-1THE EFFECT OF CATION SUBSTITUTIONS
ON THE PHYSICAL PROPERTIES
OF TRIOCTAHEDRAL MICAS
-by
Robert Miller Hazen
SUBMITTED IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE
DEGREE OF MASTER OF
SCIENCE
at the
MASSACHUSETTS INSTITUTE OF
TECHNOLOGY
June, 1971
Signature of Author .-.-.......................
Department of Earth and Planetary Sciences,
May 8, 1971
Certified by ........
' Mv ,
.
.
*. 4oW
ar.:4.
•.•.r..-.t.....
Thepis Supervisor
.-
Accepted by
.....
/11
-
. .
vuW'"r.Y'/Y...................
(.../..
Chairman, Departmental Committee
Lindgren
on Graduate Students
ABSTRACT
-2-
The Effect of Cation Substitutionp on the
Physical Propertiep of Trioctahedral Micas
by
Robert Miller fazen
Submitted to the Department of Earth and Planetary Sciences
in partial fulfillment of the requirement for the
degree of Master of Science
June, 1971
Unit cell dimensions and refractive indices have been
determined for synthetic hydrous trioctahedral micas in which
each of Co+ 2 , Cu+ 2 , Fe+ 2 and Ni+ 2 completely occupies the octahedral sites. Zn and Mn micas with excess aluminum have
also been synthesized,.but syntheses of pure Zn+ 2 , Mn+2 , Cd+ 2
and Pb+2 micas were not successful. Tetrahedral substitutions
of B+3, Fet 3 and Ga+ 3 for Al+ 3 and Ge 4 for Si+ 4 ; and interlayer cation substitutions of Rb+, Cs+, NH4+ and Na+ for K+
provide additional data on linear relationships that exist
between ionic radii (Shannon and Prewitt) and unit cell edges,
and between ionic radii cubed and unit cell volumes of these
micas. The influence of substitutions on the unit cell are
such that octahedral substitutions predominantly affect the
a-dimension, interlayer substitutions the c-dimension, and
tetrahedral substitutions affect both dimensions.
Tetrahedral and interlayer cation substitutions of a
wide range of ionic radii were found to form stable micas.
However, octahedral cations of greater than 0.78 A average
ionic radius do not form stable trioctahedral micas of the
form KR3+ 2 AlSi3OlO0(OH)2. The instability of such micas is
shown to be due to the misfit of smaller tetrahedral layers
onto a larger octahedral layer. The composition of natural
biotites are explained on the basis of this model. In addition, quantitative predictions of the amount of Fe+ 3 in octahedral and tetrahedral positions in synthetic annite were
made, and have been confirmed by M6psbauer and analytical
chemistry techniques. A nomogram is conptructed in which,
for any given composition of a hydrous trioctahedral mica,
the relative stability of the mica may be determined.
Thesis Supervisor: David R. Wones
Title: Associate Professor of Geology
TABLE OF CONTENTS
-3-
TITLE PAGE
1
ABSTRACT
2
TABLE OF CONTENTS
3
ACKNOWLEDGMENTS
5
INTRODUCTION
6
Table 1--Previous studies
7
MICA COMPOSITIONS STUDIED
8
EXPERIMENTAL TECHNIQUE
9
Table 2--Chemicals Used
11
Table 3--Mica Synthesis Experiments
14
20
UNIT CELL PARAMETERS
Table 4--Unit Cell Parameters of Synthetic Micas
21
23
OPTICAL DATA
25
Table 5--Optical Properties of Synthetic Micas
SOURCES OF ERROR
26
RELATIONS BETWEEN CELL PARAMETERS AND IONIC RADII
29
Figure 1--Monoclinic bm vs. octahedral cation radius-31
33
Figure 2--c m vs. interlayer cation radius
Figure 3--Volume vs.
ionic radii cubed for R +
+
Figure 4--Volume vs. ionic radii cubed for R
Figure 6--Octahedral layer compression
2
Figure 8--Tetrahedral layer rotation
Figure 9--a vs. ionic radius R+
and R +
3 -
41
SUBSTITUTIONS AND STABILITY
ionic radius R+
35
37
39
Figure 5--d001 vs. b
Figure 7--T vs.
2
2
43
46
48
51
-4OCTAHEDRAL CATION DISTRIBUTION IN NATURAL MICAP
Figure 10--R+ 2 coposition in natural mwicap
53
54
THE COMPOSITION OF ANNITE
56
PREDICTION OF TRIOCTAHEDRAL MICA STABILITY
58
Figure 11--a vs. cation radius R+ 2
59
Figure 12--Nomogram of cosa vs. ionic radii vs. dt
61
FUTURE STUDIES
63
REFERENCES
65
APPENDIX A--The Stability of Hydrous Trioctahedral Micas 70
and their Related Hydroxides
Introduction
70
Experiments and Data
71
Preliminary Conclusions
71
Table A-l--Stability experiments
72
Table A-2--Cell Parameters of oxides and hydroxides 74
APPENDIX B--Selected Computer d-spacings for synthetic
Micas
VITA
76
-5-
ACKNOWLEDGMENTS
I wipsh to expreps my great appreciation to Prof. David
R. Wones for his many hourp of advice and guidance.
Not only
did he provide the initial outline for this ptudy, but he
also maintained close contact as the study progressed, thus
adding direction and enthusiasm to my efforts.
I would also like to thank Messrs Robert Charles, Joseph
Chernosky , Yves Pelletier, and Dr. David Hewitt for aiding
me in many aspects of laboratory techniques and maintenance.
Many hours of labor were saved through their suggestions and
aid.
Many thanks are also due to Prof. Charles W. Burnham,
Prof. Charles T. Prewitt, Dr. Hiroshi Takeda, and Dr. James
Munoz for their stimulating discussions and many helpful
comments.
This investigation was supported by National Science
Foundation grants GAll09 and GA13092 to Prof. David R. Wones.
-6Introduction
Trioctahedral micas are subject to a wide variety of
cation substitutions.
Several authors have demonstrated
that such substitutions have a profound effect on both the
physical properties and the stabilities of these layer silicates (Hatch et al.,
1957).
1957; Wones, 1963b; Klingsberg and Roy,
A list of several recent studies on synthetic hydrous
trioctahedral micas is given in Table One.
While data is now
available for a dozen such mica end-members, there has been
little attempt tb
systematically examine changes in mica
properties with composition.
The present study is an attempt
to quantitatively define the effects of a wide range of cation
substitutions on the physical properties of hydrous trioctahedral micas.
TABLE 1.
Previous Studies of Synthetic Hydrous Trioctahedral Micas
Composition
Emphases of Study
References
KMg 3 AISi30
(OH) 2
Physical Properties & Stability
Stability
Structure
Yoder & Eugster (1954)
Wones (1967)
Steinfink (1962)
KFe
(OH) 2
Stability & Physical Properties
Stability & Physical Properties
Eugster & Wones (1962)
Wones, Burns & Carroll (1971)
Physical Properties
Stability
Wones (1963)
Wones & Eugster
(OH)2
Physical Properties
Wise & Eugster (1964)
KFe 3 FeSi30 1 0 (OH) 2
Physical Properties
Wones
Physical Properties
Physical Properties
Eugster & Wright (1960)
Stubicon & Roy (1962)
KMg9 GaSi 3 O 1 0 (OH)
KNi 3 AISi 3 0 1 (OH) 2
Stabilities only
Klingsberg & Roy (1957)
DeVries & Roy (1958)
KZn 3 AISi 3 0 1 0 (OH)2
KMn3AiSi 3 0 1 0 (OH)
2
Unit Cell Parameters
Frondel & Ito
NaMg 3 AISi
Physical Properties
Carman (1969)
Physical Properties
Eugster & Munoz
3 AISi3O0
30 10
K(Mg,Fe) 3 AISi
KMg 3 FeSi
KMg
3
BSi
3
O1
3 O1 0
0
(OH)2
3 O1 0
Nh 4 Mg 3 AISi
3
(OH)2
(OH)2
010(OH) 2
(1965)
(1963a)
(1966)
(1966)
-8.
