers, chiorite and vermiculite :
appropriate and complementary treatment such as solvation and/or d(001)(c-V)=d(OOl)c+d(OOl)v=14 + 14=28
heating. For nstance an nterlayenng of chiorite layers and vermi-
culite (inter)layers, or of chiorite and sweiling chiorite shows in the But such a peculiar reflection is only expressed when the mineral
untreated sample a d(002) at 14, with the corresponding sub- is well crysta/lized. If not, and if the interstratification is one of a
multiples of the (001) in the high angles range. The eventual only " random to regular interlayering fype, this (001) reflection will not
indication, in the natural sample, of the occurrence of a mixed layer, systematically appear.
would be sometimes the ntensity of the reflection. But when the
sample is treated with potassium or heated, there occurs a collapse Table 29 provides the highest d-spacing in various 1:1 regularly
of the d(002) that brings t to a d-spacing around 11.5 n the case interstratified minerals.

45
MINERAL d(002)n 10 11 12 13 14 15 16 17

(I-C) N
EG
500

N
(l-Cg) EG
500

N
(I-V) 500 E Q

(I-M) 500

(C-V) 500 N
EG

(C-M) 500 N pr^

N rr
(C-Cg)
500

(V-M) 500 N EG

(V-Cg) 500 N EG

(Cg-M) 500 N EG

Table 28. Position n and behaviours of the (002) reflection n some of the main types of regularly
interstratified mnerals after glycolation and heating to 500C.

d(001) i n
Composition
N EG 500C

(I-C) 24 24 24
(l-Cg) 24 31 24
(I-V) 24 24 20
(I-M) 24-25 27 20
(C-V) 28 28 24
(C-M) 28 31 24
(Cg-M) 28-29 35 24
(C-Cg) 24 31 28 Table 29. Highest d-spacing in A of the (001) for regularly inter-
(V-M) 28 31 20 stratified minerals (after VIVALDI and Mac EWAN, 1960; LUCAS,
(V-Cg) 28 30-31 24 CAMEZ and MILLOT, 1959 ; Mac EWAN and RUIZ-AMIL in GIE-
SEKING, 1975 ; THOREZ, 1975).

VI - C - 4. - GRITERA FOR THE RECOGNITION OF REGULARLY INTERSTRATIFIED MINERALS


The criteria for the recognition of regular mixed layers minerals s the wide range of X-ray pay patterns ; n the latter ones the
are the presence of an= integral series of orders, with a super- different (001) reflections will vary on account of the nature of the
lattice reflection at d() equal to the sum of the d-spacngs of component layers (thus check the variations n the basal spacings
the components, and a series of (001) reflections that dpes not after the treatments), their ordering/disordering (check the regularly,
correspond to those of a simple clay mineral, or to mechanical randomly or partially randomly interstratification), the proportion of
mixture of clays minerals (see figure 23). As t will be seen, randomly the component (1:1 ; 1:2).
interstratified structures exhibit no integral series of orders ; Several methods exist that unable the distinguishing of mixed layers.
moreover their reflections are frequently asymmetric, that s to say There are reviewed by RUIZ-AMIL and Mac EWAN (in GIESEKING,
they show increased background towards one or the two sides of 1975). Some of these have been developed by Mac EWAN and
the main reflections. The non integral series of orders are charac- BROWN (1949, 1950), Mac EWAN ef al, (1961), WEAVER (1955,
teristic of normal inter/ayer/ng while the asymmetries are characte- 1956). They concern the movement of the reflections by plotting the
ristic of zonal inter/ayering. On another hand, when the analysed position of the d-spacing of purely random mixtures of clay minerals
sample comprises a mixture of simple clay minerals and a regularly wherein the reflection is shifting from a position corresponding
(or randomly) interstratified material, the recognition of the compo- to one pur phase to the position of the nearest reflection cor-
nents must be completed with some caution ; a mximum of results responding to one other pur phase. If the distance apart the
must be taken into account and be provided by the diagnostic reflections in reciprocal spaces s small, the shift will be linear
treatments affecting the basal spacings ; also a careful inspection (figure 24). If the distance between the reflections become mportant,
of the behaviours of the different (001) reflections must be achieved. the shift will follow an S-shaped curve with the double consequence
As there exist a great variety of combinations for mixed layers of arapid movement n the shifting for the intermedate compositions,
since any of the simple clay minerals can become engaged by pair and the development of a diffuse reflection.
with one another n the interstratified material, the resulting effect

46
Thanks to the period of the structure it s possible to distinguish different types. adjacent to it. Then the sequence s expressed by
n regularly interstratified minerals, two mineral groups. AABBAABB or AAABBB (figure 25). As a consequence, it appears
The first group displays a structure wherein each layer A is for this different type of interstratification, that the number of
sandwhished between layers of type B (figure 25) ; the sequence dentical layers placed side by side must always be small enough,
can be expressed by ABABAS. Here the number of layers of type otherwise the structure would become one with regular segregation.
A is equal to half of the total number of all the layers constituting The second group of regularly interstratified minerals is characte-
the crystallite (the degree of interstratification of A with B equal rized by a degree of interstratification other than 50%, but still
50%). In the same group are also included mixed layers minerals produced within a regular repetition of a certain theme with a
whose degree of interstratification is still 50%, but n which the representative stacking like ABBABB or AABBBAABBB.
layers A may either have one or two other layers A, or a layer B of

100
%
A
A

O A
B

100 A A
B

B<
B

A
B

A A
A

100 A B
B

A
Figure 24. - Illustrating the way in which each rpflection migrates and Figure 25. - Eight types of mterstratification of A- and B-layers. Regularly
changes shape n randomly interstratified strucrure. The further apart the nterstratified minerals: alternating ABAB ; AABBAA : AAABBB ; ABBABB :
mxima for the pur phases are in reciproca! space, the more the curve AABBBAABBB ; segregated material : alternating AAAABBBB ; randomly
of the reflection movement levis out for intermedate compositions, at interstratified structures : alternating ABABBAAB, and ABAABBB, etc...
the same time as the reflection becomes diffuse (after Mac EWAN and
RUIZ-AMIL in GIESEKING, 1975).

47
VI - D. - RANDOMLY INTERSTRATIFIED STRUCTURES

VI - D - 1. - GENERALITIES
The materials are formed by the random stacking (not subdued to Then by connecting with a thick horizontal black line the two adja-
any law of repetition) of layers and (inter)layers of two or more types. cent reflections occurring at the closest position one to another
No rational series of (OOI) reflections s provided n the oriented ndependently of their serial number, t s possible to determine the
X-ray pattern. This s an mportant character : the materia/s are not regions of the X-ray pattern n which the diffraction effects are to be
true minera/s ; LUCAS (1 963) has proposed to have them designated found as single reflection, diffraction band or asymmetnc reflection.
by the terms interstratified structures (difices interstratifis, in In each of the determined point of the straight line there will occur
French). Moreover, it is not possible to give these nterstratified either a single reflection that belongs to the overlapping of these
structures a specific ame as for regularly interstratified minerals of the minerals A and B, or a narrow to enlarged diffraction zone
(corrensite, rectorite, tosudite, etc...). that replaces the two original but cise reflections of the minerals
The lack of periodicity along the c axis s expressed by the presence (layers) A and B. As the degree of interstratification of B with A
of irrational reflections (diffraction band and plateau, enlarged or ncreases from O to 1, the resulting reflection will shift from Si
asymmetnc reflections, ill-defined reflections of a rather low inten- toward 82, from 2Si toward 3S2 etc.
sity)of the (OOI)sequence.The first reflection, ntherange 10-17, Two remarks about this representation :
may be abnormal because of high intensity. In an nterstratified 1) In figure 26 the reflection zones 2S2 and 5S2 (belonging the
structure, the representative reflections take the place of the the component B of the nterstratified structure) are isolated. No
normal reflections that correspond to the two (or more) component shift does affect them ; only their shape and intensity will vary when
layers. the degree of interstratification (nameda) decreases from 1 to O,
giving rise to reflections that become flattened or that progres-
The determination of the interstratified structure s based on sively disappearing from X-ray pattern.
MERING's work (1949). The method concerns the plotting of the 2) The shift of a reflection s not linear. The curves representing
reciprocal vectors Si =1/di and S2=1/d2 on the same straight une the reflection shape and position n d(A) are in fact a function of a
(i. e. the sites of the reflections of the two simple minerals A and B) (that vares from O to 1), and can be calculated (BROWN and
on the X-ray diffractogram pattern (figure 26). Mac EWAN, 1951).
In a preliminary analysis, there will be not great error n assuming
that the peaks move linearly from the position for one pur compo-
nent toward the nearest position of the other component as the
proportions of the components alter (Mac EWAN, RUIZ-AMIL
and BROWN, 1961). This trend s expressed by the formula :
dm = dA+(dB-dA) (KUBLER, 1960)
Figure 26. - Schematic representation of the reflection zones of an inter- which allows a quick evaluation of the degree of interstratification
stratified structure formed of A- and B-types of layers (LUCAS, 1963). of B with A.

VI - D - 2. - GRITERA FOR THE RECOGNITION OF RANDOMLY INTERSTRATIFIED STRUCTURES


As t has been dealt with before, when the mineral is a regularly On a practical point of view for the determination of the composition
interstratified one, there appears a single reflection at a definite of a clay phase, when a randomly interstratified structure occurs
d-spacings due to a point effect ( = fusin of the two adjacent the (OOI) reflection of the latter are normal in shape and
and closest reflections, of the minerals A and B, into one single intensity, and are readily recognized by the fact that no rational
reflection having a d-spacing intermedate between those of the ndices can be attributed to them. The position of the basal
two former reflections). Ths new unique reflection replaces the two reflection of the interstratified structure s not fixed up by the
prevous adjacent ones, and has a definite d-spacing on account formula :
of the applicaton of the formula : d(001)AB = d(001)A+d(001)B
d(001)AB = d(001)A+d(001)B.e.d(001)AB=d(001)|+d(001)c The true (001) is not appearing in the X-ray pattern. As a conse-
=10+14=24 quence, the basal reflection and first one readily expressed
The d(004) of the regularly nterstratified mineral (I-C) will be thus corresponds in reality to the (002) of the mixed layer and s allocated
situated at a d-spacing of 24 : 4 = 6. n the d() range between 1 0 and 1 7 ; this (002) s somewhat related
to the d(001) of the A and B components by its d-spacing and will
In (randomly) nterstratified structures, the point effect does not have its passing from the d(001)A to d(001)B when the degree of
normally occur. In specific zones of the X-ray pattern, where the interstratification a increases without a linear_variation from O to 1 .
original reflections of the two components A and B are allocated, This observed basal reflection in the 1 0-1 7 zone s more or less
a new reflection will of course take place ; on account of the well-defined. Its shape s that of : a single reflection, flat-topped,
formula d m =dA+(dB'dA) t will not show any single and well-defined or a diffraction band following the type of stacking, the degree of
reflection, but rather an ill-defined one ; the latter will be more or disordering, the number of layers and nterlayers, the crystallinity
less enlarged at its base, or exhibits a fat top (diffraction band of the particles, the size distribution, the original d-spacing of
or plateau) the limits of which will rely upon the original d-spacings the components A and B engaged n the nterstratified structure.
of the components. The diffraction effect will thus represent the In such a structure, the position of the different (OOI) reflections
interconnected zones between two adjacent reflections of the com- can be roughly estimated by the application of the formula :
ponents A and B. As a consequence the shape of the resulting
reflections will vary from a straight line to various aspects.
Figure 27 tries to represent the shape of the (002) reflection as Usually this f i r s t reflection between 10 and 1 ?A is also only
the result of the randomly interstratification of layers of one com- present, and the most clearest defined one. The other (OOI) reflec-
ponent and (inter)layers of the other component. The (OOI) reflections tions are not systematically expressed. The shape of the basal
of the nterstratified structures are thus distinct from those of simple reflection may also be related to the degree of interstratification
clay minerals even in a mechanical mixture comprising a baddly (figure 27).
crystallized material (degraded mineral). The position, shape and
intensities of both the (OOI) reflections of the simple clay minerals
and mixed layers are distinguishable.

48
VI - D - 3. - DEGREES OF DISORDER AND CONSEQUENCES

Figure 27. - Schematic representation of the composition of a system consistmg of interstratified partiles,
and possible X-ray diffraction curve aspect for different mixed layers composed of A- and B-layers (interlayers).
d = degree of interstratification (vales from O to 1); n number of partiles with a given Q (modified
after KUBLER, 1961 : LUCAS. 1973 : in THOREZ, 1975).

Two cases of disorder can be considered (figure 27) : the disorder The summit of the reflection is at the dA position ; =10. but the
exists either m the particles or both in the partiles and n the clay resulting reflection shows a gentle slope (figure 27, 6) toward the
material itself. low angle side.
If the disorder exists only in the partiles, all of them give reflections It can be seen, on first analysis, how both the shape of the reflections
situated n the same d-spacing. The intensities of the resulting and the d-spacing can be provided by both the number of particles
reflections are high ;theirshapesare those of fairly narrow reflection occurring n the structure, and the degree of interstratification. For
types. Their d-spacings indcate the degree of mterstratification a comparison, if well-crystallized clay minerals are present in the
(figure 27, 4). In the case a constant degree of interstratification clay fraction, their (OOI) reflections are at a specific d-spacig, and
intervenes, the ntensity of the secondary reflections of the irrational the (001) exhibits a perfectly symmetric, narrow and intense reflec-
series (OOI) decreases rapidly from the lower to the higher terms tions (figures 27, 1 and 2) (i. e. at 1 O or at 14).
of the series. The greater the degree of disorder, the more rapid the
decrease. As a consequence, for highly disordered structures, The analysis of the asymmetry has been made by KUBLER (1961)
usually only the basal reflection will occur in the X-ray pattern. for randomly interstratified mica-montmorillonites (figure 27). As the
If the degree of order mcreases in the nterstratified structure, there distribution of the crystallites depends on the degrees of interstra-
should occur other reflections of the series (OOI), presenting an X-ray tification, different cases of shapes for the representative reflections
pattern of the interstratified structure with a progressive regularity can be observed. In figure 27, n represents the frequence of the
n the stacking of the components. There exists a continuous series crystallites, while a is the degree of interstratification or the number
of terms ranging from the complete disordered varieties toward of layers B interstratified with the layers A. Seven cases are discus-
the highly ordered ones ; the intermedate varieties can be termed sed by KUBLER (op. cit.) (figure 27, 1 to 7) :
almost regularly interstratified structures or minerals ". Figure 27, 1 :a = 0 ; unigue population of crystallites. The compo-
If the disorder exists both in the partiles and m the rock, the nen! A is only present (i. e. pur micas).
crystallites will show all the possible vales of the degree of Figure 27, 2 : a = 1 ; unique population of crystallites. The compo-
interstratification, and of the number of particles having the same nent B is only present (i. e. pur montmorillonite).
valu of a. Each partile will diffract for its own, and produces a Figure 27. 3 : a takes simultaneous all the vales between O and
d-spacing situated between those of the components A and B, at 1. and none population dommates the other.
d-spacings determined by a. Sin ce all the particles have a different Figure 27. 4 : 0<d<1 : unique population. Only one valu as for a
valu of a, none of the resulting reflections will become superposed. theoritical interstratified mineral.
No well-defined reflection does occur. All the radiations have rather Figure 27. 5 : 0<a<1 : the mximum population is statistical. If the
the same intensity, and a diffraction band (plateau) will be observed distribution s one of GAUSS type : m =true average.
instead of a single reflection. (Figure 27, 3). Figure 27, 6 : a m = 0 : the mximum population coincides with the
There are of course intermedate cases. Figure 27, 5 shows a pur component A.
particular distribution governed by a Gauss law : each partile Figure 27, 7 : a m ^1 ; the mximum population coincides with the
reflects for its own, but the ntensity of the radiation mcreases with pur component B.
the increase of the particles number with the same a. The resulting
effect is a reflection with an enlarged base, but with an apex In the case of randomly interstratified structures mica-montmoril-
dctcrmmed by the highest number of particles having the same lonites analysed by KUBLER (op. cit.), the asymmetries of the (001)
degree of interstratfcation. and (003) reflections are centrifuga! relatively to the (002). Upon
There are limited cases as for degraded Hites (KUBLER, 1961) glycolation, the reflection are not shifting, butthe change of intensity
where the partiles are formed by layers of a single type (micas). alters the shape of the reflections. These latter show a trend of

49
migration toward the low angle side. This can usually be demons-
trated by the decrease n ntensity of the (001) reflection, and by
the simultaneos increase of the background on the side of the Diffractogram
trace
low angles. In the mean time the (002) shows a hump ; the (003)
does not show any asymmetry, but s increased in ntensity. The
heating treatment collapses the asymmetries on the d-spacing
of the micas, with a parallel increase n the intensity relatively to
the original ones. Line diagram

In many examples, analysed by the present author, of degraded


ilutes showing a strong asymmetry of the (001) reflection toward
the low angle side, typically the residual 10 reflection decreases A I OOI reciprocal
in intensity upon glycolation. It becomes narrower and symmetric B I lattice points
and merges above an enlarged (and even) asymmetric diffraction
0.7 Estimated
band that extends from 10 or 14A to 1 7. 0.7
proportion of
On heating, the 10A reflection becomes symmetric and more intense
than n the natural sample. Such a behaviour typifes an illitic material Figure 28. - WEAVER's method for the analysis on the X-ray diagram of
where partly the partiles have maintained their original characters an nterstratified mineral.
of Hite while the other part of them has interlayers unstable upon
glycolation and heating (behaviour of montmorillonite).
M
Any material that swells fo 17 (after a Mg-saturation) must not 001
be systematically interpretad as a smectite. Works by REYNOLDS 17.8
and HOWER (1970) deals with such a behaviour of mixed layer
i/lite-montmoril/onites. On the basis of detailed matching of diffrac- M i\ /\
tion patterns of monomineramitic illite-montmonllonite of known che- 302 M c104 M