Mica Compositions Studied
The hydrous magnesian trioctahedral mica, phlogopite
KMg 3 AlSi 3010 (OH)2' was used as the reference composition in
Attempted 100% octahedral substitutions for Mg+ 2
this study.
+2
+2
included Mn
,Co
,Cu
,Zn
of Wones (1963b) on the Fe+2 mica
+2
+2
+2
+2
+2
,N
, and Pb
,Cd
Data
.
annite, and synthetic bio-
tites on the join phlogopite-annite, have also been employed.
Tetrahedral cation substitutions were Ga +
Al+ 3 , and Ge+
for Si+;
layer cation K
3
,
Fe +
3
,
and B
for
while substitutions into the inter-
position include Rb
,
Cs
,
Cu
,
and Ag
.
In
addition, Na+ phlogopite data of Carman (1969) and NH + phlogopite data of Eugster and Munoz (1966) have been used in
this study.
Finally, a number of double 100% cation substi-
tutions into the phlogopite structure were studied, including
ferriannite-KFe 3erant-~
+2Fe+3Si330(OH)
10
2 (data of Wones, 1963a),
nickelous ferriphlogopite-KNi 3FeSi 3020 (OH)2,' cobaltous ferriphlogopite-KCo 3FeSi 300 (OH)2 and sodium-zinc phlogopiteNaZn AlSi33 0
(OH) 2
Experimental Technique
A complete list of chemicals and their lot numbers used
in starting material preparation will be found in Table Two.
Cobaltous hydroxide was prepared by the T.A. Edison precipitation method (U.S. Patent # 1,167,484) in which ammonium hydroxide is added to a cobaltous sulfate solution.
The preci-
pitate of Co(OH) 2 is washed five times in deionized and distilled water, and then dried at 100*C for 4h.
prepared by heating AlCl 3
26H
20
y-alumina was
for lh. at 750 0 C.
The silicat
glass was cleaned both magnetically and in acid, and fired at
800°C for 2h. before using.
K-O-2SiO
2
2
was prepared by D.R.
Wones from cleaned SiO 2 glass and KHCO 3 after the method of
Schairer and Bowen (1955).
Starting materials of five types
were used:
I)
Oxide Mix
2)
K2Si 2 0 s plus oxides
3)
KA1Si30. gel plus R+ 2 oxide or hydroxide
4)
KFeSi30 8 gel plus R + 2 oxide or hydroxide
5)
Mica gel
All gels were prepared by titration of standardized nitrate
solutions.
The solution-mixes were dried and fired as de-
scribed by Shaw (1963).
Oxide mixes were prepared by weighing
and mixing dried oxides or hydroxides, and then grinding in
an agate mortar until homogeneous.
Charges were sealed with excess deionized and distilled
water, or 30% H 2 O 2 solution in Au or Ag 80 Pd 20
1/8" x 1/2"
-10-
capsules.
In several runs oxygen fugacities were controlled
by the solid buffer technique of Eugster (1957).
Standard
cold seal hydrothermal pressure apparatus was used in all
runs (Tuttle, 1949).
Pressure measurements are believed
accurate within 1%, and the error in temperature is within
±3C.
All runs were rapidly quenched (2 minutes) in a cool
water bath.
X-ray powder diffraction examination of all runs was
performed on a Picker diffractometer using Cu K
radiation,
and data was collected on a servoriter strip chart recorder.
Both CaF 2
(Baker's Analytical Reagent lot #91548; annealed
3X at 800°C for lh.; a = 5.4620 ±.0005) and BaF 2 (Baker's
lot #308; annealed 2X at 800 0 C for lh.; a = 6.1971 + .0002)
were employed as internal standards.
Least squares unit
cell refinements were performed on the Appleman, Handworker
and Evans program.
Optical data was obtained using a Zeiss
binocular polarizing microscope with a white light source.
Determination of mica indices of refraction were accomplished
with Cargille's Index of Refraction Liquids, which are accurate to within
±.0005.
All x-ray diffraction and optical
work was performed at room temperature (240 ± 1C).
TABLE 2.
Chemicals used in starting material preparation
Chemicals used in oxide mix preparation
Formulae
Manufacturer (& Grade)*
SiO
glass
Corning
(trigonal)
Fisher
*6h 20
Mallinkrodt
2
GeO 2
AICI
3
(lump cullet)
Lot Number
7940
786604
15961X
Fe203
B203
BO
23
Fisher
MgO
Fisher
MnO
K & K
10868
Mallinkrodt
n.d.
CoSO
4
J.T. Baker
*7H 2 0
762942
39315
787699
NiO
Matheson, Coleman & Bell
CuO
Mallinkrodt
ZnO
Baker & Adamson
CdO
Baker & Adamson
Ni (OH) 2
K & K
16214
NH
J.T. Baker
24037
J.T. Baker
21537
4
(OH)
KHCO 3
CB918 NX345
X40588
B354
A244X364J
TABLE 2.
Continued
Lot Number
Formulae
Manufacturer (& Grade)*
K (OH1
J.T. Baker
14890
Ag20
K & K
17692
Cu20
Fisher
n.d.
Additional chemicals used in gel preparations
"Ludox"**
Dupont
Ag Metal
Fisher
71096
Cu Metal
Baker & Adamson
N-023
Zn Metal
Merck
40678
Pb Meta I
Fisher
Ga Metal
J.T. Baker (99.999%)
n.d.
KNO 3
J.T. Baker
30158
NaNO 3
J.T. Baker
33275
RbNO 3
K & K
18088
CsNO 3
K & K
7824
(High Silica)
(8/1000" foil)
n.d.
n.d.
TABLE 2.
Continued
Formuale
Manufacturer
Mg(NO 3 ) 2* 6H20
Ma llinkrodt
Mn(NO3) 2
Mallinkrodt
(& Grade)*
Lot Number
37012
(50% solution)
27357
9H 2 0
Mallinkrodt
26829
Cr(NO 3 3" 9H20
Mallinkrodt
795204
Al (NO 3 3
*All chemicals reagent grade unless noted.
**Dupont Ludox was analyzed by F. Frey.
include by weight SiO
2
Solids after drying and firing at 300 0 C
= 99.0% and Na20 =
1.0%.
TABLE 3.
Mica Synthesis Experiments
Micas of the form R Mg 3 AISiOl
R
+
cation
+
R
ionic
Run
radius (A )
PT
(in
H 0
kbals)
T(OC)
(t+30)
K
1.38
M#1l
2.0
800
Rb +
1.49
M#105
2.0
700
0
(OH)
Duration
(hours)
140
2
Starting
Materials
Capsule
Buffer
gel
Au
gel
Au
Products
100% phlogopite
Rb-phlogopite,
Forsterite, &
RbAISi20
Cs
Ag
Cu+
1.70
1.15
0.96
M#98
2.0
300
340
gel
Au
do. plus glass
M#106
2.0
700
140
gel
Au
Cs-Phlogopite,
Forsterite, &
CsAISi206
M#99
2.0
300
340
gel
Au
Forsterite,
CsAISi20 6 & glass
M#46
2.0
310
48
gel
Au
Silver Metal & gfas$
M#67
2.0
540
48
gel
Pt
do.
M#90
2.0
600
72
Mg AISi
gl
plds
Agp
Au
Silver Metal, Chlor;e
& glass
M#122
2.0
630
96
Oxide Mix
Au
Cu20, Talc & unknown
TABLE 3.
Continued
Micas of the form KR 3 +2AISi
++
R
cation
Mg+2
Mn+
2
.
R ionic
radius (A).
Run
#
PT= PH 2 0
T(oC)
(in kbars)
( 30)
0.720
M#1I
2.0
800
70
0.83
M#13
2.0
450
96
M#18
2.0
280
M#19
2.0
M#32
Duration
(hours)
3 01 0
(OH)
2
Starting
Materials
Capsule
Buffer
gel
Products
Au
100% Phlogopite
Oxide Mix &
K2Si 2 0 5 gel
Au
a-Mn20 ; y-Mn2 0 3 &
sana ine
216
Reduced
Oxide Mix
Au
MnO; Mn(OH) 2 & glass
362
120
Reduced
Oxide Mix
Au
Tephroite, Kalsitite &
Leucite
2.0
603
120
Gel
Au
Mn(OH) 2 & Manganophyllite
M#62
2.0
725
72
Gel
Au
y-Mn203 & Sanidine
M#86
2.0
540
96
Reduced Gel
Au
Braunite, Tephroite
Sanidine & <10% Mica
M#84
2.0
580
670
Reduced Gel
Au
Braunite & Sanidine
M#91
1.0 kb
500
336
M#32
Ag-Pd
Mn(OH) 2 & Manganophyllite
500
336
Gel
Ag-Pd
Tephroite, Kalsilite &
Leucite
600
96
MnO plus
Kfs gel
Ag-Pd
Tephroite, Kalsilite &
Leucite
CH 4
M#92
1.0 kb
CH 4
M#117
1.0 kb
CH 4
ul
~I~L~
_1
_____
TABLE 3.
R+z
cation
Co
Ni
+2
+ 2
R+ 2 ionic
radius (A )
0.745
0.69
Run
#
M#114
PT = PH20
(in kbars)
2.0
T(oC)
(*30)
750
Continued
duration Starting
(hours) Materials
48
Capsule
Buffer
Co(OH) 2
plus
gel
Au
Products
100% Cobaltous
Phlogopite
SR#12
1.0
710
48
Co(OH) 2
plus
gel
Au
100% Cobaltous
Phlogopite
SR#34
0.2
880
48
SR#12
Au
CoO, Co Olivine &
Leucite
M#7b
2.0
600
145
Oxide mix
Au
100% Nickelous
Phlogopite
Ni(OH)
plus Au
gei
100% Nickelous
Phlogopite
80% Cupric Phlogopite,
glass and minor unidentified #
plus K2Si20 5
gel
M#115
2.0
750
48
M#29
2.0
600
120
Gel
M#49
2.0
703
96
Gel
50% Cupric Phlogopite,
glass and unidentified
phase
M#77
2.0
260
215
Gel
Cupric Phlogopite, CuPyroxene & Muscovite
2
Cu+
0.73
Au
I
I
TABLE 3.
R+2
cation
Zn
+2
R ionic
radius (A0 )
0.75
Run
#
M#8
PT = PH 2 0
(in
kbars)
2.0
T(OC)
°
(2I3 )
600
Continued
Duration Starting
(hours) Materials
145
Oxide mix
Capsule
Buffer
Au
Willemite, Kalsilite
& Leucite
Oxide mix
& K2Si205
Au
Willemite, Mica &
minor Leucite
& K 2 Si 2 05
0.95
Products
M#17
2.0
280
215
M#61
2.0
725
72
Gel
Au
Willemite, Kalsilite
& Leucite
M#94
2.0
530
50
Gel
Au
Willemite, Mica &
Leucite
M#101
2.0
500
290
Gel
Au
Willemite, Mica &
Leucite
M#9
2.0
600
145
Oxide mix
Au
Cd-Olivine & Leucite
& K2Si205
1.18
M#22
2.0
385
360
Reduced
Oxide mix
Au
Cd-Olivine & Sanidine
M#57
2.0
650
290
Gel
Au
Pb 4 SiO
M#66
2.0
410
170
Gel
Au
K2Pb 4Si8 021' Sanidine
6
& unknown
& Pb 3 0 4
H
_ _
Table 3.
+3
R
cation
R + 3 ionic
radius (A)
Run
#
PT
(in
PH
20
T(OC)
(-30)
kbars)
Continued
Duration
(hours)
+3
Ga+
3
0.39
M#1
2.0
800
0.12
M#30
2.0
603
M#108
2.0
720
M#46
2.0
310
0.47
Products
R+ 3 Si310(OH) 2
Micas of the form KM
Al
Starting Capsule
Materials Buffer
Gel
Au
120
Oxide Mix
& K 2 Si 2 0 5
Au
50% Boron Phlogopite,
Glass
120
Oxide Mix
& K2Si205
Au
95% Boron Phlogopite
Gel
Au
40% Gallium, Phlogopit%
Ga20 , unknown 0, &
45
100% Phlogopite
glasa
Fe
+ 3
0.49
M#109
2.0
720
120
Gel
Au
100% Gallium Phlogopite
M#100
2.0
500
265
Oxide Mix
Au
100% Ferri-Phlogopite
& X 2 SiO
5
Cr
+3
(IV)
n.d.
M#107
2.0
720
120
Oxide Mix
& K2Si205
Au
100% Ferri-Phlogopite
M#111
2.0
690
215
Au
100% Ferri-Phlogopite
M#44
2.0
700
96
Oxide Mix
& K2Si20 5
Gel
Au
Cr 0 , Forsterite &
uningwn
M#72
410
2.0
Au
Gel
Cr 2 0 3 , Forsterite &
glass
I
co
~
I
1_~1_
TABLE 3.
R+4
cation
R+ 4 ionic
radius (A*)
Run
#
P T =P
(in
H2 0
kbars)
T(OC)
(±30)
Continued
Duration
(hours)
Micas of the form KMg3AIR3+4O 1 0 (OH)
Si
Ge
+ 4
+ 4
Capsule
Buffer
Starting
Materials
Products
2
0.26
M#l
2.0
800
Gel
Au
100%
0.40
M#63
2.0
725
Oxide Mix
Au
100% Ge-Phlogopite
Phlogopite
Micas of the form KR 3 2FeSi 010(OH)
Mg+2
No+2
Co
+2
M#100
2.0
500
265
Oxide Mix
& K2 Si 2 0 5
Au
100% Ferri-phlogopite
M#107
2.0
720
120
Oxide Mix
& K2Si205
Au
100% Ferri-phlogopite
M#111
2.0
690
215
Oxide Mix
& K Si205
Au
100% Ferri-phlogopite
0.69
M#123
2.0
700
24
Ni (OH) 2 &
KFeSi 3 08
Gel
Au
100% Nickelous
Ferri-phlogopite
0.745
M#127
2.0
700
24
Co(OH)
Au
100% Cobaltous Ferriphlogopite
0.72
&
KFeSi3 8
Gel
~L~
_______
__
-20-
Unit Cell Parameters
IM unit cell dimensions and volumes, as well as molecular
weights and calculated densities, for synthetic hydrous trioctahedral micas of this and other studies are listed in Table
Four.