1.8 L 45 005 M
B.9 0 03
mical composition, these authors conclude thatthere are three types 3.58 006
5 97
of interstratification : (1) random, (2) allevardite-like ordering, and 4. 51
i
13.44 2.97
(3) superlattice units consisting of three i/lite and one montmoril- 9.;3 I 3.0
lonite layers (IMII). By comparison of suites of calculated profiles I i
i
with the diffraction patterns of many samples of illite-montmorillo- 5.7 I 1
|

nites, t s concluded that virtually all llite-montmorillonites with i Dhkl


I 1
expandabilities from about 40 to 100% are randomly nterstratified i -kX
(allevardite being exceptional); at <40% montmorillonite layers they 5.4
almost always have ordered nterstratification. All allevardite-like V .0 4. T 2 .09
ordering predomnate in llite-montmorillonites which have ordered 3.5 3.4
1
interstratifications, with the IMII superlattice varieties confined to 1
samples with about 10% montmorillonite layers. In the appendix of 10.( ) 5.0 3.33
their work, REYNOLDS and HOWER (1970) provides a set of 00 ? 004 006
calculated diffraction profiles. Among all their very interesting Mu Mu Mu
results, one deals in particular with the fact that a 17A reflection
is not necessary linked with a pur montmoril/onite phase ; when Figure 29. - Schematic representation for the reflections of mixed layers
randomly interstratified illite-montmonllonite materials are glycolated relatively (o the position and intensities of the pur phases (n this case
montmorillonite and muscovite) (after BYSTRM, 1956).
they may a/so provide a diffractogram pattern where the 17/4 is more
or less clearly defined. Quite accurate interpretaron of the propor-
tions of layers and interlayering type in illite-montmorillonites is
possible when using both the reflection positions of the low angle It is of nterest to recall the occurrence of zoned interstratifications
diffraction characteristics with calculated profiles. (VIVALDI and Mac EWAN, 1957): the representare retlectins are
typically sharp but are associated to diffuse diffraction effects on
Others authors (RODRGUEZ GALLEGO and PREZ, 1965; one side of the reflections. Such a type of interstratification occurs
HAMILTON, 1967) have respectively dealt with regular mixed layer in the Kinnekulle Ordovican bentonite analysed by Ann-Marie
Mica-Beidellite, and partially ordered mixed layer mica-montmoril- BYSTRM (1956).
lonite. They provided many diffractogram patterns some of them
having been reproduced and stylised n THOREZ's (1975) system A complete range of intermedate interstratified structures exits in
of monograma. But for these types of mixed layers the (002) the nature between chlorite and montmorillonite, and chlorite and
reflections are situated at about 11-12A (with a corresponding swelling chlorite as shown by LUCAS (1963). These intermedate
superlattice reflection n the low angle side of the X-ray pattern), varietes of nterstratified structures will be discussed later on the
and shiftto about 13,5 upon glycolation. HOWER and MOWATT ground of the proposed system of notation by LUCAS (1963)
(1966) have shown some llite-montmorillonite mixed layers having reproduced in THOREZ (1975).
their(001) reflection about.10.0-10.6 ; the glycolation provokes
a shift of the d-spacing to about 9.9 while the reflection s broader It must also be pointed out the occurrence of three-component and
and even slightly asymmetric. multicomponent systems. The method for dealing with such a system
is that of Mac EWAN (1956) which mvolves the calculation of
WEAVER (1956) has also shown diagrammaticaly how to analyse Fourier transform for the measurement of both the positions and
nterstratified structures by plotting the position of the reflections intensities of the reflections. But the method fails if the reflections
from the pur phase, but supposing the movement of the reflection are not numerous enough (at least 5 to 6 reflections are needed),
occurrmg linearly (figure 28). or if very broad reflections are existing in the X-ray pattern. The
But n the application of this method one has to keep n mind that calculation must also take into account the results of the treatments
all the reflections, as diffraction effects, will belong to the same (solvation with ethylene glycol or glycerol with/without cation-
material, and that the shift in reciproca! spaces when large s not saturation). WEAVER (1956) has dealt with such multicomponent
linear. For certain intermedate situatons, the resulting reflections systems considering successively the behaviour of the basal reflec-
tend to become wide and diffuse. tion in the range comprised between 10 and 18A after K- and Mg-
saturations, and heating treatment (400 and 500C). d-spacings and
Ann-Marie BISTROM (1956) has also published a presentaron for intensities were considerad. But this method does not take into
the reflections related to two types of mixed layers from Knnekulle consideration either the effects of different layer structure factors
(Sweden) (figure 29). Such a representation is composed with the or the possbility to have systems different than randomly inter-
reflections for the pur phases montmorillonite and muscovite. It stratfied ones. JOAS and BROWN (1959) have proposed a
s clearly shown how the reflections are moving between the vales graphic method to estmate the first order spacing from three-
related to the pur phases. component interstratified systems (figure 30). They considered the

50
four possible three-component interlayer systems including the 15.4
10 (Hite), 12.4 (Na-montmorillonite), 14 (chlorite) and 15.4
(Ca-montmorillonte) spacings given by these layers at 50% RH.
Triangular diagram (figure 30) such as that proposed by JOAS
and BROWN (op. cit.) can be useful where multicomponent inter-
stratification s found along with short sequence of basal reflections.
For two-component systems, the edges of the triangle s used ;
for four-component systems a tetrahedron with four triangles is to
be used. This method s convenient for completely randomly inter-
stratification.

Figure 30. - First-order apparent spacings for the three componen! inter-
stratifications that can be formed from 10, 12.4, 14, and 15.4A spacings 154 15.4
(after JOAS and BROWN, 1959, also reproduced in GIESEKING, 1975). 0.9 0.8 07 0.6 0.5 0.4 0.3 0.2 0.114.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

VI - D - 4. - PROPOSED NOTATIONS FOR RANDOMLY INTERSTRATIFIED STRUCTURES

A descriptivo codificaron for nterstratified structures has been reason the subscript O in IQ (designating the quality of the open
proposed by THOREZ (1967, 1973, 1975), a part of which being Hite) may be replaced by the subscripts C, V or M. This can be
nspired from LUCAS (1963). The nature of the layers and inter- done if the asymmetry and the foot of the reflection are not masked
layers is designated by different symbols which characterize and recall too much by the reflections devoted eventually to accompanying
the behaviour of the layers and nterlayers upon the diagnostic other clay minerals the basal reflections of which are situated n
treatments : the same d-spacing range as the f o o t of the 10A reflection. Three
types of degraded ilutes have been described by LUCAS (1963) :
1 ) 1 0 : nterlayer of 10 stable upon treatments, being similar in IC, IV and l|vl- They concern thus a form of random mixed layers
behaviour to Hite. that are intermediate between Hite (I), and more discrete random
2) 14c : interlayer of 14 stabie upon glycolation and heating being mixed layers llite-montmorillonites (figure 31).
similar in behaviour to chlorite.
3) 14Q or 14Cg : nterlayer of 14A ncreasing after glycolation, IC : The basal reflection at 10 in the natural sample exhibits an
but remaining stable on heating, being similar in behaviour asymmetry towards the low angle side, developed on the flank
to swe/ling chlorite. of the 10. This asymmetry remains stable after glycolation
4) 14y : nterlayer of 14, stable upon glycolation but collapsing and heating with its f o o t on the low angle side unchanged
after heat treatment, being similar in behaviour to vermiculite. and located at 14A. Because this foot remains stable at 14
5) 14M ( O r 14s) : nterlayer of 14 ncreasing after glycolation, and (and s closely related to the stability of the asymmetry), some
decreasing on heating, being similar in behaviour to montmoril- similitaries are proposed with the behaviour of a chlorite [(cf.
lonite. 14(N)-*14(EG)-14(500C)]. For this reason the subscript n
6) 7 : interlayer of 7 stable after glycolation, but destroyed on the ilute symbol, is specified as IQ. Indeed, this subscript C
heating, being similar n behaviour to kaolinite. does not indcate at all the presence of chlorite. If this .mineral
becomes associated in a mixture with IQ, it would be indicated
The above symbols indcate that the interlayers of the mixed layer by IQ, C (note the comma).
structures may have a behaviour like those of the corresponding IV : the asymmetry towards the low angle side and developed on
clay mineral Hite (I), chlorite (C), swelling chlorite (Cg), vermiculite the flank of the 10 reflection, remains stable upon glycolation,
(V), montmonllonite (M). When these symbols are used in a des- but is replaced by a narrow and symmetric reflection at the
criptive formula for an nterstratified structure, it does not preclude same d-spacing on heating. Because the foot of the asymmetry
that any discrete simple clay mineral is not present in the mixture provides some similitaries with the behaviour of a vermiculite
or even in the nterstratified structure : an nterstratified structure (cf. 14(NM4(EG)-10(500C) by the collapse on heating of the
might be generated by the weathering of a simple clay mineral ; distented interlayers, this variety of open Hite is designated
as a consequence some residual and intact particles might well by the symbol : IV-
still be preserved of the alteration while others are engaged n, and I|V] : the asymmetry on the lower angle side and developed on the
show n some nstances a modification of d-spacing due to the flank of the 10 reflection shows an ncrease of the background
distented process affecting the original layers of the mineral. and some swelling upon glycolation ; the asymmetry s
replaced by a narrow and symmetrical reflection on heating.
In the case of ////fe that undergoes an alteration the layers The movements of the 14A foot provide some similitaries with
become step by step intensively stripped of their original the ones of a montmorillonite (14(N)-swelling (EG) >10(500C).
K. A codificaron has been proposed by LUCAS (1963) that refers At the level of its distended interlayers, the open ilute behaves
explicitly to the opening character of the Hite chrystallites. The as a montmorillonitic material ; this is ndicated by the symbol :
stripping of the K determines the progressive displacement of some
of the interlayers from 10 to 14. The process provokes a modi- IM-
fication of the shape of the basal reflection at 10. The latter tends In the case of an nterstratified structure in which 10 layer
to become more and more asymmetric, with its foot situated near an/or 14A nterlayers (14c, 14y, 14Cg, 14|y|) are ntervening the
14 on the side of the low angles. The behaviour of the distended use of hyphen (outs/de and inside the parentheses), parentheses,
spaces after the treatments (glycolation, heating) allows to consider and the symbols : 14p, 14y, 14M, 14pg, 14|\/|, and I, C, V, M allows
and to compare the behaviour of the 14 foot reflection with similar to describe all the different types of inferstratified structures found
behaviours for chlorite, vermiculite, montmorillonite. There is the by several authors n natural clay samples. These latter comprise

51
clay material where the disorder may exist in the partiles or both 3)C-(140-14M)-M : The interstratified structure consists of :1) par-
in the partiles and n the material. Some examples, taken from tiles which are not affected by treatments ( = C) ; 2) partiles
THOREZ (1975) are here provided to Ilstrate how the notation all the interlayers of which expand to 1 7 ( = M) ; 3) interstratified
and description of the randomly mixed layers are constructed in partiles consisting of the above two types, with a degree of
a concise manner that emphasizes the type of stacking, the nature interstratification varying from O to 1.
and predominance of both the layers and inteHayers (figures 31 to 37).

VI - D - 4c. - RANDOMLY INTERSTRATIFIED STRUCTURES


VI - D - 4a. - RANDOMLY INTERSTRATIFIED STRUCTURES WITH 140 and 14Q
WITH 140 AND 14v
In the series with 140 and 14Q, the following varieties have been
1)(140-14v) : the interstratified structure is composed either by described by LUCAS (1963):
chlorite layers (14c) and vermiculite layers (14y) randomly inter- 1) CG (swelling chlorite) : the typical 14 with broad base n the
stratified ; or by chlorite layers (14Q) with distended interlayers natural sample s replaced especially by a large asymmetrical
(as revealed on heating) that behave like vermiculite ; such a reflection at 1 6.5 after glycolation ; on heating the 1 4A reflection
process takes place when a chlorite undergoes a weathering reappears and s very similar to the one of the untreated sample
at the level of the brucite layers. but with a slightly asymmetry toward the large angles. This inter-
Gradations in the intensity of the structural modification, when pretation s sufficient for the determination of a swelling chlorite.
the nterlayers are becoming progressively predominant upon the Certain layers are similar to true chlorite while others are closer
residual chlorite layers can be expressed in more detailed nota- to montmorillonite ; this situation corresponds to the presence
tions as follows. of nterlayers that are more or less filled with brucite sheets,
2)O-(140-14\/) :beside the randomly interstratified material (struc- thus provoking an expansin of some of them. The asymmetry
ture) (140-14v) there still exists some discrete chlorite (C) which arising on heating and glycol indcales the presence of nterstra-
cannot readily be distinguished from the (14q-14\/) in the X-ray tified layers.
pattern. Typically this notation is n relationship with a diffraction 4) (140-14Q) ; the displacement of the 14 reflection to 15.5A
band that extends from 14 (cf. the residual chlorite) to 12 after glycolation, and the unchanged d-spacing of the basal
(cf. the (140-14y) mixed layer after heating treatment.) reflection on heating (symmetrical reflection at 14) prove that
3)V-(140-14v) indicates a degraded chlorite mineral which has some swelling layers are occurring in the structure. However
undergone a more sensitive alteration than the previous case 1) the swelling s less than of a true swelling chlorite. This is due
and 2). In the untreated and glycolated sample, the basal reflection to the interstratification of interlayers stable to glycol and inter-
is situated at 14. But on heating, this single reflection is replaced layers sensitive to this treatment. But on heating, all the nterlayers
by a diffraction band extending from 1 2A [cf. the theoritioal po- are stable. It is concluded that certain layers behave as chlorite
sition of the (002) of the mixed layer (14c-14\/)], and a basal while others behave as layers of swelling chlorite.
spacing near 10 (that s related to the collapse of the v e r -
3) C-(140-140): the 14 reflection n the natural sample s replaced
miculite behaving nterlayers n the mixed layer on heating).
by a horizontal plateau stretching from 14 to 15.5A after glyco-
4)O(140-14v)-V corresponds to a highly randomly interstratified lation while a single 14 reflection reappears on heating. This
structure where both chlorite (C), vermiculite (V), and chlorite- behaviour indicates the interstratified structure being composed
interlayers with different behaviours of vermiculite, are all together of : 1) partiles stable upon glycolation, that provide the edge
represented. On heating the (001) s represented by a dif- of the plateau at 14A = chlorite C ; 2) an aggregate of partiles
fraction band extending from a d() of about 14 to one near 1 O. with variable degrees of interstratification, composed by 14
stable layers and 14 nterlayers which swell upon glycolation.
If a discrete chlorite or vermiculite s clearly identified in the clay The mximum swelling at 15.5A ndicates that the mximum
fraction, the notation might be as follows : C, C-(140-14v) or degree of interstratification does not exceed 0.5, the complete
V, (140-14v), C, depending on the accuracy n the evaluation of range of the degree of interstratification being from O to 0.5.
the quantitative and qualitative occurrence of the components, and The heating proves that all the particles are stable like those
the proportions of the components in the clay mixture. of a swelling ohlorite.
4) C-(140-140)-Cg : this structure s similar to the preceeding one,
but the plateau upon glycolation stretches from 14 to 17,
VI - D -4b. - RANDOMLY INTERSTRATIFIED STRUCTURES while a single 14A reflection appears on heating. This ndicates
WITH 140 and that the 14A oomplex consists of : 1) partiles all the nterlayers
of which are stable at 14; 2) particles all the nterlayers of
A complete sequence of descriptive notations has been ntroduced which expand fully on glycolation ; 3) an aggregate of interstra-
by LUCAS (1963) in the case of 1 4 complexes ; these comprise tified partiles with both the above mentioned types of nterlayers.
both chlorite (C) and interstratified structures with 140 and 14|\/| Here the degree of interstratification possesses all the vales
types of nterlayers. The following varieties are noted : from O to 1.
1)(140-14|\/|) : the nterstratfed structure s composed of 140 A mixture of the two different interstratified struotures may occur :
layers (not affected by glycolation and heating, as n chlorite), and (140-14Q)+(140-14|V|) which is typified both by the behaviour
of unstable nterlayers that behave like montmorillonite (that after glycolation and heating. In the glycolated sample, the original
swells at 15. 5 and collapses to 1 2 on heating). All the partiles 14A reflection s replaced by one the apex of which s situated at
have a similar composition. Although this structure has both about 15.5-15.7A. On heating a doublet appears at 12 and 14.
chlorite- and montmorillonite -type spacings, t may not be clas- The shifting of the 14 reflection to one at 15.5A upon glycolation
sified as corrensite, this latter being only devoted to a regularly ndicates that the particles responsible for the expansin are inter-
interstratified mineral built up by chlorite and montmorillonite stratified, and that there exists two types of nterlayers : stable and
layers. unstable. The two reflections observed after heating reveis that
2)C-(140-14|\/|) : the interstratified structure s composed of stable two different structures are coexisting. The 14A reflection after
chlorite partiles, and other partiles which are unstable and heating could be nterpreted for Chlorite, but no reflection or break
show a continuous transition of their degree of interstratification n the slope is noted after the treatment with ethylene glycol ;
from O to V. In these unstable partiles, there are two types of This corresponds to an interstratified structure that can be noted :
nterlayers, like n (140-1 4|V|) ; some of them are stable upon (140-14Q). On the other hand, the 12A reflection indicates the
glycolation and heating, the others are unstable with a mximum presence of nterlayers unstable to the heating, and therefore cor-
of swelling of 15.5. Chlorite s not distinctly separated from responds to an interstratified structure noted : (140-14|V|). The
the interstratified structure ; this situation s emphasized by the entire structure can be indicated as (1 40-14Q)+(140-1 4[\/|).
hyphen placed between C and the parenthesis. If chlorite does
occur as an mportant component beside the interstratified struc-
ture, the transcription will take the form : C, C-(140-14|\/|).

52
VI - D - 4d. - RANDOMLY INTERSTRATIFIED STRUCTURES WITH asymmetries that modify the shape of the reflection. A similar
10 LAYERS AND 14M AND 14v INTERLAYERS situation intervenes with structure like (10-14v) where, also, the
basa/ reflection has its apex remaining at 10.
THOREZ (1967, 1973, 1975) has developed a specific notation for This first type of interstratified structures is of course more or less
the description of randomly interstratified structures composed by different n both their descriptivo transcription and X-ray pattern
Hite layers and swelling interlayers. The former are desgnated by than other mixed layers of the random type where the basal reflec-
the symbol 10, and the latter, because their similitude of behaviour tion is allocated, n the natural sample, at d-spacings higher than
with montmorillonite , are denoted 14(V|. If discrete Hite s present, 10. For nstance, there are some structures involving or composed
this will be ndicated by a separated symbol, I. Because there s of ////fe layers and montmorillonite (inter)layers that exhibit a basal
a rather continuous transition between stable Hite partiles, I, and spacing at about 12. On glycol this reflection splits into two
the nterstratified structure, the symbol I may be linked by a hyphen distnct reflections, one situated at about 10, the other at the low
to the representativo formula of the structure. angle valu. In this case it s rational to describe the material by a
somewhat different notation. The case is encountered in K-bentonites.
A complete sequence of transitional terms can be developed with If one must take into account the variation and relative amount of
defined notations : (10-14|\/|); lQi(10-14M), 10-(10-14|v|); 10-(1 14M interlayers in these structures, it s possible to adopt the system
10-(10-14M)-14M; (10-14M)-14M710-14M)-14M (figure 35). mtroduced by JEHL and LEIKINE (1968) : (|Q-14|y|), (10-14^),
From JLQ;(10-14|\/|) to (10-14|\/|)-J_4j\/|, there occurs a progressive (10-14M), (10-14[y|), (IO-MM). the underlining emphasizing the pre-
transition between structures where, firts, the ilute layers 10, are dominance of either the Hite layers or the montmorillonite inter-
largely predominant comparatively to the montmorillonite-like inter- layers.
layers, toward structures where these swelling interlayers are pre-
dominant.
Generally these structures exhibit in the natural sample a very asym-
metrical reflection toward the low angle side of the diffractogram REMARKS
pattern, but with its apex situated at 10 as for micas. On heating
this asymmetry is replaced by a narrow, more intense and more or As pointed out and shown in this chapter, randomly interstratified
less perfectly symmetrical 10A reflection. The different terms of the structures have a very wide range of compositions, diffraction
above quoted sequence of nterstratified structures are determined patterns, and behaviours upon the treatments. Such a situation is
by the characters pf the diffraction band that stretches on glycol possible, and s found in the nature, because each type of the
from 10 to 17 following the predominance of the inter- nterstratified structures is built up by two (or more) types of ele-
layers. mentary layers (and interlayers). Upon the different diagnostic
Of interest to note s the fact that Hite, I, can be associated to treatments, these interlayers behave like Hite (10), chlorite (14c),
the structure as well in the mixture. Such a character is shown by the treat- swelling chlorite (14cg), smectite (14|\/i), vermiculite (14v). Further-
ment with ethylene glycol, by a more narrow reflection at 10A (with more, there are different degrees of ordering in these materials.
a sensitively decreased intensity), that develops above or beside a Some of them are completely random, other tend to some regularity.
diffraction band related, on its side, to the interstratified structure. In the wide range of nterstratified structures, there are some of
Also smectite may occur in the sample, and may be identified by them which are composed of a clay mineral that undergoes different
a discrete 1 7 (on glycol), that is linked to the diffraction band. degrees of weathering. For these, the all weathering process is
based on the fact that progressively some of the layers become
Hlne PAQUET (1969) has found different terms in interstratified unstable and behave like montmorillonite or vermiculite, while the
structures where the ////fe layers, 10, are nterstratified with inter- parental clay s ilute (mica) or/and chlorite.
layers behaving like vermicu/ite , 14y. The sequence comprises
the following intermedate terms : l-(10-14\/)-V, (10-14v)-V, and An extensivo presentation of the variability among the mixed layers
|-(10-14v)-V. These interstratified structures are stylised in figure 37, exceeds the scope of this handbook or chaper. But the Laboratory
and are determined by the d-spacings, shapes and behaviour of Handbook published by the present author (THOREZ, 1975) has
the basal reflection (which d-spacing s situated at 10, 12, and 14) tried to provide a presentation of all the possible and noted cases
following the importance of the vermiculite interlayers n the inter- that exist n natural conditions. The reader, teacher or student, is
stratified structure. thus invited to refer to this Handbook to get an llustration of all
the characters shown by the variable mixed layers, both regular and
One can see the differences n both the notation system and dif- random. The combination of the present handbook with the pre-
fractogram patterns for the randomly interstratified structures. One viously published one provides a rational and didactic approach
type of structures is described with notations like i. e. 10-(10-14|\/|) to the problem of the X-ray diffraction analysis of the clay mineral,
or (10-14y)-14v because the geological or pedological conditions including the mixed layers minerals and structures. Mac EWAN and
have shown that these materials are generated after the weathering RUIZ-AMIL (n GIESEKING, 1975) have published complementary
of Hite or still show some parental links with Hite. In the case of data about the mixed layers, in particular some relative to the struc-
the (10-14M) structures, the main character s that the basal tural characters which has not be dealt here with n details in
reflection has always its d-spacing situated at 10 despite the order to not dupplicate the informations.

53
FORMULA
9 10 U 12 13 14 1? 20 25

NATURAL d(002)A d(001)B


MIXTURE
d(003)B d(004)A
OF A AND B
MINERALS

REGULARLY d(OOI)=
INTERSTRATIFIED AB
MINERAL dA(ool)+dB(OOI)

RANDOMLY d(OQ2) A DIFFRACTION


INTERSTRATIFIED
MINERAL
d(005)AB (FORMED OF
A AND B-TYPE
LAYERS

2SA SB
u SA
J I I I J

KEY CODE MONOGR. N


REFERENCE:

54
FORMUL REGULAR MIXED LAYERS WITH C, C g , M V GENERAL
o
d(A) 8 9 10 11 12 13 14 17 20 25 30 3 9 10 11 12 13 14 17 20 25 30 ] 9 10 11 12 13 14 17 20 25 30

N 4 E(3 530
VS

A M
(C-V)R
2t}

28
W

24

1
i1
1', 15' ,5
-4
?

VS

s 21 31
B (C-M)R .
1 24

vw
W
|
1
<
4
14,5 12

VS

s 3
2t

34
24
c (Cg-M)R
1
W

vw
1
> i

14 1,5

vs
31
28
D 1 (Cg-V) R
1 1 24
W

vw
1 1

1<1,5 15,5

VS

2( 3 31
E M (M-V)R

vw
W
\
20

i
4-
KEY CODE MONOGR. N
REMARK:
IREFERENCE; VARIABLE 105
Figure 31. Position n d() of the (001) and (002) reflections for regularly nterstratified minerals :
(C-V), (C-M), (Cg-M), (Cg-V) and (M-V) after diagnostic treatments (ethylene glycol and heatmg). 55
FORMUU j (14C-14V)IRR VARIETS GlENERAL
0 .
d(A) 6 7 B 9 10 11 12 7 20 25 30 6 7 8 9 10 11 12 13 14 17 20 25 30

N OR EG 550 E
VS
c,v, (14C-14V)
s (14C-14V)
12 13
M

W
1
4
i1
550 14 A 550 F
VS
C* V, (14C-14V)
s
M 10 12
W

VW
ii
550
4
B 550 G
VS 14
C, V* V - (14C-14V)
S

L
M 10 12
W

VW
IM

550 _r
550 H
VS
C + (14C-14V) i C - (14C-14V) - V
s 2 14

LJ
M 10 14
W

VW
i
550 D 550
VS
C - (14C-14V) V*
s 12 Vt
M

]I
10
VW
~ I T
i

*GIVEN FOR COMPARISON KEY CODE MONOGR. N


REFERENCE THOREZ (1973) VARIABLE 113
Figure 32. Behaviour of the basal reflection of random mixed layers (14c~14v) upon diagnostic
56 treatments fethylene glycol and heating).
(14C-14M) MIXED LAYERS VARIETS GENERAL

d(A) 8 9 10 11 12 13 14 1? 20 25 30 9 10 11 12 13 14 17 20 25 30 8 9 10 11 12 13 14 17 20 25 30

EG 550


14 15,5


14
12 14

C-(14C-14M)


14
vs 14 17 10
C-
(14C-14M) - M

KEY CODE MONOGR. N


*GIVEN FOR COMPARISON
REFERNCE LUCAS (1963) VARIABLE 125
Figure 33. Schematic presentation ofthe characteristic behaviourand s h a p e o f t h e " basal > reflection
of random mixed layers (14c~14M) upon diagnostic treatments (ethylene glycol and heating). 57
FORMULA r(14c-14G) VARIETS, GENERAL

d(A) 8 9 10 11 12 13 14 17 20 25 30 8 9 10 11 12 13 14 17 20 25 30 8 9 10 11 12 13 14 17 20 25 30

14
EG 550
vs
s
M

w
vw

15,5 14

vs

I
14

vs

- (14C-14G)

14

vs
c- 14 17
(14 C -14 G )-C G
w
vw

155

vs
12 14

REMARK: KEY CODE


U MONOGR. N
LUCAS (1963) VARIABLE 140
Figure 34. Schernatic presentaron of the characterisic behaviour and shape of the basal reflec
58 ton of random mixed ayer (14Q140) upon diagnosic treaments (ethylene glycol and healng).
LA (10-14M) RANDOM MIXED LAYERS GENERAL
13 14 17 20 25 30 14 17

I + (10-14M) - 14

I + 10 - (10-14M) (10-14M)-14M

+ 10-(10-14 M )-14 (10-14M)-14M

10-(10-14M)-14M, M (10-14M)-14M,M

KEY CODE MONOGR. N


EMARK. *AFTER GLYCOLATION
THOREZ (1973) VARIABLE
Figure 35. Schematic presentaron of the characteristic behaviour and shape of the < basal reflec-
tion of random mixed layers (10-14M) u pon dagnostic treatments (ethylene glycol and heating). 59
|_A (10-14) MIXED LAYERS VARIETS

14 1? 20 25 30 14 1? 20 25 30 10 11 12 13 14 I/ 20 25 30

REFERENCE:
Figure 36. Schematic presentaron of the characteristic behaviour and shape of the < basal reflec-
60 tion of random mixed layers (10-14) upon dagnostic treatments (ethylene glycol and heating).
(10-14V) MIXED LAYERS VARIETIES

9 10 II 12 13 14 I/ 20 25 30 9 10 11 12 13 14 17 20 25 30 I 10 11 12 13 14 I/ - 20 25

12 PAQUET(1969)

PAQUET (1969) I - (10-14V) - V


14

(10-14V) - V

I - (10-14V) - V

KEY COPE MONOGR. N


REFERENCE: VARIABLE
Figure 37. Schematic presentaron of the characteristic behaviour and shape of the basal reflec-
tion of random mixed layers (10-14\/) upon diagnostic treatments (ethylene glycol and heatmg). 61
Vil - ROUTINE IDENTIFICATION INDEX FOR CLAY MINERALS
AND MIXED LAYERS
Two series of co/oured indexes are presentad here in order to Four columns divide the tables. The fourth one, on the right hand,
provide the user with a computation tool allowing a rapid and provides the possible ame of the material, described with appro-
routine identificaron of the possible compositions of both simple priate symbols. Beside these formula are bald figures that refer to
clay minerals and mixed layers (regularly and randomly interstratified the numbering of the stylised diffractograms (monograms) in
minerals and structures). THOREZ (1975). The reader may thus directly refer to the monno-
The system takes only into account the behaviour of the basal grams in the latter Laboratory Handbook.
reflection (untreated sample ; glycolation and heating). The identifi- The first three columns are divided horizontally n order to display
cation keys here proposed are built up with an appropriate colour the X-ray characters for untreated (N), glycolated (EG) and heated
chart, and with different symbols (hese being related to the d-spa- (500C) samples.
cings of the (001) reflections. (See legend). By the proposed system The vertical subdivisions are achieved by considering successively
of notation, t is intended to reach the dentification of the clay the d-spacing ranges of the (001) reflection of the materials from
minerals at the level of the species or group. In some cases, the 7 to 15.3. These subdivisions are based on both the colour chart
classical tests succeed to provide this aim. In other cases and for and the mnemotechnicalsymbols ; this allows to Ilstrate a narrower
an accurate identification, it is necessary to investgate the material range of the d-spacings (see legend).
in more details (cation-saturations, attack by acid, reaction with
other inorganic and organic compounds). The entire X-ray patterns The subdivisin s completed for the natural samples, by taking
of both the oriented aggregate and random powder mounts might into consideration the successive ranges of the d-spacings within
be analysed at the level of the d-spacings, shapes and intensities the corresponding coloured subdivisions and symbols. For the
of the reflections, in particular the d(060) characters. Such an characters of the (001) reflection on glycolation, the same principie
objective cannot of course be provided in this routine identification is adopted n the column subdivisin. Finally, the third column
keys. It is published elsewhere (THOREZ, 1975). provides a similar subdividion as for the two others by taking into
consideration, thanks to the coloured and symbol system, the character
The principie of the presentaron here followed in the tables (or (d-spacing, shape of the basal (001) [cf. (002)] for regular and
keys) s to limit the dentification to the effects of the classical random mixed layers) after having examined the oriented X-ray
treatments (N, EG, 500) on the (001) reflections, and toemphasize pattern of the heated sample.
the modifications of d-spacings and shapes. Indeed in the regularly
interstratified minerals there occurs a superlattice reflection stretch- By this system a classification and a particularization of the
ing from about 20 to higher vales in d() that are not shown characters of the (001) reflection can be rather quickly grasped,
in these tables. In random mixed layers and because of the lack of allowing the matching and synthesis of the behaviour. For instance,
the superlattice reflection (long spacing) the dentification of the f the analysed X-ray pattern shows a 14 basal reflection n the
composition of the material lies only on the behaviour of the dif- natural sample, that shifts to 1 ?A on glycol, and collapses to 10
fraction effects (asymmetry, symmetry, diffraction band or plateau on heating, the user proceeds to the following step-by-step proce-
occurring in the range stretching from about 10 to 1 7A); the dure :
analysis is achieved by taking into account the behaviours of these 1) refer to the table where the 14 reflection is represented by both
reflections -the so- called basal reflection that corresponds its colour (the green) and symbol (star).
to the d(002)- after the different diagnostic treatments (the classical 2) in the second column, check the corresponding square or com-
ones plus, eventually if needs, the complementary ones). partment where the 17A reflection is provided : the blue colour, plus
the appropriate symbol, a solid circle.
Generally speaking, these tables take into consideration the 3) check in the third column the representation (colour and symbol)
characters of the basal reflections after glycolation and heating, corresponding to a d-spacing of 10 : the yellow compartment,
following a progressive system of classification that will be later and then the vertical solid rectangle (Symbol),
explained. On account of the specific characters of the X-ray pattern 4) at the level of the horizontal subdivisin of the table, the wanted
(n the low angle side), the possible composition is given following ame will be provided by the successive sequence " of co/ours
the adopted notations introduced in this handbook and already and symbols for the (001) reflection for nstance :
published elsewhere (THOREZ, 1975). (14=green+star)->(1 7 = blue+solid crcle)-10(yellow solid rec-
N EG 500
The tables collect a larger range of varieties for the mineral species tangle).
than t has been dealt with until now in the previous chapter.
On another hand, they take into account all the tendencies that By the procedure of checking the behaviour of the basal reflection
characterize some minerals or interstratified minerals (and struc- of the trested mineral, and by using a concise formula to emphasize
tures) thanks to a particular character (d-spacing, shape). the behaviours, t is possible to reach and characterize the mineral
composition or the probable one. The characterization is indicated
The construction of the set of tables is based on the following by an appropriate symbol for simple clay minerals, by a formula
parameters. with parentheses for the mixed layers, both minerals and structures.