Smith and Yoder (1956) have shown that trioctahedral
micas often possess an ideal pseudo-trigonal unit cell, defined by am = bm/NrJ
and
m = 99054
'.
The conversion from the
monoclinic IM to trigonal 3T cell is accomplished by a = a
t
m
and ct =
3 cm.sin$s.
Of the micas examined, only sodium and
boron phlogopites depart appreciably from these ideal relations.
Crowley and Roy (1960) have demonstrated that pressure of
formation does not significantly affect unit cell parameters
of phlogopite.
Similarly, synthetic micas examined in this
study showed no systematic variations of cell parameters with
temperature or pressure.
However, Eugster and Wright (1966)
have noted that the physical properties of boron phlogopite
appear to vary with temperature and pressure of formation.
Also, Carman (1969) has clearly documented the tendency of
sodium phlogopite to hydrate below 800 C.
Thus, sodium and
boron phlogopiteonce again depart from the ideal case.
It
should be noted that sodium and boron phlogopites have the
smallest cell dimensions of all micas studied.
TABLE 4.
Unit Cell Parameters of Synthetic Hydrous Trioctahedral Micas
Micas of Known Composition
Composition
am (AO)
bm (AO)
KMg3A1Si OI0 (OH)2
5.315±.001
9.204±.002
10.311±.003
99054' ±4
5.314 ±.001
5.314 ±.01
9.208 ±.002
10.314±.005
99054'
9.204 ±.02
10.314±.005
99054' 5
497. 0±1. 0
497.0±1. 0
Na Mg 3 A1Si 301 0 (OH)
2
5.265±.008
9.203 ±.006
9.994 ±.001
97045' ±8
NF4 +
5.311±.008
9.224±.004
10.443±.007
5.34 ±.01
9.24 ±.02
5.37 ±.01
5.340 ±.001
+
Rb
Cs
+
+
KCo~ 2 AISi
3 O1 0
(OH)2
-+2
Fe+2
e3
(FeMg)
3
-Mole % Fe
). 169
GFW
Pcalc.3
gm/cm
Run# or
Reference
497.0±0.6
417.3
2.79
M#1
Wones (1966)
Yoder & Eugster (1954)
479. 8 ±0 .8
401.2
2.78
Carman (1969) 1
99042
504.2
396.2
2.61
Eugster & Munoz
10.48 ±.05
99 54 '
510.0
463.6
3.02
M#105
2
9.30 ±.02
10.83
99054
'
516.8
510.8
3.18
M#17y6
2
9.240 ±.005
10.345±.002
502.8±0.3
521.1
3.44
M#114
5.341±.001
9.240±.002
5.303 ±.005
9.172±.001
+.05
10.347±.002
10. 286±.002
F.
r
±2'
990581'±2
'
99054 1
99056'±31
'
5.297±.003
n.d.
9.175±.003
n.d.
10.281±.004
99050'±3
10.17
n.d.
5.334±.001
9.238±.002
10.314±.004
99054
5.330±.001
9.234±.002
10.316±.003
99056'1±2'
5.401±.01
9.347±.005
10.297±.01
5.397±.001
9.348±.002
10.316±.005
99054'±
5.339±.006
9.230± .001
10.311±.002
99050'+4'
10.312±.001
10.293±.006
99*56'1i
0.250
5.333± .002
9.242±.001
0.352
5.349±.005
9.260±.002
5.343± . 007
0. 450
9.276±.001
10.312±.003
10Go
498.8±.4
512.0
500.6
'
500.6
99038'±6'
502.6
'
3.51
535.0
3.56
Klingsberg & Roy (1957)
M#29
2
M#49
511.9
3.32
Wones
Wones,
Carrol
Wones
(1963b)
Burns &
2
(1971)
(1963b)
I\
H
507.3
5.373± .01
9.312± .003
10.297±.009 10003' ±6'
~CO~ ~P~
520.5
M#7b
M#115
504.5
0.765
~
2
±1'
9.285+.003
10.322±.004
(1966)
503.4
99057'+4
5.358±.003
9.335±.002
SR#12
497.8±.2
10' ±12'1 511.7
0.550
5.389±.003
503.3
493.1±. 5
492.3±.3
n.d.
'
10.297+.002 1000'
0.880
P rm(_
Vol (A o )
cm (AO)
990581±4'
511.4
TABLE 4.
Compo 3sition
KMg3 B 3 S i 0
am (AO)
(OH)
G +3
Fe
+3
KMg 3 AlGe+4 0 (OH) 2
b
m
(A*)
Cm (A0 )
Continued
GFW
401.1
Pcalc 3
gm/cm
2.77
460.0
3.05
Run # or
References
M#108
Eugster & Wright (1960)
Stubicon & Roy (1962)
M#109
446.1
2.93
Klingsberg & Roy (1957)
M#107
2
10.35 ±.01
99058'1±4 1'
99055'+10 '
505.0±.2
505.2±.3
505.6
526.1+1.0
550.8
3.48
M#111
3
Wise & Eugster (1964)
2
M#63
525. 5±1.0
519.9
550.8
M#68
540.76 3.45
Wones (1963a)
501.5± .08
549.34 3.63
M#123
510.1+.04
550.00 3.58
M#127
5.29U. 002
9.177±.001
10.246±.002
5.321. 01
9.165±.02
10.29 ±.01
5.310
5.327±. 002
9.150
9.218±.005
n.d.
5.354±.001
n.d.
98034 '±4'
100010'-10'
10.234
1000 8'
'
10.359±.002 99049'1±2 1
10.26
n.d.
10.316±.004 99054'1
5.358±. 003
5.34 ±.01
9.273±. 002
9.276±. 003
9.28 ±.005
5.393± .002
9.341i .004
10.600±.002
99o54'
5.387± .002
9.378± .02
10.593± .003
99043'1±2'
±
KFe 3+2Fe+3Si 3 0 1 0 (OH)25.430 .002
±
KNi Fe
i3010(OH) 2 5.335 .005
5.368±.001
KCo3Fe+3Si30 1 (OH)2
0
Vol (A)
491. 9±.2
m
10.321±.004
'
9.237± .005
10.341±.006 10004'±10
'
10.332±.006 99055'±101
9.329±. 002
10.346±. 002
9.404± .005
99050'-+5'
3
496.5
489.5
501.2±.3
n.d.
Synthetic Micas of Unknown Composition
R+ 2 Cation & Extra Phases
Zn+ 2
5.31 ±.02
9.205±.01
10.25± .05
9s050' ±10 1'
Willemite
5.30 3±.004
9.214±.005
5.32 8.002
5.32 5±.005
9.226 ±.002
25% in
all runs
Willeriite reported
492.5±1. 0
M#17
10.285±.003
9c041't±3
'
495.4±.4
M#94
10.312±.004
99059'±1'
498.9±.2
M#101
9.210 ±.005
10,210
990501±10',
493.0±+1.0
Frondel & Itc
5.27±.01
9.20±.02
10.17±.03
99050'+10
5.31±.01
9.21±.01
10.31±.01
990451±
5.32±. 01
9.394±.01
1b.32±.01
99050'±10 '
4
(1966)
from all runs
Mn
+2
MN(CH) 2
25%
in all runs
Tephroite reported
'
6 '
M#22
M 912
503 ±3
Frondel
&
Itc
in all runs
_________
__
1.