62
SYMBOLS FOR THE TABLES 30-36

N-EG-500 ROUTINE IDENTIFICATION KEYS


FOR CLAY MINERALS AND MIXED LAYERS,
WITH REFERENCES TO THE NUMBERING
OF THE ILLUSTRATING MONOGRAMS

d-spacing m for the (001) of clay d-spacing in A for the (001) of clay
Symbols minerals & (002) of mixed layers Symbols minerals & (002) of mxed ayers Symbols Signifioation

^
- No reflection 13,5-13,8 S~\ Broad reflection

7 ~7 13,9-14,3
11 Diffraction band

OJ^
9-9,7
0
* 14,6-15,3 Doublet

1 9,8-10,1
e 15,5-15,8
L
Asymmetry towards
low angles

A 10,3-10,5
<x> 16 -16,5 A Asymmetry towards
high angles

Reflection with
V 10,6-11
0 16,8 17,2
J enlarged foot

A 11,2-11,7
17,3-18
*M#)
(#) Origin, n , of
the tailing reflection

Doublet Possibility of two d-spacings


1 |J 11,9-12,3
[i.e. (10+13)] S for the basal reflection

3 i 12,5-13,3 v /*
^
/' '
Diffraction band
[i.e. (11-14)] + Variation of the d-spacing
for the basal reflection

63
NATURAL-WITHOUT PRETREATMENTS K-SATURATION
COMPOSITION 300 500

Table 30. Coloured key for the routine dentification of curren! regularly nterstratified
minerals, based on the behaviour of the (002) reflection after different treatments.
Comparison with the one of simple clay minerals (after THOREZ, 1975).
Composition Composition
EG 500 +(monogram n, in THOREZ 1975) EG 500 +(monogram n, in THOREZ 1975)

CHLORITE C

VERMICULITE V

CHLORITE + VERMICULITE C, V

(C-V)
**<)

C. (C-V)

C-(14 C -14 V )

V. (14 C -14 V )

+ (14Q-14 V )

V, (14 C -14 V ). C

V-(14 C -14 V )-C

SWELLING CHLORITE C

MONTMORILLONITE M

CHLORITE with montmorillonite


behaviour CM

ic-c

(C-M)

(Cg-M)

C-(14 C -14 G )

C-(14 C -14 G )-C g

C-(14 C -14 M )

C-(14Q-14 M )-M

e (14 C -14G)-(14 C -14 M )

Table 31. Identification keys for o mixed layers nvolving Hite 10


layers (left hand column) and 14 layers (right hand column) with
different types of (inter)layers (after THOREZ, 1975).

Table 31 65
Composition Composition
EG 500 +(monogram n, n THOREZ 1975) EG 500 +(monogram n, n THOREZ 1975)

A PALYGORSKITE 24

v|) 85C

A
GLAU (20%M)21B

(10-14 V -14 M ) 156

A 1 A (I-M) (20-25%M)

(10-14|v])-14M 89B

(10-14v) 70A

(10-14M) 95

(I-M) 98

Tale 4 / Paragonite 6 / Pyrophyllite (TALC-SAP)

I 8A-8B / Mu 5, 9-11 / GLAU (1 0%M


21 A / I (%M or 1 4 V <10)101,1027

(1_0-1-1M) 93 / (I-M) M-15b


(I-M)R / (Mu-Bei)

(10-14^)870

JD)
D) k.(V)

ly 8D / (10-14M) / GLAU 15, 16A (I-M) M>25'o

IC 8C / 2M-)+1M Mi (10-15%M) 12 GLAU 50"oM


-(*)

I M 8 E / I + IM GLAU 19B

U 10-(10-14 M ) 60, 83A-83D /


(10-14 V -14M> 55 / (10-14y) 70C
10-(10-14 M )-14 M 86E, 87E, 91

>(*) o/* A (I-M) 99

14M 83E-83I AMMERZOITE / GLAU 22A

HM 84B / I + 10-(10-14 M ) 84D, 86B ,


HO-(10-14M)-14M 84E

H M 84C

84A K10-(10-14 M ) 86A

10-(10-14 M )-14 M 85D

A METAHALLOYSITE (I-M) with Al-lnterlayers

(10-14v-14M)
Tables 32 to 35 : Identification keys (after THOREZ, 1975).
1 T B.G. = Increase of back-ground.
I B.G. - Decrease of the ntensity.

66 Table 32
Composition Composition
EG 500 +(monogram n, n THOREZ 1975) +(monogram n, in THOREZ 1975)

GLAU 10-15 Type 17, 18C

(10-14 M -14 V ) /(10-14M-14 C ) ;10-14 M )-14M 89C

(10-14M-14C) / (10-14V) 75D /


(10-14 M )88A

Va 31 / (10-14v) 75B / V Layers 30

SEP 25 / (I-V) 71 / (Mi-V) 152 /


(BIO-V) 74 / l-(10-14u)-V

(I-C) / (SER-Su) 68 / (Bio-C) 67

(10-14g) /(10-14c-14M) 75E

(10-14 M ) / (10-14v-14M) /
10-(10-14M) 86 C

[10-14M)96 / (10-14 M ) 87B

(10-14 M )-14M 88C, 85E / GLAU 19C /


+ 10-(10-14 M )-14 M 85A, 85B ;TALC-SAP) 76, 77

(Mi-M) 78, 79 / Mu-BEl) 80

!I-M) / (10-14g) / (BEI-HyMi) 81

(10-14 M )-14M 89D (M-I2-V) / (10-14M) 87A

Table 33 67
Composition Composition
500 +(monogram n, in THOREZ 1975) EG 500 +(monogram n, in THOREZ 1975)

V-(14 C -14 V ) 113G / (14c-14v) 168

IE X -(14)I / (C-V) / (14


V-(14c-14v) / Al(14c-14y)

Ve 84 / (V-Mi)=(PHLOG-V) 151

Cs

V-(14c-14y) / (14c-14 v ) 167 /


Al(14c-14v) / lEx'< 14 A)l /
Cryptomontmonllonite 45

2:1-2:2 Al(lnt.) g / Cs

I14 c -14v) 165, 166 / (C-V) 106, 107,


105A. 109, 110, 117, 118, 119

(14c-14v) 113E

C-(14c-14\/) 113D

) 113C / C-(14c-14v)

CH2O

CM 54, 125A

C 25, 113A / Al-lnterlayers

C-(14c-14 M ) 125C, 135, 136

C-(14C-14M)

OV^te I14C-14G)/C-(14C-14G)

(14C-14G) 143 /C-Cg) /


V 27 / V<c 11 31 / V>c / Vp e / VAI 33 C-(14 C -14 M ) 144 / C-(14C-14G) 140C

(14 M -14 V )

C-(14 C -14 M )-M / (14 C -14 M ) /

(14c-14Q)-(14 c -14 M ) 149

(14 C -14 G )-(14 C -14 M ) / (C-Cg)


C-(14 C -14 M )

C-(14 C -14 M )

C-(14 C -14 G )-C g

(14 C -14 G H14 C -14 M )

Table 34
68
Composition Composition
500 +(monogramn,in THOREZ 1975) EG 500 +(monogram n, n THOREZ 1975)

e/ (C-M) 159

V / (not Mg-saturated)

(14C-14M)

(C-M)

C14C-14M) 127, 132, 172 / (Cg-SAP)


124 / (C-M) 120 / (M-|2-C) / C g -M) /
O (14 C -12 M )

(C-M) 121

C-(14c-14 M ) 128

(14c-14 M ) / (C-M)

) / (C-M) / Cq 53 /
C-(14 C -14 M ) 137

Cg 140 / lEx-Cs / lEx'Cg

VAI / vFe

M / BEI / Sm<c / Sm>c 1 Smpe


Smy\| / Intermedate Sm-V

Cg + M / C+M

gs

(C-M)

SAP / M / BEI

(14)lEx / Ex(14)l g 13 / lg /
NON 20D, 41, 42 / Sm 38, 39 / BEI 40 /
GLAU 23 / NONFe 42 / Ms 43 /
BEIS 44 / SAP 46-48 / Bentonite 49

C gs 55, 56

e (C-Cg) / (14 Cg -14 M ) 161

GLAU 16C, 16D

(10-14 M )-14M 89E

o** Ms / (14 c -14v) 114

Table 35 69
VIII. - DECREASING (001) IN d(A) OF PHYLLOSILICATES AND CLAY
MINERALS, AND (001) AND/OR (002) OF REGULAR MIXED LAYER
MINERALS - air dried state

d() : basal d() : basal


reflection Mineral ame reflection Mineral ame

43,75 Tarasovite 14,15 llb Chlorite ; Ripidolite ; Kmmererite ;


31.5 (CD-MT) Sheridanite; Kotschubete ; Prochlorite
30.5 (M-C) 14,1 llb Mg-Chlorite ; b(90") Fe-Chlonte ;
30,4 Tosudite : AI(14c-14M) : (OCg) Ripidolite ; Kmmererite ; Thuringite ;
30,o AKM-OD ; (M-C) Aphrosidente ; Leuchtenbergite ; Sheridanite ;
29,9 (C-V) Orthohexagonal Chlorite : Monoclinic
29,8 (C-M) Chlorite ; la Cookeite ; (C-Cg) ; Dioctahedral
29.6 (C-M) Chlorite ; Corundophyllite
29.4 (C-SAP) 14,0 Bavalite ; Diabantite ; Grochauite ;
29.2 (M-C) ; Tosudite Cr-Ni-Pennine : Mg-Chamosite ; (C-V)
29,0 (C-M) ; (C-V); (Hydrobiotite-Vermiculite)
28.5 Corrensite
28.44 (C-M) + (C-Cg) 13,85 (Mi-Allevardite) ; Corundophyllite
28.3 Corrensite 13,77 Fern-Nontronite
28.0 (Hydrobiotite-Vermiculite) 13,7 Sheridanite
27.6 (C-Cg) 13,6 Sheridanite ; Prochlorite ; Thuringite
27.5 (Mi-M) 13,4 (Mi-BEl) ; Stilpnomelane
27.3 (Mi-M) 13,3 Chloritized Montmorillonite
26.7 (I-M) 13,1 Leuchtenbergite ; Mn-Sepiolite
26.3 (Mi-BEl) 13,0 Stilpnomelane
26,0 (10-14M) 13,0-12,1 Stevensite
25.8 (Mi-M)
25.5 Hydrobotite ; (10-14v)
25.2 (Mi-M): (Mi-V) 12,8 Loughlinite
25.0 (I-M) 12,7 (Mi-M)
24.8 Hydrobiotite : (10-14v) ; (TALC-SAP) 12,6 (Mi-M); (BIO-C)
24.7 Allevardite 12,59 Ganophyllite
24,5 (TALC-SAP) : Stevensite 12,5 (10-14M) ; (I-M)
24.2 (SER-SU); (Mi-Su) 12.45 (I-M)
24.0 Stevensite ; (BIO-C); Hydrobiotite 12,4 (Mi-M) ; Hydrobiotite
23.8 (TALC-SAP) 12,4-11,2 Stevensite
23,0 Hydrobiotite 12,33 Bannisterite ; Stilpnomelane ; Hydrobiotite ;
(Mi-Su) ; (Ser'Su)
12,3-11,7 (TALC-SAP)
16 Saponita 12,2 Sepiolite : Stilpnomelane ; (Mi-V)
15,66 Zebedassite 12,17-12,11 Stilpnomelane
15.4 Griffithite ; Sauconite ; Nontronite : Stevensite 12,05 Sepiolite ; Zeophyllite ; Mn-Sepiolite
15.2 Fe-Saponte : Fe-Montmorillonite ; 11,8-11,,77 (TALC-SAP)
AI(14p-14M) ; Tosudite 11,7 (I-M) ; Aquacreptite
15.1 Chlorite (Dioctahedral) 11,5 Pyrosmalite
15.0 AI(M-C)D : (C-M) ; Al(C-Cg) : Chlorite 11,4 Hydrobiotite
(Dioctahedral) ; Diabantite ; Montmorillonite 11,3 (Mi-M)
12-15 Montmorillonite ; Hectorite 1 1,0 (Mi-BEl) ; Aquacreptite ; (10-14M) ; Karpmskite
14,9 Saponite
14.8 Expandable Chlorite-like mineral
14.7 Nontronie ; Montmorillonite ; Beidelite ; 10,6 Glauconite ; Astrophyllite
(C-SAP); ( C - V ) ; (C-M); (CD-MT) 10.5 Astrophyllite ; Palygorskite (Attapulgite) ;
14,65 Saponite Niobophyllite
14,6 Phlogopite ; (C-V) ; (C-M) ; Gonyerite 10,44 Palygorskite (Ortho) ; Glauconite Garnierite
14.5 la Al-Chlonte ; Kmmente ; Vermiculite ; 10,35 Palygorskite (Mono.)
(M-C) ; Chlontized Vermiculite 10,3 Annite
14.48 (C-Cg) 10,25 Hydromuscovite
14.5-12,5 Ghassoulite 10,2 Glauconite ; Phlogopite ; Hendricksite
14,4 Ib Monoclinic Chlorite ; Batavite ; Vermiculite ; 10,18 Glauconite
Volchonskoi'te ; Cr-Chlorite ; Chlonte (Dioc.) 10,13 3T Phlogopite
14.38 White Penninite 10,1 Biotite ; Fernphlogopite ; Hydrated Halloysite ;
14.3 Penninite ; Clinochlore ; Leuchtenbergite ; 1 Md Illite ; 1 M Hydromuscovite ; 1 M Illite ;
Dioctahedral Chlorite ; (C-M) -i- (C-Cg) Biotite ; Glauconite ; Garnierite ; Muscovite
14.2 llb Fe-Mg Chlorite ; llb Al-Chlonte ; la Chlorite 10,7 Hydromuscovite
Ib (Orthohexagonal) Chlorite ; Dioctahedral 10,05 1 M+3T Phlogopite ; Ilute ; 1M Illite-Muscovite
Chlorite ; Sudoite ; Kmmererite ; 10,0 Fully Hydrated Halloysite ; Hydrated Cr-Halloysite ;
Corundophyllite ; Clinochlore ; Nimite ; 1 Md Ilute ; 2M2 Hydromuscovite ; Mangan-
Saponite ; Vermiculite ; Corrensite Muscovite ; Hydromuscovite ; Muscovite ;

71
d(A) : basal d() : basal
reflection Mineral ame reflecton Mineral ame

Phlogopite ; Trioctahedral Ilute ; 2M and 7,50 Hydrated Halloysite


1M Mariposites ; (Ledikie) ; 2M Illite-Muscovite ; 7,48-7,47 Cr-Halloysite (Hydrated)
Trilithionite ; Garnierite ; 1M Roscoelite : 7,43-7,42 Dehydrated Halloysite : Pecorate ; Hydrated
2M2 Gmbelite ; Alurgite Cr-Halloysite
9.99 Muscovite ; Cryophyllite (Ferroan Lepidolite) ; 7,41 Metahalloysite : Lizardite
Trilithionite 7,37 Lizardite
9,98 Illite, Ba-Muscovite ; Fluor-Phlogopite ; 7,36 Lizardite ; Lizardite + Orthochrysotile ;
Celadonte Clinochrysote ; Clino+Orthochrysotile
9,96 Sericite ; Glauconite ; 3T Fluor-Phlogopite 7,35 Lizardite + CImochrysotile ; Co-Serpentine
9,95 1M Fluor-Phlogopite ; Iron Rich Muscovite 7.33 Orthoantigonte ; 6L Orthoserpentine ; Tale
2L Monoclinic Lithian Muscovite ; Alurgite 7,31 6L Orthoserpentine+Clinochrysotile ;
9,94 Glaucomte ; 1M Phlogopite Clinochrysotile
9,92 Anandite : Phengite 7,30 b-Axis Disordered Kaolinite ; Fire Clay ;
9,91-9,9 3L Hexagonal Lepidolite ; 1L Monoclinic Bemonite ; Antigorite ; Clinochrysotile ;
Lepidolite : Illite ; Hydrated Cr-Halloysite ; 6L Orthoserpentine
Muscovite : Ferroan Lepidolite (cf. Cryophyllite) 7,29 Antigorite
9,89 6L Monoclinic Lepidolite ; Zircophyllite 7,28 Ni-Serpentme
9,87 Lepidolite 7,25-7,24 Antigonte Clay ; Al-Serpentine :
9,86 Polylithionite 1 L Orthoserpentine ; Clinochrysotile ;
9,85-9,81 1M Zinnwaldite Orthochrysotile ; Lizardite ; Nepouite
9,7 Paragonite 7,23 Nacrite
9,68 Clintonite (Xanthophyllite) 7,22 Disordered Kaolinite+Silica (cf. Anauxite)
9,65 Xanthophyllite ; Paragonite 7,21 Greenalite
9,62 Paragonite 7,20-7,19 Fully Hydrated Halloysite ; Ball Clay ;
9,60 Minnesotaite ; Paragonite ; Hydrated Cr-Halloysite Antigorite ; Lizardite
9,59 Ephesite 7,18 b-Axis Disordered Kaolinite ; Flint Clay ; Amesite
9,56 Margante ; Minnesotaite 7,17 Nacrite, b-Axis Disordered Kaolinite
9,53 Minnesotaite 7,16 Dickite
9,47 Margante ; Na-White Mica 7,147 b-Axis Disordered Kaolinite
9,46 Bityite ; Willemseite 7,13 Kaolinite
9,42 Ni-Talc (Synthetic) 7,12 Ferrous Chamosite ; Chamosite ; Al-Serpentine
9,40 Willemseite 7,11 Al-Serpentine
9,34-9,3 Tale 7,10 Fraipontite
9,21 Pyrophyllite (Monoclinic) 7,09 6 ( 2 ) L Al-Serpentine
9,20 Pyrophyllite (Triclinic) 7,08 Chamosite ; Gronstedtite
9,14 Pyrophyllite 7,07 Chamosite
9,0 Partially Hydrated Halloysite ; Pyrophyllite 7,06 Amesite
8,0 (M-K); (M-Halloysite) 7,05 Chamosite ; Nimesite ( = Ni-Amesite)
7,84-7,81 Apophyllite 7.02 Amesite ; Ortho-Chamosite

72
IX. - LIST OF THE (001) REFLECTIONS - (001) TO (006) - FOR CURRENT CLAY
MINERALS, INCLUDING MIXED LAYERS (Natural state)

d-spacings in decreasing order; series of harmonio (OOI) reflections out to the 3


regin of the diffractogram.

d()l d() I d() I d()l d() I COMPOSITION REFERENCES


(001) (002) (003) (004) (005) (CODIFIED)

43,75 (100) 21,8 (70) 10,55 (93) Tarasovite LAZARENCO & al. (1970)
30,5 15 7,37 6,06 (C-M)R SIAT & al. (1959)
30,5 (M) 14,5 (VS) 9.7 (W) 7,25 (W) (C-M)R EARLEY & al. (1956)
30,46 (90) 14,48 (100) 9,82 (25) 7,37 (55) 5,86 (5) (C-Cg)R STEINER (1968)
30,4 (320) 15,2 (240) 10,0 (3) 7,557 (20) 5.98 (3) Tosudite SHIMODA (1969)
30,2 (VS) 13,85 (VS) 9,45 (M) 7,09 (VW) 5,438 (W) (Mi-AII) MACHAJDIK & al. (1970)
30,0 (16) 15,0 (24) 9,96 (4B) 7,52 (4B) 6,01 (3B) Al, (M-O+R SUDO & al (1957)
30 (W) 14,4 (VS) (C-Cg) HECKROODT & al. (1965)
29,9 (48) 14,7 (100) 9,71 (8) 7.31 (10) 5,82 (3) (C-V)T SUDO & a l . (1969)
29,8 (10) 14,7 (15) 10,3 (4B) 7,18 (20) 4,95 (10) (C-M)R, Dioc, SUDO (1954)
29,7 (80) 14,4 (50) 9.66 (10) 7.3 (2) 5,72 (2) LI-AKM-OD BROWN & al. (1974)
29,6 (10) 14,7 (18) 9.8 (3) 7.32 (5) 5.99 (3) (C-M)p, Dioc. SUDO (1954)
29,6 (VW) 14,6 (VS) 9,8 (W) 7,18 (M) (C-Cg) VENALE & a l . (1969)
29,5 (S) 14,3 (VS) 7,12 (W) (C-M) SARKISYAN & al. (1972)
29,4 (M) 14,7 (VS) 7.4 (M) Corrensite PETERSON (1961)
29,4 (VS) 14,7 (VS) 9,8 (W) 7,30 (M) 5,8 (5) (C-SAP)R ALIETTI (1957)
29,2 (50) 14,6 (100) 9,73 7,3 (25) 5,9 (3) (M-C) BRADLEY & al. (1956)
29,2 (VW) 14,48 (VS) (Bei-V) HEYSTEK (1963)
29,0 (9) 14,6 (100) 7,26 (39) (C-V) JOHNSON (1964)
29,0 (100) 14,5 (71) 9,65 (8) 7,27 (6) (C-M) EGGLESTON & al. (1967)
29 14,2 9,7 7,3 5,9 (C-V) R BRADLEY & WEAVER (1956)
29 (30) 14 (100) 7,08 (60) (C-V)R BROWN B.E. (1967)
28,9 (M) 14,4 (VS) 9,6 (VW) 7,23 (M) (C-SAP)R VENALE & al. (1969)
28,8 14,3 9,5 7,14 5,76 Sangarite DRITS & al. (1963)
28.5 (21) 14,26 (100) 9,51 (7) 7,14 (46) 5,08 (3) (C-V), (Mg Saturated) JOHNSON (1964)
28,5 (W) 14,2 (VS) 9,43 (VW) 7,23 (W) (C-V)R WILSON (1973)
28,5 14,2 9,5 7,1 Corrensite LUCAS (1963)
28,5 (VW) 14 (VS) 7,1 (S) (C-V)R SARKISYAN & al. (1972)
28,44 (S) 8,08 (W) 5,94 (VW) 4,77 (W) (C-M)R + (C-Cg) ALIETTI & a l . (1963)
28,3 (M) 14,2 (S) 7,08 (W) 4,72 (M) 3,53 (S) Corrensite LIPPMAN (1954)
28,1 (W) 12,1 (VS) (Mi-M)R HAMILTON (1967)
28 (22) 16 (10) 11,5 (100) 8,43 (8) HyBio + 30%V FERLAJ & al. (1972)
28 (M) 14,27 (VS) 7,1 (M) (C-M) R FRANSOLET (1970)
27,6 (204) 14,1 (344) 9,72 (56) 7,15 (49) 5,75 (3) (C-EXP. Clay) 1:1 TETTENHORST & al. (1968)
27,3 (90) 12,4 (100) 5,06 ( 2 0 ) (Mi-M)R HAMILTON (1967)
26,77 12,45 5,06 (I-M) STEINER (1968)
26,3 (100) 13,4 (92) 9.1 (16) 5,2 (10) (Mi-Bei)R GALLEGO (1968)
26,1 (W) 12,8 (VS) (Bei-HyMi) HEYSTEK (1963)
25,8 (100) 12,6 (55) 8,49 6,32 5,02 (Mi-M)R SUDO & SHIMODA (1969)
25.8 (100) 12.4 (80) 4,3 (40) HEYSTEK (1954)
25,5 (100) 12,4 (100) 8.2 (30) 6.15 (10) 4,92 (60) HyBIO MIDGLEY & al. (1960)
25,2 (54) 12,25 (93) 8,33 (6) 4,95 (25) (Mi-V)R GRADUSOV (1971)
25.2 (30) 11,3 (100) 7,25 (2) 5,51 (5) 4,67 (4) (Mi-M) R HAMILTON (1967)
25 12,5 5 Rectorite
25 (S) 11,7 (VS) 5,03 (M) (I-M)R
24,8 (50) 12,4 (150) 8.3 (18) 5,0 (12) HyBIO EROSHCHEV-SHAK (1970)
d()l d()l d()l d()l d() I COMPOSITION REFERENCES
(001) (002) (003) (004) (005) (CODIFIED)

24,8 (VS) 12,5 (VS) 8,11 (W) 4,80 (VW) (SAP-TALC) ALIETTI (1956)
24,7 (100) 12,4 (50) 8 (5) Allevardite-Rectorite KOROLEV (1961)
24,7 (W) 12 (VS) 8,3 (VW) HyBIO VENALE & al. (1969)
24,5 (VS) 11,77 (S) 8,11 (M) 4,8 (M) (TALC-SAP)R ALIETTI (1960)
24,2 (VW) 12,36 (M) 8,01 (M) 6,09 (VW) 4,83 (VS) (Mi-Su)R SHIROZU & a l . (1971)
24 (25) 11,9 (100) 8,15 (4) 4,89 (18) HyBIO + 50% V FERLAJ Sal. (1972)
24 (VW) 12,6 (VS) 7,98 (S) 6,25 (W) 4,87 (S) (BIO-C)R EROSHCHEV-SHAK (1970)
24 11,2-12 ,4(100) 4,89-4,96 (20) Stevensite FAUST & al. (1953)
23,8 (VS) 11,8 (S) 8,1 (W) 6,09 (VW) 4,79 (VW) (TALC-SAP) VENALE & al. (1966)
23 (70) 12,3 (210) 8,03 (6) 4,87 (28) HyBIO EROSHCHEV-SHAK (1970)
22,8 (66) 11,04 (100) 5,22 (40) (Mi-Be)R GALLEGO & PREZ (1965)
15,85-14 ,05 (VS) 5,07 (W) 3,13-3,05(3) (Na-Ca)M ALIETTI & al. (1962)
15,4 (VS) 5,15 (M) 3,0 (W) Volchonskote 14M SARTORI (1967)
15,1 (100) 7.17 (20) 4,75 (66) 3,56 (31) Chlorite, (Dioc) : 1 4c : CD FUJII & a l . (1971)
14,8 (47) 7,325 (28) 4,844 (32) 3,59 (30) EXP. like Chlorite SHIMODA (1969)
14,4 (VS) 4,79 (VW) SAP
14,4 (M) 7,07 (VS) 4,714 (W) 3,535 (S) Ripidolite : 14c = RIPI POST & PLUMMER (1972)
14,38 (75) 7,18 (100) 4,79 (55) 3,60 (80) White penninite : 14c : PENN CERNY & al. (1965)
14,3 (60) 7,18 (180) 4,79 (100) 3,59 (100) Pennimte : 1 4c : PENN BRINDLEY (1961)
14,31 (68) 7,156 (103) 4,77 (74) 3,578 (64) Penninite : 14Q: PENN POST & PLUMMER (1972)
14,3 (35) 7,14 (65) 4,74 (40) 3,55 (15) Leuchtenbergite 14c : LEUCHT SAKAMOTO & SUDO (1958)
14,3 (70) 7,12 (100) 4,63 (70B) 3,56 (80) Clinochlore : 14Q: CUNO ASTM 19-749
14,2 (62) 7,14 (60) 4,72 (122) 3,54 (74) Al-Chlorite 14Q: (AI)C HAYASHI & al. (1964)
14,24 (64) 7,12 (100) 4,74 (48) 3,56 (68) Corundophyllite : 1 4Q : CORUN STEINFINK (1958)
14,2 (3) 7,1 (10) 4,68 (2B) 3,55 (8) Chlorite : 14c : o-hC SHIROZU (1958)
14,2 (7) 7,1 (10) 4,72 (7) 3,54 (10) Ilb-Fe-Mg Chlor 14c : (llb)(Fe-MG)C SHIROZU (1969)
14,2 (25) 7,1 (100) 4,74 (16) 3,55 (45) Nimite : 14c : NIM DEWAAL (1970)
14,2 (41) 7,13 (34) 4,86 (100) 3,53 (58) Sudoite : 14c: Su MULLER (1967)
14,2 (60) 7,14 (60) 4,72 (100+) 3,54 (74) Al-Chlorite: 1 4c : (AL) C HAYASHI & al. (1964)
14,19 (30) 7,094 (50) 4,73 (30) 3,547 (39) Clinochlore : 1 4c : CLINO POST & PLUMMER (1972)
14,16 (38) 7,08 (100) 4,72 (12) 3,54 (44) Ripidolite : 14p : RIPI SHIROZU & BAILEY (1965)
14,16 (84) 7,08 (100) 4,72 (21) 3,54 (59) Prochlorite : 14c : PROCHL STEINFINK (1958, 61, 62)
14,16 (78) 7,08 (147) 4,72 (72) 3,54 (96) Sheridanite: 14c: SHERID POST & PLUMMER (1972)
14,15 (35) 7,11 (95) 4,74 (90) 3,56 (95) Kochubete: 14Q: KOTSC BROWN (1961)
14,15 (8) 7,05 (10) 4,72 (6) 3,54 (10) llb Chlorite : 14c: MbC BROWN & al. (1962)
14,1 (60) 7,11 (70) 4,75 (50) 3,558 (50) Sheridanite: 14c: SHERID GILLERY - ASTM 7-77
14,13 (45) 7,13 (32) 4,71 (100) 3,517 (47) Chlorite, dioct. : 1 4 : CD VAN OOSTERWYCK (1968)
14,1 (7) 7,09 (9) 4,72 (8) 3,54 (10) Chlorite mono.: 1 4c : rnC SHIROZU (1958)
14,1 (90) 7,07 (100) 4,726 (30) 3,541 (60) Thurmgite : 1 4Q : THUR GILLERY - ASTM 7-78
14,1 (70) 7,07 (90) 4,72 (80) 3,54 (100) Leuchtenbergite: 1 4Q : LEUCHT SHIROZU (1958)
14,1 (10) 7,1 (10) 4,7 (10) 3,55 (10) Corundophyllite: 1 4c : CORUN GAUDEFROY & al. (1965)
14,1 (8) 7,05 (7) 4,7 (9) 3,52 (9) la Chlorite: 14c : (la) C BROWN & BAILEY (1963)
14,1 (50) 7,05 (100) 4,69 (50) 3,52 (90) Aphrosiderite : 1 4c : APHRO SHIROZU (1958)
14,1 (5) 7,05 (10) 4,69 (5) 3,52 (5) lb(90")Fe-Chlonte: 1 4c : (lb90")FeC SHIROZU (1969)
14,1 (5) 7,05 (10) 4,69 (5) 3,52 (9) Chlorite (orthohex.): 14c : o-h C SHIROZU (1958)
14,1 (8) 7,05 (7) 4,7 (10) 3,52 (10) Cookeite 14c : COOK BROWN & BAILEY (1963)
14 (90) 7,1 (100) 4,70 (70) 3,53 (100) Mg-Chamosite : 1 4c : (Mg) CHAM BANNISTER & al. (1945)
14 (S) 7,1 (VS) 4,69 (MS) 3,53 (VS) Mg-Chamosite : 1 4p : (Mg) CHAM JASMUND (1955)
14 (9) 7 (10) 4,6 (1) 3,53 (10) Mg-Chamosite : 14c : (Mg) CHAM BRINDLEY (1950)
14,0 (40) 7,08 (85) 4,75 (95) ,562 (100) Cr-Ni-Pennme : 1 4c : (Cr-Ni) PENN VARADARAJAN (1964)
13,7 (7) 7,04 (8) 4,68 (9) 3,51 (10) Sheridanite : 14c : SHERID JASMUND (1955)
13,6 (6) 7,02 (7) 4,7 (9) 3.525 (10) Sheridanite: 1 4Q : SHERID BRINDLEY & al. (1951)
13,6 (4) 6,9 (8) 4,65 (6) 3,48 (10) Prochlorite : 14Q : PROCHL JASMUND (1955)
13,6 (MS) 6,89 (VS) 4,62 (S) 3,48 (VS) Thuringite : 14c : THUR JASMUND (1955)
13,1 (6) 6,97 (9) 4,68 (9) 3,52 (10) Leuchtenbergite: 14Q: LEUCHT JASMUND (1955)
13,06 (VS) 6,18 (W) 3,83 (M) Na-Montmorillonite : 1 4|\/| : (Na) M ALIETTI & al. (1962)
12,4-11 ,2(10 + ) 3,5-3 (5) Stevensite : 14y : STEV BRINDLEY (1955)
12,36 (S) 8,01 (M) 6,09 (VW) 4,83 (VS) (Ser-Su) SHIROZU & al. (1971)
12,1-13(10) 4,78-5,2(1) Stevensite : 14|V| : STEV FAUST & al. (1959)
12,17 (100) 4,03 (8) 3,02 (M) Stilpnomelane: 12 : STILP GAY (1966)
d(A) I d() I d(A) l d(A) l d(A) I COMPOSITION KI u w N :;
(001) (002) (003) (004) (005) (CODIFIED)

11,2 (33) 5,06 (45) 4.50 (30) (Mi-M) SHIMODA & SUDO (1969)
11 (VS) 4,47 (M) (I-M) BOCCHI & al. (1965)
10,1 (VS) 5 (VVW) 3,3 (VS) Biotite : 10 : BIO
10,1 (80) 5,03 (60) 3,35 (80) Muscovite : 1 O : MU KODAMA (1962)
10,05 (VS) 5 (M) 3.3 (VS) Ilute : 10: I HOWER & MOWATT (1966)
9,91 (S) 4,98 (S) 3,33 (VS) Lepidolite: 10 : LEPI LEVINSON11953)
9,65 (S) 4,82 (MS) 3,21 (VS) Paragonite : 9 : PAR ZEN & ROSS (1964)
9,604 (VS) 4,818 (VS) 3,218 (VS) Margante, trigonal: 9 : MAR DIETRICH (1956)
9,34 (VS) 4,56 (S) 3,11 (S) Tale : 9 : TALC ROSS & al. (1968)
9,21 (VS) 4,58 (S) 3,08 (VS) Pyrophyllite : 9 : PYR KODAMA (1958)
9,14 (M) 4,57 (S) 3.04 (VS) Pyrophyllite : 9 : PYR MOLLOY & al. (1961)
7,43 (8) 3,66 (6) Pecoralte : 7 : PECOR FAUST & al. (1969)
7,36 (18) 3,65 (16) Lizardite : 7 : LIZ MU.CHI & al. (1968)
7,30 (10) 3,65 (9) Clmochrysotile: 7 : C H R Y S KRASTANOVIC & al. (1967)
7,30 (100) 3,63 (100) Antigorite : 7 ANTIG HESS & al. (1952)
7,30 (100) 3,62 (100) Orthoserpentine : 7 : o SERP JASMUND & SYLLA (1971)
7,25 (100) 3,65 (100) Orthochrysotile : 7 : o CHRYS MONTOYA & al. (1963)
7,25 (100) 3,62 (100) Nepouite : 7 : NEP MONTOYA & al. (1963)
7,24 (100) 3,619 (100) Antigorite (Clay) : 7 : ANTIG BRINDLEY & al. (1971)
7.21 (VS) 3,60 (S) Greenalite : 7 : GREEN
7,22 (VS) 3,59 (VS) Kaolinite (disordered) 7 : Kd
7,2 (VS) 3,59 (VS) Ball Clay: 7 : K(b.c) MURRAY (1954)
7,19 (80) 3,59 (100) Amesite : 7 : AMES MONTOYA & al. (1963)
7,16 (10) 3,587 (10) Dickite : 7 : DICK NEWMHAM & al. (1956)
7,13 (100) 3,566 (66) Kaolinite : 7 : K DRITS & al. (1960)
7,11 (100) 3,55 (64) Al-Serpentine : 7 : (AI)SERP JAHAMBAGLOO & al. (1968)
7,07 (10) 3,52 (10) Chamosite : 7 : CHAM BRINDLEY (1951)
7,05 (100) 3,527 (75) Nimesite : 7 : NIM MAKSIMOVIC (1972)