2.
X-ray diffraction performed at 130 0 C.
iM unit cell calculated from ideal 3T cell data.
3.
4.
Mbss auer analyses of ferriphlogopites by W. Burns reveals 5 to 15% Fe+ 2 in all runs.
Unit cell parameters calculated on the Appleman, Handworker & Evans Program by this
author from Frondel & Ito (1966), Table 7, p. 1421.
'
a,=at, bm=/?-at, cm= ct/3*sin 99054 , a
99-541
(196-
-23-
Optical Data
Indices of refraction for synthetic hydrous trioctahedral
micas of this and other studies are found in Table Five.
Due
to the psuedo-trigonal habit of these micas, y=8 , and thus
two refractive indices are definitive.
Other optical para-
meters considered include birefringence B =y -a and the ob_
served mean refractive index n = /&7
32 =
+
.
While syn-
thetic crystallites seldom exceeded 20p in size, thus making
O .
2V determination difficult, all observed 2V
Micas are
colorless except for those containing cations of the transition metal series.
Intense pleochroism was observed only in
iron-bearing trioctahedral micas, whereas faint pleochroism
was noted in cobalt and copper phlogopites.
A useful, but seldom used optical property is the specific refractive energy K, defined by K = n-1/p where n is the
mean refractive index and p the density.
Gladstone and Dale
(1864) demonstrated that K for liquids may be calculated from
the formula:
kj,
K = k (PI/100) +
k2 (P2 /100)
+
etc., where
k2 , etc. are the specific refractive energies of the com-
ponents of the liquids and P1 , P,,
etc. are the weight per2
centages of these components.
H.W. Jaffe
(1956) applied the
rule of Gladstone and Dale to minerals, treating oxides as
the components of the minerals.
Jaffe
obtained reasonable
agreement between observed and calculated n in this manner.
However, it is interesting to note that the calculated n for hydrous
silicatesydisplayed consistent positive deviations from
considered in Jaffe's study
-24-
Deviations ranged from a low of -.001 to as high
observed n.
as +0.064 for the twenty-five hydrous-silicates discussed.
Similarly, synthetic hydrous micas of this study display consistently positive deviations of
cal:c. from nobs..
Only annites display a negative deviation, and positive deviations as high as +0.087 are noted.
It would thus appear
that the value cited for k(H 2 0) by Larsen and Berman (1934)
of 0.034 cannot be applied directly to water in the silicate
minerals.
A significantly smaller value for k(H2 0)is implied
by the above data.
Another source of error in the calculated
K for silicates may result from erroneous k values for transition metals.
Jaffee (1956) notes that k(Fe 20 3 ) varies from
0.290 in silicates to 0.404 in oxides.
It thus appears that
k for transition metals may be lowered considerably in a
silicate environment.
However, k values for copper, cobalt,
nickel, etc. are known only for the oxide environment.
This
may, in part, explain the anomalously high values for n calculated.
It seems that further refinement of k values are
needed before the rule of
Gladstone and Dale may be effective-
ly applied to silicate minerals.
TABLE 5.
2
nobs
- ca3
lc
Deviation
.002
1.587 .002
0.037
1.575
1.586
+0.011
.002
1.581 .001
0.031
1.571
+0.016
.003
1.588 .003
0.040
1.575
+0.011
.003
1.569 .004
1.575 .01
0.024
0.035
1.561
1.560
1.581
1.647
+0.020
+0.087
"
Colorless
Colorless
1.605 .01
1.700 .002
1.690 .002
0.035
0.067
0.055
1.590
1.678
1.672
1.601
+0.011
Colorless
1.667
-0.011
-0.005
Pleochroic:
X = Red or yellow-brown
Z = light green
1.668 .002
1.675 .002
0.061
0.061
1.648
1.654
1.688
1.702
+0.040
+0.048
Pale Purple to Lavendar
2V=0O
Medium green
M#115
Klingsberg & Roy (195 ;7)
M#29
a
KMg 3 A1Si30 1 0 (OH)2
1.550
1.550
1.548
1.545
1.540
1.570
1.633
1.636
1.607
1.614
n.d.
1.588
1.549
1.546
1.558
n.d.
1.601
1.600
1.596
1.705
1.715
.002
Rb
+
Cs
Fe3+2
Co3 +2
N+2
3
Ga+
Fe
3
Ge +4
Fe3 +2 L- 3
+2
3
+3
.01
.01
.002
.002
.002
AI
1.730
- ---.I-,
-e
Color, Pleochroism &
other remarks
Run# or
Reference
Colorless, 2V=00
M#1
Wones (1966)
Yoder & Eugster (1954)
4
Carman (1969)
2V 0 0
1.652
M#105
M#106
Wones (1963b)
Wones & Carroll (1971 )
M#114
.004
1.630 .004
0.042
1.616
1.690
+0.074
Medium blue
.002
1.580 .002
1.568 .002
0.031
1.570
1.581
+0.011
0.022
1.560
+0.021
Colorless
to
.003
1.598 .003
1.598
0.040
1.585
n.d.
n.d.
Colorless
.002
1.642 .002
0.041
1.628
1.656
+0.028
.001
1.642 .001
1.646 .003
0.040
1.629
0.050
1.623
n.d.
n.d.
Pleochroic:
X = reddish-brown
Z = pale orange
Colorless
.005
1.748 .003
0.043
1.734
1.711
-0.023
n.d.
Wones (1963a)
.005
1.760
0.0
1.745
1.787
+.042
M#127
.005
1.770 .005
0.040
1.757
1.799
+.042
x=red-brown
z= pale purple
x=red-brown
z=pale green
.002
.003
.005
+0.027
+ Fe3
M#108
Eugster & Wright (196 0)
M#109
Klingsberq & Roy (195 7)
M#111
Wise &
M#123
B =y- a
3.
Icalc. = P'k + 1, where p = density in gm/.m 3 and k = specific refractive energy
after the rule of Gladstone and Dale (1864).
4.
Indices of refraction determined on mica heated to 800 C and immediately placed
into oil.
Recent Mossbauer work reveals appreciable Fe '3 in all synthetic annites.
--..~--,,.....I...
,,
3ugster (1964)
M#63
1.
5.
---~-
B1
obs
-
1I
Compositon
Na+
Optical Properties of Synthetic Hydrous Trioctahedral Micas
-26Sources of Error
The majority of trioctahedral micas pynthepized represent 100% reaction from starting materialp, and are thus agsumed to be of ideal composition.
However, rubidium and
cesium phlogopitep represented only =20-25% of the reactants
in those runs.
These micas are thought to approximate ideal
composition on the basis of the observed trioctahedral x-ray
patterns and the predicted unit cell parameters.
Due to dif-
ficulties in standardizing gallium in nitrate solution, the
gallium phlogopite gel may be slightly difficient in Ga+ 3
explaining why a maximum reaction of only 95% was obtained.
Another .possible source of error in the assumed compositions
was revealed through Mbssbauer studies of iron-bearing phlogopites.
3 in all
Roger Burns pas shown a minimum of 10% Fe ++3
annites, and from 5 to 15% Fe+ 2 in ferriphlogopites.
Thus,
one might also expect multiple valence states in Ni, Co and Cubearing micas.