-o
o
X. - ALPHABETICAL LIST OF CURRENT CLAY MINERALS INCLUDING MIXED LAYERS,
WITH THEIR d(OOI) VALES IN , AND THE CORRESPONDING INTENSITIES OUT TO
THE 3 REGIN OF THE DIFFRACTOGRAM - oriented aggregate, natural state

It has seemend of nterest to group here some specific d(spamngs) and ntensities (ex. : mxed layers) or, on the contrary the list will only provide the (001) and
for the (001) harmonio sequence of reflections for different clay mnerals and (002) in d() for others (kandites).
mixed layers (regular).
Some sensitive differences may appear in the d(spacing) as well in the ntensities
The data are only provide up to the 3 zone of the diffractogram pattern ; that for specific minerals or mixed layers (regular) ; such a situation is due to the various
will say that may be related at least to the (005) reflection for some minerals authors references.

d(A)l d(A) I d(A) I d(A)l d()l


AME (001) (002) (003) (004) (005) REFERENCE

Allevardite 24,7 (100) 12,4 (50) (5) KOROLEV (1961)


Amesite 7,19 (80) 3,59 (100) MONTOYA & BAUER (1963)
Antigorite 7,30 (100+) 3,63 (100) HESS & al. (1952)
Antigorite Clay 7,24 (100 + ) 3,619 (40) BRINDLEY & al. (1971)
Aphrosiderite 14,1 (50) 7,05 (100) 4,69 (50) 3,52 (90) SHIROZU (1958)

Ball Clay 7,2 (VS) 3,52 (VS) MURRAY(1954)


Biotite 10,1 (VS) 5- (VVW) 3,34 (VS)

Chamosite 1 : 1 mono/ortho 7,07 (VS) 3,52 (VS) BRINDLEY (1951)


Chamosite, Mg - 14 (9) 7 (10) 4,7 (6) 3,53 (10) BRINDLEY (1951)
14 (90) 7,1 (100) 4,70 (70) 3,53 (100) BANNISTER & al. (1945)
14 (S) 7,1 (VS) 4,69 (MS) 3,53 (VS) JASMUND (1955)
Chlorite, dioctahedral 15,1 (100) 7,17 (20) 4,75 (66) 3;56 (31) FUJII & al. (1971)
14,13 (45) 7,13 (32) 4,71 (100) 3,517 (47) VAN OOSTERWYCK (1968)
monoclinic 14,1 (7) 7,07 (9) 4,72 (8) 3,54 (10) SHIROZU (1958)
orthohexagonal 14,1 (5) 7,05 (10) 4,69 (5) 3,52 (9) SHIROZU (1958)
14,2 (3) 7,1 (10) 4,68 (2B) 3,55 (8) SHIROZU (1958)
lb(90"), Fe- 14,1 (5) 7,05 (10) 4,69 (5) 3,52 (5) SHIROZU (1969)
Mb C 14,15 (8) 7,05 (10) 4,72 (6) 3,54 (10) BROWN & BAILEY (1962)
14.2 (7) 7,1 (10) 4,72 (7) 3,54 (10) SHIROZU (1969)
la - 14,1 (8) 7,05 (7) 4,7 (9) 3,52 (9) BROWN & BAILEY (1963)
14,2 (6) 7,1 (10) 4,73 (4) 3,55 (8) BROWN & BAILEY (1962)
Al - 14,2 (62) 7,14 (60) 4,72 (122) 3,54 (74) HAYASHI & OINUMA (1964)
Chlorite, Expanded like- 14,8 (47) 7,325 (28) 4,84 (32) 3,59 (30) SHIMODA (1969)
Clinochlore 14,3 (70) 7,12 (100) 4,63 (70B) 3,56 (80) ASTM 19-749
14,19 (31) 7,09 (50) 4,729 (31) 3,547 (39) POST & PLUMMER (1972)
Clino-chrysotile 7,30 (10) 3,65 (9) KRASTANOVIC & al. (1967)
ortho - 7,25 (100) 3,65 (100) MONTOYA & BAUER (1963)
Cookcite, la 14,1 (8) 7,05 (7) 4,7 (9) 3,52 (9) BROWN & BAILEY (1963)
Corundophyllitc 14,24 (64) 7,12 (100) 4,74 (48) 3,56 (68) STEINFINK (1958)
14,1 (10) 7,1 (10) 4,7 (10) 3,55 (10) GAUDEFROY & al. (1965)
Corrensite 29,4 (M) 14.7 (VS) 7,4 (M) PETERSON (1961)
28,3 (M) 14,2 (S) 7,08 (W) LIPPMAN (1954) n BROWN (1961)
29,5 14,2 9,5 7,1 LUCAS (1963)
d() I d(A) I d(A) I d(A)l d(A) l
AME (001) (002) (003) (004) (005) REFERENCE

Dickite 7,16 (10) 3.58 (10) NEWNHAM & al. (1956)

Glauconite 10,2 (VS B) 5 (VVW) 3,34 (MB)


Greenalite 7,21 (7) 3,60 (4) YOUELL & a l . (1958)

Ilute, dioctahedral 9,98 (S) 5 (M) 3.31 (M)


trioctahedral 10 (VS) 5 (VVW) 3.32 (VS)
with less than 10% Montmorill. 10,05 (VS) 5 (M) 3,3 (VS) HOWER & MOWATT (1966)

Kaolinite, ordered 7,13 (100) 3,56 (66) DRITS & al. (1960)
disordered 7,2 (VS) 3.59 (VS)
Kotschubete 14,15 (35) 7,11 (100) 4,74 (90) 3,56 (95) BROWN (1961)

Lepidolite 9,91 (S) 4,98 (S) 3,33 (VS) LEVINSON (1953)


Leuchtenbergite 14,3 (35) 7,14 (65) 4,74 (40) 3,55 (15) SAKAMOTO & SUDO (1958)
14,1 (70) 7,07 (90) 4,72 (100) 3,54 (100) SHIROZU (1958)
13,1 (6) 6,97 (9) 4,68 (9) 3,52 (10) JASMUND (1955)
Lizardite 7,36 (VS) 3,65 (VS) MUCHI & al. (1968)

Margarita 9,60 (VS) 4,81 (VS) 3,218 (VS) DIETRICH (1956)


Montmorillomte (Na,Ca-) 15,85-14,05 (VS) 5,07 (W) 3,13-3,05(3) ALIETI & a l . (1962)
Muscovite 2Mi + 1 M 2 : 1 10,1 (100) 5.03 (60) 3,35 (80) KODAMA (1962)
2M-| + 1M 1 : 2 10,2 (72) 5.04 (54) 3,35 (100) KODAMA (1962)

Nepouite 7,25 (100) 3,62 (100) MONTOYA & BAUER (1963)


Nimesite (N-amesite) 7,05 (100) 3,527 (75) MAKSIMOVIC (1972)
Nimite 14,2 (25) 7,1 (100) 4,74 (16) 3,55 (45) DE WAAL (1970)

Paragonite 9,65 (S) 4,82 (Ms) 3,21 (VS) ZEN & ROSS (1964)
Pecoraite 7,43 (VS) 3,66 (S) FAUST & al. (1969)
Penninite 14,31 (68) 7,156 (1007) 4,77 (74) 3,578 (64) POST & PLUMMER (1972)
14,2 (55) 7,13 (90) 4,74 (70) 3,57 (100) MONTOYA & BAUER (1963)
14,3 (60) 7,18 (100 + ) 4,79 (100) 3,59 (100) BRINDLEY (1961)
14,38 (75) 7,18 (100) 4,79 (55) 3,60 (80) CERNY & al. (1965)
Cr-Ni-Pennine 14,0 (40) 7,08 (85) 4,75 (95) 3,562 (100) VARADARAJAN (1964)
Prochlorite 14,16 (84) 7,08 (100) 4,72 (21) 3,54 (60) STEINFINK (1958, 61, 62)
13,6 (4) 6,9 (8) 4,65 (6) 3,48 (10) JASMUND (1955)
Pyrophyllite 9,21 (VS) 4,58 (S) 3,08 (VS) KODAMA (1958)
9,14 (40) 4,57 (50) 3,04 (100) MOLLOY & KERR (1961)

Rectorite 25 12,5
Ripidolite 14,16 (38) 7,08 (100) 4,72 (12) 3,54 (44) SHIROZU & BAILEY (1965)
14,4 (54) 7,07 (100+) 4,714 (43) 3,535 (89) POST & PLUMMER (1972)

Saponite 14,4 (VS) 4,79 (VW)


Serpentina, Al- 7,11 (100) 3.55 (64) JAHANBAGLOO & al. (1968)
Mg-, Ortho- 7,30 (100) 3,62 (100) JASMUND &SYLLA (1971)
Ni- 7,28 (10) 3,65 (10) FEITKNECHT & al. (1942)
Sheridanite 14,16 (78) 7,08 (100) 4,72 (72) 3,54 (96) POST & PLUMMER (1972)
14,1 (60) 7,11 (70) 4,75 (50) 3,558 (50) GILLERY, ASTM 7-77
13,7 (7) 7,04 (8) 4,68 (9) 3,51 (10) JASMUND (1955)
13.6 (6) 7,02 (7) 4,7 (9) 3,525 (10) BRINDLEY & al. (1951)
Stilpnomelane 12,11 (100) 4,03 (8) 3,02 (4) GAY (1966)
Sudote 14,24 (41) 7,13 (34) 4,86 (100) 3,53 (58) MULLER (1967)

Tale 9,34 (VS) 4.56 (S) 3,11 (S) ROSS & al. (1968)
Thuringite 14,1 (90) 7,07 (100) 4,726 (30) 3,541 (60) GILLERY, ASTM 7-78
13,6 (MS) 6,89 (VS) 4,62 (S) 3,48 (VS) JASMUND (1955)

Volchonskote 15,4 (VS) 5,15 (M) 3,0 (W) SATORI (1967)


V]
CO
d()l d(A) I d(A)l d(A) I d(A)l
AME (001) (002) (003) (004) (005) REFERENCE

Mixed Layers - Interstratifis (001) (002) (003) (004) (005)


(Natural) See annexed key.

Tarasovite 43,75 (100) 21,8 (70) - 10,55 (4) LAZARENKO & al. (1970)
Sangarite 28,8 14,3 9,5 7.14 7,14 5,76 DRITS & al. (1963)
Hydrobiotite + 30% V 28 (22) 11,5 (100) 8,43 (8) FERLAJ & al. (1972)
Hydrobiotite - (I-V) 25,5 (100) 12,4 (100) 8,2 (30) 6.15 6,15 4,92 (60) MIDGLRY & MIDGGLEY (1960)
24,8 (50) 12,4 (150) 8,3 (18) 5.0 (12) EROSHCHEV-SHAK (1970)
24,7 (W) 12 (VS) 8,3 (VW) VENALE & al. (1969)
23,0 (70). 12,3 (210) 8,3 (6) 4,87 (28) EROSHCHEV-SHAK (1970)
Hydrobiotite + 50% V 24 (25) 11,9 (100) 8,15 (4) 4,89 (18) FERLAJ & al. (1972)
(Mica-Vermicu lite) 25,2 (54) 12,25 (100) 8,33 (6) 4,95 (25) GRADUSOV (1971)
Stevensite 24 11,2-12,4(100) 4,89-4,96 (20) FAUST & al. (1 953)
(Talc-Saponite) 24,52 (58) 10,5-10,9 (92) GUENOT(1970)
24,5-24,8(92) 11,7-12,3(100) 4,80 (13) ALIETTI (1960)
23,8 (VS) 11,8 (S) (W) (W) 6,09 (VW) 4,79 (VW) VENALE & al. (1966)
(Mica-Beidellite) 22,8 (66) 11,04 (100) - 5,22 (40) GALLEGO & PREZ (1965)
(Mica-Montmorillonite) 25,2 (30) 11,3 (100) - 5.07 (10) HAMILTON (1967)
(Illite-Montmorillonite) 25 (S) 11,7 (S) - 5,03 (M) BOCCHI & al. (1969)
(Mica-Montmorillonite) 27,3 (90) 12,4 (100) - 5,06 (20) HAMILTON (1967)
(Mica-Montmorillonite) - 11,2 (33) - 5,06 (45) SHIMODA & al. (1969)
(Illite-Montmonllonite) 25 (S) 11,7 (VS) - 5,03 (M)
(Mica-Montmorillonite) 25,8 (100) 12,4 (80) - HEYSTEK (1954)
25,8 (100) 12,6 (55) 8,49 6,32 5,02 SUDO & SHIMODA (1969)
(Beidellite-hydromica) 26,1 (W) 12,8 (VS) - HEYSTEK (1963)
.(Mica-Beidellite) 26,3 (100) 13,4 (92) 9,1 (16) 5,20 (10) GALLEGO (1968)
(Illite-Montmorillonite) 26,77 12,45 - 5,06 STEINER (1968)
(Mica-Montmorillonite) 28,1 (W) 12,1 (VS) - HAMILTON (1967)
(Mica-Allevardite) 30,2 (VS) 13,85 (VS) 9,45 (M) 7,09 (VVJ) 5,438 (W) MACHAJDIK
(Sericite-Sudoite) 24,2 (VW) 12,36 (M) 8,01 (M) 6,09 (VW) 4,83 (VS) SHIROZU & al. (1971)
(Biotite-Chlorite) 24 (VW) 12,6 (VS) 7,98 (S) 6.25 (W) 4,87 (S) EROSHCHEV-SHAK (1970)
(Be idel lite-Vermicu lite) 29,2 (VW) 14,48 (VS) - HEYSTEK (1963)
(Chlorite-Vermiculite) 29 (30) 14 (100) - 7,08 (60) BROWN (1967)
29,9 (48) 14,7 (100) 9,71 (8) 7,31 (10) 5,82 (3) SUDO & SHIMODA (1969)
28,5 (VW) 14 (VS) - 7,1 (S) SARKISYAN & al. (1972)
28,5 (W) 14,2 (VS) 9,43 (VW) 7,23 (W) WILSON (1973)
29 14,2 9,7 7,3 5,9 BRADLEY & WEAVER (1956)
29,0 (9) 14,6 (100) - 7.26 (39) JOHNSON (1964)
Tosudite 30,4 (320) 15,2 (240) 10,0 (3) 7,557 (20) 5.98 (3) SHIMODA (1969)
(dioctah. Chlorite-Montmorill.) 31,5 (79) 14,7 (100) - SUDO & KODAMA (1969)
(Chlorite-Montmorillonite),Dioct. 29,6 (10) 14,7 (16) 9,8 (3) 7,32 (5) 5.99 (3) SUDO (1954)
Li-AI (Chlorite-Montm., Dioct. 29,7 (80) 14,4 (50) 9,66 (10) 7,3 (2) 5,72 (2) BROWN & al. (1974)
(Chlorite-IViontmorillonite), Dioct 29,8 (10) 14,7 (15) 10,3 (4B) 7,18 (20) SUDO (1954)
(Montmonllonite-Chlonte), Dioct 30,0 (16) 15,0 (24) 9,96 (4B) 7,52 (4B) 6.01 (3B) SUDO & KODAMA (1957)
(Montmorill.-Chlonte), Trioct. 30,5 (S) 14,5 (VS) 9,7 (M) 7,25 (M) EARLEY 4 al. (1956)
(Chlorite-Montmorillonite) 30,5 15,0 - 7,37 6,06 SIAT & al. (1959)
(Chlorite-Montmorillonite) 29,5 (S) 14,3 (VS) - 7,12 (W) SARKISYAN & al. (1972)
Corrensite : (C-M) 29,2 (50) 14,6 (100) 9,73 (12) 7,3 (25) 5,9 (3) BRADLEY & WEAVER (1956)
(Chlorite-Montmorillonite) 28 (M) 14,27 (VS) - 7,1 FRANSOLET (1970)
29,0 (100) 14,5 (71) 9,65 (8) 7,27 (6) EGGLESTON & al. (1967)
(Chlonte-Exp. Clay) 27,6 (204) 14,1 (344) 9,72 (56) 7,15 (49) 5,75 (3) TETTENHORST & al. (1968)
(Chlorite-Saponite) 28,9 (M) 14,4 (VS) 9,6 (VW) 7,23 (M) VENALE & al. (1969)
(Chlorite-Saponite) 29,4 (VS) 14,7 (VS) 9,8 (W) 7,3 (M) 5.8 (S) ALIETTI (1956)
Mixed layer Swelling Chlorite 30,46 (90) 14,48 (100) - 7,37 (55) STEINER (1968)
+ 11 (Chlonte-Montmo.) + 28,44 (S) - 8,08 (W) 5,94 (VW) ALIETTI & al. (1963)
(Chlorite-Swelling Chlorite)
(Chlorite-Swelling Chlorite) 30 (W) 14,4 (VS) HECKROODT & al. (1965)
29,6 (VW) 14,4 (VS) 9,8 (W) 7,18 (M) VENALE & al. (1969)
30,46 (90) 14,48 (100) 9,82 (25) 7,37 (55) 5,86 (51) STEINER (1968)
XI. - INCREASING (060) IN d() OF PHYLLOSILICATES AND CLAY
MINERALS

Mineral ame d(060) Mineral ame

Bityite 1.530 Fraipontite ; Glinochrysotile ; Clino +


1.476 Paragonite (Trigonal) Orthochrysotile ; 6L Orthoserpentine
1.478 Ephesite + Clmochrysotile ; Fluor Phlogopite ; 1 M Fluor
1,480 Halloysite (Dehydrated); Halloysite (Hydrated); Phlogopite ; Trioctahedral Illite ; 1 M + 3T
Margante ; Paragonite ; Rectorite Phlogopite ; Ledikite ; Shendanite ; Zebedassite ;
1.482-1,483 Cr-Halloysite Hectorite ; Saponite ; (BIO-C) ; (TALC-SAP);
1.484 Cr-Halloysite ; Matahalloysite Chernykhite
1.485 Cr-Halloysite ; b-axis disordered Kaolinite 1.531 Amesite ; 6L Orthoserpentine ; Phlogopite ;
1.486 Cr-Halloysite ; Paragonite Leuchtenbergite ; Ferroan Nontronie
1.487 Kaolinite ; Cookeite 1.532 Amesite ; Chrysotile ; Al- 6(3)L Serpentino ;
1.488 b-axis Disordered Kaolinite ; Nacrite 3T Fluor Phlogopite ; Thuringite ; Saponite
1.489 Nacrite ; Dickite ; la Al-Chlorite ; la Cookeite 1.533 Iron Rich Saponite ; Hydrobiotite
1.490 b-axis Disordered Kaolinite ; Dickite ; Pire Clay ; 1.534 Lizardite ; Lizardite + Orthochrysotile ; Al 6(2)L
Flint Clay ; 1 Md Ilute ; Al (C-Cg) ; Volchonskoite Serpentine ; Orthoserpentine ; 1 M Phlogopite ;
1.491 Beidellite llb Mg-Chlorite ; Monoclinic Chiorite ;
1.492 Pyrophylhte ; Montmorillonite ; (M-Halloysite) ; Leuchtenbergite ; Sheridanite ; Swelling
(C-M); (Mi-M) Chiorite (Cg); Vermiculite ; Nimite
1.493 Pyrophyllite ; Tosudite ; Sudoite 1.535 6L Orthoserpentine ; Orthoantigorite ; Lizardite +
1.495 Dioctahedral Chiorite ; Glauconite ; Alurgite Clinochrysotile ; Lizardite ; Clinochlore ;
( = Mn Mica) 3T & 1 M Corundophyllite ; Trioctahedral Montmorillonite ;
1.496 Hydromuscovite Phlogopite
1.497 Ilute ; Polylithionite : Hydromuscovite ; Pyrophyllite 1.536 Leuchtenbergite ; Cardenite ; Lembergite :
1.498 Beidellite ; Chloritized Montmorillonite Vermiculite ; Phlogopite ; Al-Serpentine
1.499 2M-| Mn-Hydromuscovite 1.537 Kotschubeite (Cr-Chlorite) ; Orthoserpentine ;
1.500 1M Hydromuscovite ; 2M2 Hydromuscovite ; (C-SAP) ; Saponite ; Fe-Saponite ; Batavite ;
Mangan Muscovite ; Barum Muscovite ; Ilute Vermiculite
(1Md, 1M) ; Sericite ; 2M Mariposites ; 1.538 llb Chiorite ; Grochauite ; Kmmererite ;
Glauconite ; Xanthophyllite ; Penninite ; Sheridanite
2L Lithian Muscovite ; Lepidolite ; Montmorillonite ; 1.539 Lizardite ; Antigorite ; Penninite ; Prochlorite
(M-Mi) ; (10-14M) ; (I-M) 1.540 Antigorite ; Kmmererite ; Sheridanite ;
1.501 Muscovite ; Hydromuscovite Corundophyllite ; (C-V); Al (C-V) (Trioctahedral)
1.502 2L Lithian Muscovite (monoclinic) ; 1.541 Orthoserpentine ; Biotite ; Cr-Chlorite ;
Celadonite ; Na-Ca Montmorillonite Kmmererite ; Griffithite
1.503 2M2 Hydromuscovite ; Muscovite ; Volchonskole 1.542 Ni-Serpentine ; Pennmite
1.504 Muscovite ; (SER-SU) ; Tosudite ; (CQ-Mj) 1.543 Vermiculite
1.505 Clintonite ; (C-M) 1.544 Sauconite
1.506 6L Monoclinic Lepidolite ; Phengite ; 1.545 Corundophyllite ; Chloritized Vermiculite ; Diabantite
Volchonskoite ; AI-(M-C) (Dioctahedral) ; 1.547 Ripidolte ; Ferriphlogopite
Alurgite (Mn-2M-| Mica) 1.548 Ib Chiorite (monoclinic = or orthohexagonal)
1.507 Celadonite ; Muscovite ; Chiorite (Dioctahedral) 1.549 llb Mg-Fe Chiorite ; la Chiorite
1.509 Celadonite ; Ferroan Lepidolite (= Cryophyllite); 1.550 Chamosite ; Co-Serpentine ; Diabantte ;
llb Al-Chlorite ; Al-Chlorite ; (M-C) Prochlorite ; Sauconite
1.510 Ferroan Muscovite ; Zinnwaldite ; Glauconite ; 1.551 Thuringite
1 M Mariposites ; Chiorite (Dioctahedral) ; 1.552 Mg-Chamosite
Nontronite ; Fe-rich Montmorillonite 1.555 Chamosite ; Mg-Chamosite
1.511 1 L Lepidolite (monoclinic) ; 3L Lepidolite 1.556 Chamosite ; Annie ; Ripidolite
(hexagonal) ; Sudoite ; Chiorite (Dioctahedral); 1,557-1,558 Chiorite Orthohexagonal
Glauconite 1,559 lb(90) Fe-Chlorite ; Aphrosidente ;
1.513 Pimelite Chiorite Orthohexagonal
1.516 Glauconite ; Ghassoulite 1,56 Bavalite
1,518 Karpinskyite 1.561 Chamosite ; Stilpnomelane
1.520 Tale ; Hectonte ; Saponite ; Stevensite 1.562 Mmnesotaite ; Mn-Mica
(TALC-SAP) ; Nimesite ; Zinnwaldite ; Roscoelite 1.563 Ferrous Chamosite ; Minnesotaite
1.521 Stevensite 1,564-1,566 Stilpnomelane
1.522 Nontronite 1,567 Mmnesotaite ; Stilpnomelane
1.524 Willemseite ; Tale 1.570 Minnesotaite
1.525 (TALC-SAP) 1.571 Gonyerite
1.526 Fe-Chamosite 1,602-1,608 Greenalite
1.527 Biotite ; Tale ; Garmerite 1,627 Antigorite
1.528 Saponite ; Vermiculite ; Al-Serpentine 1,634 Bemontite
1.529 Phlogopite ; Pecoraite

79
XII. - GLOSSARY OF PHYLLOSILICATES AND CLAY MINERALS

CLASSIFICATION OF PHYLLOSILICATES (After BRINDLEY, 1962), and the recommandations of the


AIREA nomenclature committee, (Madrid 1972, MODIFIED) + REFERENCE CODE (Basal spacing)

Layer Interlayer Layer Basal spacing Subgroup


Group Speces
Type Interlayer charge code () (Octahedral layer)

Without Kaolinite, Halloysite,


Kaolinite Di : Kaolmites
Nacrite, Dickite
1/1 O 7
Chrysotile, Lizardite,
-Serpentine Tri : Serpentines
Antigorite

Pyrophyllite ~9
Di : Pyrophyllites Pyrophyllite
Without O
-Tale Tri : Tales Tale

Montmorillonite, Beidellite
Montmorillonites Di : Montmorillonies Saponite, Hectorite,
~0,25<x<~0,6 14M
or Smectites Tri : Saponitas Sauconite
Dry or
2/1 Hydrated
cations ~0,6<x<~0,9 Vermiculites Di : Vermiculites Vermiculite
14y
Tri : Vermiculites Vermiculite

Micas Di : Muscoves Muscovite(IO) Paragonite(9)


x~1 10 (9)
Tri : Biotites Biotite, Phlogopite

Brittle Di : Margante Margarite


x~2 ~9
Micas Tri : Clmtonite Seybertite, Xanthophyllite

Di : Sudotes Sudote, Cookeite


Hydroxyde X
Chlorites 14C Tri : Chlorites Penninite, Clinochlore
Layers variable
Di-Tr : Donbassite Donbassite

Subgroup Structural
AME REMARKS GROUP (SUBGROUP) Octah. Layer type

AI-Biotite Fe-Mg Mica Micas (Biotite) Tri 2/1


Al-Chlonte Chlorites Di 2/1
Al-Celadonite Micas (Muscovite) Di 2/1
AI-Hydromca Hydromicas Di 2/1
Aliettite Regular mixed layer Talc-Saponite Mixed layers Tri
Allevardite - Rectorite Regular mixed layer Illite-Montmonllonite Mixed layers Di
AI-Nontronite Montmorillonites Di 2/1
Al-Serpentine Serpentines Tri 1/1
Aluminian Montmorillonite-Chlorite Regular mixed layer Aluminous Montmorillonite-dioctahedral Mixed layers (Di-Di) i (Di-Tri)
(or trioctahedral) Chlorite
Alumino-Chrysotile Alumino-magnesian Berthierine Septechlorites
Aluminious Serpentine Serpentines Tri 1/1
Alurgite Mn-Muscovite or Phengite Micas (Muscovite) Di 2/1
Alushite Mixture of Dickite. and Hydrous Mica and Montmorillonite Mixed layers
Amesite Aluminous Berthierine Septechlorites = 7-Chlortes Tri 1/1
Ammerzoite Dioctahedral Vermiculite or Beidellite
Annite K-Fe Biotite group Tri 2/1
Anandite Ba-Fe Brittle Mica Brittle Micas Tn 2/1
Anauxite (Discredited) Mixture of Kaolmite and Silica Tri 2/1
Andreattite Intermediate between Ilute and Montmorillonite Di
Annite Lepidomelane Mica Micas
Antigorite Serpentines Tn 1/1
Apophyllite K, Ca Sheet slicate
Aphrosiderite = Ripidolite Chlorites Tri 2/1
Aquacreptite Sepiolite-Attapulgite
Astrophyllite Na, K, Fe and Mn chain slicate
Attapulgite = Palygorskite

80
Subgroup Structural
'.-'.'E REMARKS GROUP (SUBGROUP) Octah. Layer type

Avahte Chromian Ilute Micas (Ilute)

Banmstente Dimorphous with Ganophyllite Tri


Banum-Muscovite Vanety of Musccvite Micas (Muscovite) Di 2/1
B-V-Muscovte Variety of Muscovite Micas (Muscovite) Di 2/1
Bastonite Hydrobiotite Micas (Biotite) Tri 2/1
Batavite Mg-Vermiculite Vermiculites Tri 2/1
Baumite Talc-Chlorite
Bavalite Fe-Chlonte = Daphnite Chlorites Tri 2/1
Beidellite Montmorillonites Di 2/1
Bementite Mn siicate
Bentonite Generally Montmorillonite with high absorption
Berthierine Cronstedtite (Chlorite) 7-Chlorites Tri 1/1
Biotite Mg-Fe Mica Micas (Biotite) Tri 2/1
Bityite = Bowleyte (Margarite family): Ca-Li Brittle Micas (Margarite) Di 2/1
Bowlingite Ferroan Saponie ; fibrous ; Priority ame on Cardenite Montmorillonites-Saponite Tri 2/1
Brammalite Na-lllite Hydro (Muscovite) Di 2/1
Brandesite Brittle Micas (Clintonite) Tri 2/1
Bravajsite Mixed layer (Randomly) Illite-Montmorillonite Mixed layers Di
Brunsvigite Chlorites Tri 2/1

Calcium-Gmbelite A calcian variety of Gmbelite (=Hydromuscovite) Di 2/1


Ca-Montmorillonite Monmonllonites Di 2/1
Celadonite Mg-Fe Mica Micas Di 2/1
i> -Cerolite Sepiolite
/>-Cerolite Montmorillonites (Saponite) Tri 2/1
Cerolite also considered as a mixture of Serpentme and Stevensite,
with a structure near Antigorite
Chamosite = Berthierine (Septechlorite) 7-Chlontes Tri 1/1
Chernykhite Ba-V-Mica, Ba-analogue of Roscoelite Micas (Muscovite) Di 2/1
Chlorites Varieties : on account of chemical composition, and structural Orthochlontes Chlorite Di & T r
type ; also polymorphs la, Ib, llb Septechlorites (Di-Di)
(Di-Tri)
(Tri-Tri)
Amesite Tri 1/1
Aphrosiderite (Mg : Fe<1:1). variety of Daphnite Tri 2/1
Al-Chlonte Di 2/1
Bavalite (Mg : Fe<1:1), identical to Daphnite Tri 2/1
Berthierine - Chamosite Tri 1/1
Brunsvigite (Mg : Fe<1:1) Tri 2/1
Chamosite = Berthierine
Clmochlore (Mg : Fe>1:1) Tri 2/1
Cookeite - Li-AI-Chlonte Di 2/1
Corundophylhte (Mg : Fe>1:1) Tri 2/1
Cronstedtite Tri 1/1
Daphnite (Mg : Fe<1:1) Tri 2/1
Delessite = Meianolite Tri 2/1
Diabantite (Mg : Fe>1:1) Tri 2/1
Fe-rich Manganiferous = Thuringite Tri 2/1
Gonyerite (Mn-Ferro-Ferri Chlonte) Tri 2/1
Graugesite Tri 2/1
Grochauite (Mg : Fe>1:1) = Sheridanite Tri 2/1
Grovesite Tri 2/1
Kmmererite Cr-Chlonte Tri 2/1
Kotschubeite Cr-Chlonte Tri 2/1
Leuchtenbergite = Clinochlore (Mg : Fe>1:1) Tri 2/1
Manandonite Di 2/1
Melanolite Tri 2/1
Mg-Chlorites Tri 2/1
Mg-Fe-Chlorites Tri 2/1
Moravite Tri 2/1
Nemaphyllite-Chlorite with Serpentine composition
Nimesite = Ni-amesite Tri 1/1
Nimite = Ni-Chlorite Tri 2/1
Orthochamosite Tri 1/1
Pennantte (Ferro-Ferri Chlorite) Tn 2/1
Pennmite (Mg : Fe>1:1) Tri 2/1
Prochlorite Tri 2/1
Ripidotite (Mg : Fe>1:1) Tri 2/1
Sheridanite (Mg : Fe>1:1) Tri 2/1
Sudote Di 2/1
Tatc-Chlorite (Mg : F>1:1)
Thuringite (Ferro-Ferri Chlorite) Tri 2/1
Chlorite-Montmorillonie Regular or Randomly mixed layer Mixed layers (Di-Di)
(Di-Tri)
(Tn-Tn)
Chlonte-Swelling Chlonte Mixed layer Mixed layers (Tri-Tri)

81
Subgroup Structural
AME REMARKS GROUP (SUBGROUP) Ootah. Layer type

Chlorite-Vermiculite Regular mixed layer/or Randomly Mixed layers (Tri-Tri)


interstratified (Tri-D)
Chrome-Muscovite Variety of Muscovite Micas (Muscovite) Di 2/1
Chrome-Pyrophyllie Variety of Pyrophyllite Pyrophyllite Di 2/1
Chrysotile Serpentines Tri 1/1
Cnochlore Mg-Fe Chlorite Chlorites Tn 2/1
Clinoantigorite Serpentines Tri 1/1
Clinochrysotile Serpentines Tri 1/1
Clintonite = Xanthophyllite (priority on Seybertite and Xanthophyllite) ; Brittle Micas (Clintonite) Tri 2/1
Ca-Mg-Brittle Mica
Cookeite Li-AI Chlorite Chlorites Di 2/1
Corrensite Regular mixed layer Chlorite-Montmorillonite Mixed layers (Tri-Tri)
Co-Serpentine Variety of Serpentme Serpentines Tri 1/1
Corundophyllite Chlorites Tri 2/1
Cronsledtte Ferro-Ferri Berthierme 7-Chlorites Tn 1/1
Cryophyllite Variety of Zinnwaldite Micas (Lepidolite) Tn 2/1
Cr-Halloysite Variety of Halloysite Kaolmites Di 1/1

Damourite Partially hydrated Muscovite or Sericite, transitional to Hydromica


Daphnite Mixed layer with Serpentme-Chlorite structure
Delessite Considered as mixture of Montmorillonite and Celadonite ; or
a Ferro-Ferri Chlorite (Leptechlonte)
Dewcylito Mixture of Clinochlore and Stevensite/or Serpentine-Stevensite
Diabantite Fibrous variant of Saponite
Dickite Kaolinites Di 1/1
Donbassite Dioctahedral Berthierine Di-Tri

Eastonite Mg-Fe Mica Tn 2/1


Ekmanite Manganean Stpnomelane Tri
Ephesite Na-Li Brittle Lica Brittle Micas (Margante) Di 2/1