Seifert and Schreyer (1971) have demonstrated
+ 2 in tetrahedral
the presence of Mg +2
coordination in Mg-rich
synthetic trioctahedral micas.
However, the assumption is
made that all R+2~cations in this study are in octahedral coordination unless noted otherwise.
In the investigqatiodn'byFrondel and Ito (1966), and in
this study, end-member zinc phlogopite KZn 3 AlSi 3 0 1 0 (OH)2 wap
not achieved.
duced,
In all experiments in which mica was pro-
.25% willemite-Zn 2 SiO 4 with minor leucite and/or
glass were also present.
While the mica is clearly zinc-
bearing, having cell parameters and indices of refraction
higher than phlogopite, the excess willemite is evidence of
less than three Zn
+2
atoms per mica formula unit.
Neumann
(1949) has well documented the great preference of zinc for
tetrahedral coordination.
Thus, one possible explanation
for such a zinc-poor mica is that the zinc enters the tetrahedral layer, while aluminum fills the three octahedral sites;
i.e., KA
1 +3
(Zn
+2
,Si
+4
2
)3 0 1 0 (OH)2 . A structural study of
the natural zinc mica hendricksite from Franklin, New Jersey,
would aid in an understanding of zinc's role in the layer
silicates.
Synthesis of end-member manganese phlogopite-KMn3 AlSi 3 010(OH)2 was also unsuccessful.
Frondel and Ito (1966) report
that tephroite-Mn 2 SiO 4 is present as a major phase in all
mica-bearing runs, while in the present study pyrochroiteMn(OH)2 accompanies the mica phase.
Thus, while the unit
cell parameters of the mica are greater than those of phlogopite, there are fewer than three manganese atoms per mica
formula unit.
Burns (1970, p. 43) has demonstrated from
absorption spectra evidence that the distorted octahedral
site of the phlogopite structure may stabilize manganese in
the plus-three valence state.
Furthermore, natural mangano-
phyllites invariably contain aluminum in more than 10% of
the octahedral sites.
Therefore, the manganese-poor mica
synthesized in this study may represent a solid solution between the components KMn 3 +2
+2AlSi
0 10 (OH)2 + KMn 2 +3
+3AlSi33 0 10 (OH)2
33
+ KAl2 AlSi 3 00
(OH)
.
Further study on natural manganophyl-
define the extent of Mn+3/ M+2 substitution
lites is
toneeded
lites is needed to define the extent of Mn
/ Mn
substitution
-28-
in the mica's distorted octahedral sites.
-29Relations between Cell Parameters and Ionic Radii
There exist several systematic relations between unit
cell parameters and ionic radii of substituting cations.
For example, the cell dimensions am, bm and cm are each proportional to the Shannon and Prewitt (revised 1970) ionic
radii of cations substituting into the tetrahedral, octahedral or interlayer positions.
This relation is clearly de-
monstrated by Figure One of bm vs. octahedral cation ionic
radii.
The single exception to this rule is that of cm vs.
interlayer cation ionic radii (Fig. #2).
The distinct nega-
tive curvature has been explained by Prewitt as the result
of increasing coordination number of the interlayer cation
with increasing ionic radii of this cation.
For a given
cation, an increase in coordination number is accompanied
by a decrease in effective ionic radii.
As expected, unit
cell volumes are linearly related to the cube of the substituting cations' ionic radii for octahedral and tetrahedral
substitutions, and display a slight negative curvature in
the interlayer case (Figs. #3 and #4).
It is of interest to consider how bm (the cell dimension
within the mica layers) varies with respect to d0 0 1 (the dimension perpendicular to the layers) for each type of cation
substitution.
A plot of bm vs. d001 (Fig. #5) demonstrates
that octahedral, tetrahedral and interlayer cation substitutions have differing effects on the size and shape of the unit
cell.
For example, octahedral substitutions have a profound
influence on bm, while d 0 0 1 remains virtually constant.
The
+2
near-vertical plope of the R
fact.
line is a result of this
On the other hand, interlayer cation substitutions
alter the thickness d0 0 1 of the layers, while having a
3
much smaller effect on bm.
R+
and R
tutions influence both bm and d 001
.
tetrahedral substiIt should be noted that
these observations agree with the theoretical predictions
of Takeda and Morimoto (1970).
-31-
Figure #1--Monoclinic bm unit cell dimension vs. ionic
radius of the octahedral cation for micas of
+2
the form KR3 A1Si30 (OH)2. Black dots
represent biotites on the join phlogopite-annite synthesized by Wones (1963b).
32-'
0.78
0.7
CUC
2u+
0
0.70
Ni+2
bm cc Ionic
0.66
9.20
9.24
9.28
bnmA 0
-33-
Figure #2--Monoclinic cm unit cell dimension vs. ionic
radius of the interlayer cation for micas of
the form R +Mg3AlSi3010 (OH) 2.
-34-
1.60
1.40
z0
n,
0
<1
H
0z
1.20
w
X
w
z
-1.00
1.0
10.0
10.2
10.4
.
Cm in A
10.6
10.8
-35-
Figure #3--Monoclinic unit cell volume vs. ionic radius
of the octahedral R+ 2 cation cubed, for micas
+2
of the form KR2 AlSi 3 O1 0 (OH)2 . Black dots
represent biotites on the join phlogopite-annite synthesized by Wones (1963b).
---
IIYPP-~- ---
-
-
of*
Mg*
O0
0.35 -
IM
OO0.35
) o WONE S (19 6 3)
*WONE S (19 63)
UNIT CELL VOLUME
510
500
4 90
IM
UNIT CELL VOLUME (As)
I
-37-
-37,
Figure #4--Monoclinic unit cell volume vs. the cube of
+ R + cation radius for micas of
the interlayer
the form R Mg 3 AlSi 3 0 1 0 (OH)2 , and vs. the cube
of the tetrahedral R+ 3 cation radius for micas
of the form KMg 3 R+3Si 3 0 1 0 (OH)2.
-38-
to
*4
C 4.0
w
cm
S3.0
a
2.0
0
m
TEl RAHEDRAL CATION
SUBSTITUTIONS
KMg 5 F' 3 Si 3 0 10 (OH)
a
Fe+ 3
I
I
G+3A
-,-I
2
Al
0.6
S0.3
BAI+
3
0
z
0
cme
4k
c
490
Bj
__
495
IM UNIT CELL VOLUME
500
I
505
Figure #5--Monoclinic interlayer spacing d001 vs. monoclinic
bm
cell dimension.
The four lines
represent micas of the form KMg3AIR+4010 (OH)2
KMg 3 Al
KMg
3
R+Mg
R
3
+3
Si30 1 0 (OH)
AlSi30 1
0
+2
2
, KR
(OH)2"
AlSi 0
3
(OH)
010 (H
and
2,
-- - --
s
9.4--
* Fe+2
sl-~---~ -
1?*4
4
R-0+
2
*
o
I
--
R
+R
Go
4
*
*
R
9.3
<f
*
C
Fe+
0
E
+
oCo
f
.
Co3
C2
No+
9.214..
Rb
Wones (1963)
(NH4)*
A
,..s.......u,
Eugster 8 Mun
.o o,.
Phlogopite
Carman (1969)
SB
10.0
2Ni
10.2
dool = Cm-s
10.4
in,
m (A)
10.6
Substitutions and Stability
Interlayer and tetrahedral cation substitutions demonstrate that a wide range of ionic radii are possible in these
positions.
Interlayer cations vary from sodium (ionic radius
= 0.98 A*) to cesium (1.70).
Tetrahedral cations from boron
(0.12) to iron III (0.49) form stable micas.
However, octa-
hedral cations seem far more restricted in their ability to
substitute into the phlogopite sturcture.
No R
2
ation of
radius greater than iron II (0.78), including lead (1.18)
cadmium (0.95) and manganese (0.83), was found to form a stable mica.
Furthermore, Eugster and Wones (1962) have demon-
strated that the Fe
phlogopite.
+2
mica
annite is far less stable than
Thus, it appears that the stability of triocta-
hedral micas may be in part a function of the octahedral
cation's ionic radius.
It is well known that in phlogopite the ideal AlSi
tetrahedral layer is larger than the Mg 3 layer (Radoslovich
and Norrish, 1962).
If the trioctahedral mica is to be sta-
ble, then these two layers must coincide, either by expansion
of the octahedrtyaiong
am and b m or by contraction of the
A
tetrahedral layer along a and b . Radoslovich and Norrish
m
m
suggest four ways to accomplish this:
1)
Altering bond lengths of the ideal layers,
2)
tetrahedral layer tilting or corrugation,
3)
octahedral layer flattening, or
4)
tetrahedral layer rotation.
-42The altering of bond lengths is energetically far more
difficult than altering bond angles.
Thup, while such dis-
tortions have been noted in dioctahedral mica structure
studies (Takeda and Burnham, 1969), bond stretching or contraction is assumed to be a minor effect.
Tetrahedral
tilting or corrugation is also well documented by Takeda
and Burnham in their study of dioctahedral fluor-lithionite.
However, these authors believe that tilting of tetrahedra
will be minimized when all three octahedral positions are
filled.
Donnay, Donnay and Takeda (1963) have demonstrated that
the octahedral 001 projection may conform to the larger tetrahedral layer by octahedral layer flattening (See Fig. #6).
In this way bond lengths are preserved while bond angles are
altered.
The amount of compression may be represented by the
angle P, which has the value 54044 ' in an ideal octahedron.
If the assumptions are made that:
1)
there is no tetrahedral tilting or corrugation
(i.e., basal oxygens in each tetrahedral sheet are
coplanar),
2)
001 projections of tetrahedra are equilateral triangles, and
3)
am = bm/
,
then q is a simple function of the mean octahedral bond length
d and cell dimension b :
om
sin Y = b /3Y/d .
mn
o
hedral bond length for Mg-(O,OH) and Fe
-
The mean octa-
(O,OH)
are given
by Donnay, Donnay and Takeda (1963) as 2.07 A* and 2.12 Ao
-43-
Figure #6--Expansion of the octahedral 001 projection by
octahedral layer compression.
OC TAHEDRAL
S= Arc
LAYER
sin (b/3
COMPRESSION
*T
do.)
boa 3.
do * E
001
Projections
Ideal Octahedron:
Y =54P44 '
Flattened
Y> 54044
Y Axis
Projections
_
~i~ __f_~l_
_I_~____~___
1_ _lll_____~__~____F_
IFI1-~----__.~~__sl1~_l____I
~___1_-__-_1~~----~~~~..
.~11111111~
B
Octahedron:
-45respectively.
Mean bond lengths for other octahedral cations
maybe calculated by interpolation.
Thus, knowing bm , we
can calculate T for each octahedral layer substitution.
In.
Figure #7, T is plotted vs. octahedral cation ionic radius.
As ionic radius increases, the value of T is noted to decrease slightly.
Thus, larger octahedral cations require
less site flattening to expand the 001 octahedral projection.
While octahedral layer flattening is a real effect in hydrous
trioctahedral micas, this structural parameter does not explain the instability of 100% octahedral substitutions of
cations larger than iron II.
Tetrahedral layer rotation is a fourth means of fitting
the non-equivalent octahedral and tetrahedral layers (see
Fig. #8).
Donnay, Donnay and Takeda
(1963) have shown that
by rotating each tetrahedron through an angle a about an axis
perpendicular to the 001 plane, the effective size of the
tetrahedral sheet is reduced.
Structure studies by Steinfink
(1962) and others reveal values for a may be greater than
100 in natural micas.
Thus, in phlogopite the strain between
octahedral and tetrahedral layers may be released primarily
through tetrahedral layer rotation.
If the conditions assumed by Donnay, Donnay and Takeda
(1963) for octahedral layer flattening are correct, then
a
is defined by the mean tetrahedral bond length dt and the
cell dimension bm:
cop Q = b/4*4.-d
t .
bond length for the AlSi
The mean tetrahedral
layer is known to be 1.643 ± .002A 0
from studies of muscovite (Guven, 1967 and Burnham and
Figure #7--Octahedral layer compression angle T vs. ionic
radius of the octahedral R+ 2 cation in micas
+2
of the form KR2AlSi30 (OH)2. Black dots
represent biotites on the join phlogopite-annite synthesized by Wones (1963b).
-47-
I
0.78
I
I
m~+1
0
*
0
Co~ 2
0.74 LC U+2
n,
0
02 0.70 1-
Ni+2
* Wones (1963)
0.661-
I
580
I
590
I
P = Arc sin (bm / 3V-do )
I
600
48-
Figure #8--Contraction of the tetrahedral 001 projection
by tetrahedral layer rotation.
_ _~
_~_~
~
~
TETRAHEDRAL
LAYER ROTATION
a = Arc cos (b/42dt)
S= 30
D
cru~ar~-UI
--------_lr-~~~~Il
I-----
- -1
~~_
---arn*n~---aq\cr.PI-Y~-~----r~naaanr~
_ 1.
Or
-50-
Radoslovich, 1964), biotite (Franzini, 1963) and fluorphlogopite (McCauley, 1968).
known values of bm,
With this value of dt, and the
a plot of R+ 2 ionic radius vs. a has been
constructed for micas of the form KR 3
Fig. #9).
2A1Si
O02(OH)2
(see
As the octahedral cation ionic radius increases
to 0.76 AO, a approaches the critical value of 0*.
For octa-
hedral cations of ionic radius greater than f0.76 AO, the
tetrahedral layer cannot expand further by rotation.
It
might therefore be expected that hydrous trioctahedral micas
with an AlSi
tetrahedral layer would not be stable for an
cation
3octahedral
A0 .
0.76 A
than about
about 0.76
greater than
of radius
radius greater
cation of
layer
octahedral layer
Figure #9--Tetrahedral layer rotation angle a vs. ionic
radius of the octahedral R+ 2 cation for micas
of the form KR+2
Black dots
3 2A1Si 3 O1 0 (OH)2 .
represent biotites on the join phlogopite-annite synthesized by Wones (1963b).
-52-
!
I
0Fe+2
0.78
I
-
0
*
•0
-
._-
Cu
Cu42
++
N
-0.70
z0
Ni
* Wones (1963)
0.66
I
00
oI
50
S= Arc cos (bm/4r- d t)
100
-53-
Octahedral Cation Diptribution tn Natural Micasp
Foster (1960) has plotted the octahedral cation distribution for over 200 natural phlogopites, biotites and piderophyllites (Fig. #10).
As the iron II content of these micas
increases, so does the octahedral aluminum content.
Trivalent
aluminum in R + 2 sites requires a corresponding substitution
of aluminum for silicon in the tetrahedral layer.
Thus, alu-
minum has the dual effect of increasing the size of the tetrahedral layer, while decreasing the effective octahedral cation
radius.