Fe-Biotte Variety of Biotite Micas (Biotite) Tri 2/1


Fe-Monmorillomte Variety of Montmorillonite Montmorillonites Di 2/1
Fe-Muscovte Variety of Muscovite Micas (Muscovite) Di 2/1
Fe-Nontronte Variety of Nontronite Montmorillonites Di 2/1
Fe-Palygorskite Fe-rich Palygorskite
Fedonte X-ray pattern of a micaceous silicate
Flmt Clay Kaolinites Di 1/1
Fire Clay Pseudomonoclinic disordered Kaolinite Kaolinites Di 1/1
Ferrianmte Fe-nch Annite, ferroan Biotite Micas (Lepidomelane) = (Biotite) Tri 2/1
Ferribeidellite Ferrous Beidellite, synonymous of Nontronite Montmorillonites Di 2/1
Ferriberthierme Prefered ame to ferric Chamosite
Ferrihalloysite Ferrous Halloysite Kaolinites Di 1/1
Ferrimetahalloysite Variety of Metahalloysite
Ferrimuscovite Ferrous Muscovite Micas (Muscovite) Di 2/1
Ferri-Palygorskite Variety of Palygorskite
Ferri-Phengite Variety of Muscovite Micas (Muscovite) Di 2/1
Ferri-Phlogopite Variety of Phlogopite Micas (Biotite) Tri 2/1
Ferrisepiolite - Gunnbarjarnite
Ferro-Ferri-Margarte Ferroan Margante Brittle Micas (Margante) Di 2/1
Ferroan-Antigorite Ferrous Antigorite Serpentines Tn 1/1
Ferroan-Lepidolite Variety of Lepidolite (Li-Mica) Micas Tri 2/1
Ferroan-Saponite = Lembergite of SUDO. Cardenite, Cathkinite, Bowlingite Saponlte Tri 2/1
(priority ame)
Ferro-Phlogopite Variety of Phlogopite Micas (Biotite) Tri 2/1
Ferrous Chamosite Variety of Chamosite Tri 1/1
Fe-Saponte Ferroan Saponite Montmorillonites (Saponite) Tri 2/1
Fe-Sepiolite Fe-rich Sepiolite
Fluor Biotite Variety of Biotite Micas (Biotite) Tri 2/1
Fluor-Le pido me lae Variety of Lepidomelane Micas (Ferroan Biotite). Tri 2/1
Fluor-Phlogopite Variety of Phlogopite Micas (Biotite) Tri 2/1
Fluor-Polylithionite Variety of Polylithionite Micas (Lepidolite) Tri 2/1
Fluor-Taeniole Variety of Taeniolite (Li-Mica) Mk;as (Lepidolite) Tri 2/1
Fraipontite Zn-Berthierme 7-Chlontes Tri 1/1
Fuchsite Cr-Mca Micas 2/1

Ganophyllite Dimorphus of Bannisterite Hydrobioite Tri


Garnierite Ni-Antigorite Serpentines Tri 1/1
Ghassoulite = Hectorite ; identified as Stevensite or Mg-Vermiculite Saponites Tri 2/1
Glauconite Fe-Mg-Hydromica Micas Di 2/1
Gonyerie Mn-Chlonte Chlorites Tri 2/1
Graugesite Mn-Chlorite = Brunsvigite Chlorites Tn 2/1
Greenalite Fe-Antigorite Serpentines Tri 1/1
Griffithite Ferroan Saponite Saponites Tri 2/1
Grochauite Variety of Sheridanite Chlorites Tri 2/1
Grovesite Near Pennantite ; Mn-Berthierine. X-ray pattern similar to Septechlorites Tri 1/1
Berthierine and to Cronstedtite

82
Subgroup Sructural
AME REMARKS GROUP (SUBGROUP) Octah. Layer type

Gmbelite Fibrous Mg-Hydromuscovte Hydromicas Di 2/1


Gunnbjarnite Ferri-Sepiolite (cf. Xylotile) Sepiolites

Halloysite Synonimous : Endellite, hydrated Halloysite, Hydrohalloysite, Kaolinites Di 1/1


Indianite, Milanite. Miloschite.
Varieties : fully hydrated ; partially dehydrated ; dehydrated.
Hectonte Saponitas Tn 2/1
Hendrickste Zn, Mn Biotite group Biotites Tri 2/1
Hinsegerite X-ray data near Nontronite ; ferrosilicic gel or poorly crystallized
Nontronite
Hydrobiotite Mixed layer Illite (Muscovite) - Vermiculite ; regular or randomly Mixed layers (Tri-Tri)
mterstratification (Di-Di)
(Tri-Di)
Hydromica Synonimous : llite
Hydrornuscovite AI-Hydromica, Illite Hydromica Di 2/1
Hydroparagonite (= Brammalite) Hydrornuscovite Di 2/1
Hydrophlogopite Hydrobiotite Tn 2/1
Hydroserpentine Variety of Serpentme

Ihtes) Synonimous : Hydromica : clay Muscovite ; Hydrous Mica ; Di 2/1


detntal Muscovite
Polymorphs : 1 M, 1 Md, 2M
Varieties :
- Al-lllite (Fe-poor Illite) =
- Mixed 1 M Muscovite-Montmorillonite (10%)
- Iron Ilute (Fe-lllite)
- Brammalite
- Glauconite
- Celadonite
- Open Ilutes (le, IV, IM of LUCAS, 1963)
Materials relatad to Illite :
- Hydrated Illite
- Interstratified Illite-Expanded (14)
- Illite degraded Illite, or Hydrous Mica, or Illie-Montmorillonite
(randomly interstratified structure)
- Expanded (14) Ilute, or open Illite. other ames : Vermiculite-
like clay (dioctahedral) ; soil Vermiculite ; dioctahedral soil
Vermiculite
Iron-nch Saponite Variety of Saponite Saponites Trl 2/1
Iron-rich Serpentina Variety of Serpentme Serpentines Tn 1/1
Iron Sericite Variety of Muscovite Micas (Muscovite) Di 2/1

Jeffensite Vermiculite Tn 2/1


Jeffersonite Vermiculite Tn 2/1
Jenkinsite Ferroan Antigonte Serpentines Tn 1/1

Kmmerente Cr-Chlonte Chlontes Tri 2/1


Kanbaraite Actually related to no known mineral ; hexagonal clay of Japan
Kaolinite Varieties : ordered ; b-axis disordered Kaolinites Di 1/1
Polymorphs : 1T, 2M-|, 2M2
Kaolinite-Montrnorillonite or Mixed layers
Kaolmite-Smectite
Karpinskyite Mixture of Leifite and of a Zn-bearing clay of the Montmorillonte
group
Karrenbergte Clay between Nontronite and Saponite
Kellyite Serpentme group
Kerolite Cerolite = non-swelling or difficul swelling 10A Talc-like
Magnesium silicate
<i - Kerolite Sepiolites
/i-Kerolite Saponites
Kinoshitalite Mg analogue of Anandite
Kmaite Fe, K-rich Celadonite (Mg-Fe Mica) Micas Di 2/1
Kolskite Mixture of Lizardite and Sepiolite Serpentines
Kotschubeie Cr-Chlorite or Clinochlore with 4o Cr2O3 Chlorites Tri 2/1
Kyanophilte Mixture of'Paragonite and Muscovite
Tn
Ledikite Fe-Mg Illite Hydrobiotite 2/1
Leifite Na
Lembergite Fe-rich Saponite Saponites Tri 2/1
Lepidolite Li-Mica Micas Tn 2/1
Lepidomelane Ferroan Biotite Biotites Tri 2/1
Leuchtenbergite = Clinochlore Chlorites Tri 2/1
Leucophyllite AI-Mica
Levierrieritc Mixture of Kaolmite and Illite (Muscovite)
Lithian Muscovite Li-Muscovite Micas (Muscovite) Di 2/1
Lithmm-Muscovite (of STEVENS) Synonimous of Trilithionite
Lithimuscovite Li-Mica

83
Subgroup Structural
AME REMARKS GROUP (SUBGROUP) Octah. Layer type

Lizardite Serpentines Tri 1/1


Loganite Penninite Chlontes Tn 2/1
Loughlimte Hydrous Na-Mg silicate

Manandonite Li-B-Chlorite AI-Li-Chlorite Di 2/1


Manganiferous Smectie Mn-rich Montmorillonite Montmorillonites Di 2/1
Mangan-Muscovite Variety of Muscovite Micas (Muscovite) Di 2/1
Mangan ophlog opile Manganean Phlogopite Micas (Biotite) Tri 2/1
Manganophyllite (of IGGLESTRM) Variety of Biotite with 18o MnO Micas (Biotite) Tr 2/1
Magnesian Margante Variety of Margante Brittle Micas (Margarite) Di 2/1
Magnesium-Beidellite Variety of Beidellite Montmorillonites Di 2/1
Mahadevite Mica intermedate between Muscovite and Phlogopite Micas
Margante Ca-AI Brittle Mica Brittle Micas (Margarite) Di 2/1
Manposites Chromian variety of Phengite (AI-Mica) Micas (Muscovite) Di 2/1
Medmontite Mixture of Chrysocolle and Mica, placed in Saponite group Tn
Melanolite = Delessite
Metahalloysite - Halloysite of U.S. authors
Mg-Chlorites Chlontes Tn 2/1
Mg-Fe-Chlorites Chlontes Tri 2/1
Mg-orthoserpentine Variety of Serpentine Serpentines Tn 1/1
Mg-parahalloysite Kaolinite Di 1/1
Mica Group ame Comprises subgroups : Muscovitee, Di&Tn 2/1
Biotite, Lepidolite
Mica-Chlorite Mixed layer (regular, random) Mixed layers (Di-Tri)
(Di-Di)
Mica-Monmorilonite Mixed layer (regular, random) Mixed layers (Di-D)
Mica-Vermiculite Mixed layer (regular, random) Mixed layers (Di-Di)
Minguetite = Stilpnomelane s.l. Hydrobiotie
Minnesotaite Fe-nch Tale Pyrophyllite-Talc Tri 2/1
Miloschite Cr-variety of Halloysite Kaolmites Di 1/1
Mn-Palygorskite Variety of Palygorskite
Mn-Sepiolite Variety of Sepiolite
Montmorillonite Varieties ; Montmorillonites-Saponites Di&Tri 2/1
(Na-Montmorillonite ; Dioctahedral : Montmorillonite. AI-Montmonllonite. Nontronite,
Na-Ca-Montmorillonite ; Fe-Nontronite, Beidellite.
Ca-Montmorillonite ; etc...) Trioctahedral : Saponite, Hectorite, Sauconite.
Montmorillonite-Chlonte Mixed layer (regular, random) Mixed layers (Tri-Tri)
(Tri-Di)
(Di-Di)
(Di-Tri)
Montmorillonite-Mica Mixed layer (regular, random) Mixed layers (Di-Di)
Montmonllomte-Muscovite Mixed layer (regular, random) Mixed layers (Di-Di)
Montmorillonite-Vermiculite Mixed layer (regular, random) Mixed layers (Di-Di); (Tri-Tri)
Moravite Chlorites Tri 2/1
Muscovite Micas (Muscovite) Di 2/1

Nacrite Kaolinites Di 1/1


Natro-alummobiotite Variety of Biotite Micas (Biotite) Tri 271
Nefedyevite Nickelian Montmorillonite
Nemaphyllite Chlorite with a Serpentine composition
Nemecite Fe-rich hydrated Silicate
Nepouite Ni-Antigonte or Ni-contammg platy Serpentine Serpentines Tri 1/1
Ni-Antigorite Variety of Antigonte Serpentines Tri 1/1
Nickel-/} -Kerolite Variety o f / j -Kerolite
Nimesite Ni-Amesite (Berthierme) 7-Chlorites Tri 1/1
Nimite Cr-Chlorite (30% NiO : llb polytype) Chlontes Tri 2/1
Ni-Montmorillonite Nickelian Montmorillonite Montmorillonites
Niobophyllites Niobum analogue of Astrophylllte
Ni-Serpentine Ni-rich Serpentine Serpentines Tri 1/1
Nontronite Fe-rich Montmorillonite Montmorillonites Di 2/1
Noumeite Ni-rich Tri 1/1

Oellachente Barium Muscovite with 10% BaO Micas (Muscovite) Di 2/1


Orthoantigorite Serpentines Tri 1/1
Orthochamosite Orthorhombic dimorph of Chamosite
Orthochrysotile Orthorhombic dimorph of Chrysotile
Orthoserpentine Orthorhombic dimorph of Serpentine
Oxybiotite Variety of Biotite Micas (Biotite) Tri 2/1

Palygorskite
Parabiotite A Biotite with a higher conten of H2O
Parachrysotile
Paragonite Micas (Muscovite) Di 2/1
Parahalloysite Similar to Halioysie in composition, and a silica-poor
Montmorillonite in Structure
Pennantite Fe-Mn Chlorite Chlorites Tri 2/1
Penninite Mg-Fe Chlorite Chlorites Tn 2/1

84
Subgroup Structural
.-VE REMARKS GROUP (SUBGROUP) Octah. Layer type

Re<xxaite Ni-Clinochrysotile Tri 1/1


Riengite AI-Mica Micas (Muscovite) Di 2/1
Phlogopite K-Mg-Mica Micas (Biotite) Tri 2/1
Pilolith Ferri-Palygorskite
- --: '-; Ni-Saponite Montmorillonites (Saponite) Tri 2/1
- - - Muscovite pseudomorph after Cordierite
Polylithiomte Variety of Lepidolite (Li-Mica) Micas Tri 2/1
Polassium-Bentonite = Metabentonite
Prochlonte Chlorites Tri 2/1
Protolithionite (of SANBERGEN) Variety of Zmnwaldite Micas (Lepidolite) Tri 2/1
Pseudothunngite Variety of Thuringite Chlorites Tri 2/1
".- : "/ te Pyrophyllite Di 2/1
Pyrosmafite Mn-Fe

Radiophyllite = Zeophyllite
Rectorite = Allevardite = Mixed layer Illite-Montmorillonite Mixed layers
Ripidolite Chlorites Tri 2/1
Romannechite = Psilomelane
Roscoelite V-Mica Micas (Muscovite) Di 2/1

Sangante Mixed layers


Saponita Saponitas Tri 2/1
Saponite-Talc Mixed layer Mixed layers
Sarospatite Mixed layer Mixed layers
Sauconte Saponites Tri 2/1
Schuchardtite Ni-Chlorite, la polytype Chlorites Tri 2/1
Sepiolite
Septechlorite = Berthierine = Chamosite 7-Chlonte Tri 1/1
Sencite Micas (Muscovite) Di 2/1
Sericite-Sudote Mixed layer Mixed layers Di
Serpentme Serpentines Tri 1/1
Serpentine-Talc Mineral between Tale and Serpenine
Seybertite Bnttle Micas (Clmtomte) Tri 2/1
Sheridamte Chlorites Tri 2/1
Siderophyllite Annite Micas (Biotite) Tri 2/1
Sideroschisolite = Cronstedtite (Berthierine) Septechlorites Tri 1/1
Skolite Hydrated Silicate near Glauconite (AI-Hydromica) Illite Di 2/1
Soda-Margante a-Margante Bnttle Micas (Margante) Di 2/1
Soil Montmorillonite Baddly crystallized Montmorillonite ; randomly interstratified Illite-
Montmorillonite (Montmorillonite nterlayers predommant)
Soil Vermiculite = Expanded (14) Ilute or degraded Illite Di
Spodiophyllite Lepidolite group Micas (Lepidolite) Tri 2/1
Stevensite Saponites Tn 2/1
Stilpnomelane Hydrobiotite
Subdelessite Identical with Chamosite Septechlorite Tn 1/1
Sudote = Kolskite Chlorites Di 2/1
Sungulite Variety of Serpentino (Lizardite + Sepiolite)
Svitalskite Unnecessary ame for Celadonite ; X-ray pattern analogue to the
Phlogopite-Biotite seres
Swelling Chlonte Chlorite with labile (swelling) nterlayers Chlorites Tn 2/1/1
Swmefordite Montmorillonite series

Taeniolite Lepidolite group Micas Tri 2/1


Tale Tale Tri 2/1
Talc-Chlonte Chlorites
Takarkaie Chlorites
Tarasovite Mixed layer
Thuringite Chlorites Tri 2/1
Tosudite Mixed layer Montmorillonite-Chlorite Mixed layers (Tri-Di)
(Di-Di)
Tosalite Mn = Fe = 1, Intermedate member n the Bementite-Greenalite Series Serpentines Tri 1/1
Trilithionite Synonymous of Lithium Muscovite of STEVENS

Vermiculite Vermiculites Tri 2/1


Volchonskote Montmorillonite with 20% Cr2O3 Montmorillonites Di 2/1

Willemseite Ni-Talc Tale Tn 2/1

Xanthophyllite Mg-Ca Mica, variety of Seybertite Bnttle Micas (Clintonite) Tri 2/1
Xylotile Fe-bearing Palygorskited
Zedebassite = Saponite Saponites Tri 2/1
Zeophyllite Ca-F hydrated silicate
Zinalsite Zn- ; mixture of Sauconite and Berthierine
Zinc-Montmorillomte = Sauconite Saponites Tri 2/1
Zincsilite Montmorillonites
Zinnwaldite Lepidolite group Micas Tri 2/1
Zircophyllite X-ray analogue to Astrophyllite
Zn-Mica

85
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90
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Maquettes et dessins d'Edouard Rusinowski.
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