The maximum observed effective octahedral ionic rad-
ius, for the most iron-rich, aluminum-poor specimens, is 0.74
A0 .
Similarly, manganophyllites are known with almost 20%
MnO substituting for MgO (Jakob, 1925), resulting in an effective octahedral ionic radius of 0.74 A0 .
Thus, while octahe-
dral cations in natural micas of the form KR 2 AlSi3 010 (OH)2
the ionic
radius
of
0.76
A,
arer
approach the critical
obnoto
critical
ionic radius
of 0.76
A0°3approach
,tethey
b
served to exceed this value.
-54-
Figure #10--The composition of the octahedral layer of
more than 200 natural phlogopites, biotites
and siderophyllites from Foster (1960).
~_I_
____
1~1_
___
__
~-7~7
/2
vI
10
*
Siderophyllites and
lepidomelanes
S
P+ 3
+ 90
90
80
so70
70
60
50
40
30
20
0
60
50
40
30
20
10--
I
_
~
+
Fc-
(+ 2
)
The Composition of Annite
Synthetic annite was noted to be the only hydrous trioctahedral mica of the form KR3 +2AlSi30
1 0 (OH)2
which appears
to have an average octahedral ionic radius greater than the
critical Value of 0.76 AO.
Eugster and Wones (1962) have
demonstrated that trivalent iron (VI ionic radius = 0.63 A0 )
may substitute for octahedral divalent iron (0.78 A*) in
annite as expressed by the oxyannite reaction:
+2
KFe
2
3+ AlSi3 0 10(OH)
2-
+3
+H
K(Fe +2Fe2 +3) AlSi 0 2+
An annite with 212 mole percent octahedral Fe
H.
(i.e. Q,18
mole percent oxyannite) has an average octahedral cation
radius of 0.76 A0 , and it was thus predicted that even the
most reduced synthetic annites may have appreciable oxyannite
content.
Subsequent study by Wones, Burns and Carroll (1971)
employing Mssbauer and analytical chemistry techniques have
confirmed that at least 10 mole % of octahedral iron in all
synthetic annnites is in the trivalent state.
It therefore
appears that octahedral cation size restrictions, resulting
from the misfit between octahedral and tetrahedral mica
layers, may have a profound effect on the valency of iron in
annite.
From Fig. #MR it can be seen that for synthetic biotites
of high iron content, tetrahedral rotation (i.e., a ) is
zero.
Therefore, from Donnay, Donnay and Takeda (1963):
cos a = 1 = bm/4-e4
.dt
for these micas.
However, Wones (1963b) has shown that values for bm increase
-57with increasing Fe content, in these high-iron biotites.
is
It must therefore be assumed that d
also increasing in
order to maintain the relation bm/dt = 4'f for these micas.
One possible way to increase the mean tetrahedral bond
length dt is by substitution of Fe
hedral layer.
+3
for Al
+3
in the tetra-
Since bm for annite = 9.348 AQ, then dt =
9.348/4q2 = 1.652 A*.
Donnay, Donnay and Takeda (1963) have
suggested a value of 1.68 A0 for d of the FeSi 3 tetrahedral
t3
layer, as opposed to the smaller 1.643 A0 mean tetrahedral
bond length for an AlSi 3 sheet.
plies a composition of (Fe0
2,
Al
Therefore, d t = 1.652 ime) Si3
(i.e.
7% total
iron is trivalent and in tetrahedral sites) for annites'
tetrahedral layer.
Indeed, M05ssbauer studies by Burns
(see Wones, Burns and Carroll, 1971) confirm that 6.5% total
Fetetrahedral
is
Fe+3
Fe is tetrahedral Fe
-58Prediction of Trioctahedral Mica Stability
It has been phown that bm is proportional to the octahedral cation ionic radius (Fig. #1).
is proportional to bm/d t
.
But we know that cos a
Therefore, cos a is proportional
to octahedral ionic radius/dt.
This linear relation is de+2
monstrated in Figure #11, a plot of cos a vs. R
radii for varying mean tetrahedral bond length dt.
ionic
The line
for an AlSi 3 tetrahedral layer (dt = 1.643) has been developed
previously (Fig. #9).
Donnay, Donnay and Takeda (1963) sug-
gest a value of d t = 1.68 AQ for the FeSi 3 tetrahedral layer,
line on
to
used
2
and this value has been
F+2
o+2 a second
+2 obtain
Ni+
Figure #11 defined by Ni,
pites.
Mg + 2 , Co2 and Fe 2 ferri-phlogo-
By noting that these two lines are parallel, and by
calculating additional mean tetrahedral bond lengths from
data of Shannon and Prewitt (rev. 1970), additional lines
can be drawn for the BSi 3 , GaSi
3
and AlGe 3 tetrahedral layers.
The resulting nomogram is found in Figure #12.
The inter-
section of any line with cos a = 1.00 defines the critical
octahedral cation radius for a hydrous trioctahedral mica
with a mean tetrahedral bond length corresponding to that
line.
Thus, if the composition of a hydrous trioctahedral
mica is known, systematic relations between composition and
ionic radii enable us to predict unit cell dimensions,
structural parameters, and even the stability of the mica.
-59-
Figure #11--Cosine of the tetrahedral layer rotation
angle a vs. octahedral cation radius for
+2
micas of the form KR (AlSi3 )O 0 (OH)
3
3 10
2
0
[d = 1.643 A ] and of the form KR+2(FeSi)
t
[t
3
3)
0
01 0 (OH)2 [dt = 1.68 A ].
-60-
7a:
.970
.980
bm /41 d,
.990
(= Cos ex)
1.000
-61-
Figure #12--A nomogram for cos a vs. octahedral R+ 2
cation radius vs. mean tetrahedral bond
length dt for all hydrous, potassic, trioctahedral micas.
0.84
00tOBO
v<
.80
S0.76
S
0.72
0.68
0
-O.7
0.68
0.96
0.94
- ~~
~
~
-~
~ -----~--- ~
-d t
bm /4-V
4
0.98
1.00
(= COS a)
~ cx)
dt (=cos
v'---~~.~-.----------b / ~l_~l~la~_..
~
~
JI-
'r
-
FUTURE STUDTES
Several future studies are suggested by the present
work.
Of primary importance is the need for a structure
While nearly
determination of a hydrous trioctahedral mica.
pure specimens of natural hydrous phlogopite exist (Foster,
1960), no x-ray crystal structural study of such a mica has
been published.
Structure studies of natural Zn and Mn
micas would enhance our understanding of both mica structure
and the role of Zn and Mn in these hydrous silicates.
It is well known that transition metal cations may
induce site distortions in silicates.
Examinations of the
absorption spectra of Ni, Cu, Co, Fe and Mn-bearing micas
might provide information regarding the nature and extent
of such distortions.
The greatest difficulty in performing x-ray and spectral
single crystal work on synthetic hydrous micas is that such
crystallites rarely exceed 20P in diameter.
A technique for
growing larger crystals under hydrothermal conditions would
benefit both this and many other researches.
Several alter-
ations in the standard hydrothermal apparatus might facilitate single crystal growth.
The use of higher ratios of
H20 to starting material might increase mobility of solids
while decreasing the number of nucleation sites.
A larger
volume of starting materials, requiring a larger capsule,
might also aid in macrocrystal development.
A third tech-
nique for increasing crystallite size might be to super-
-64impose a directional stress onto the hydrothermal system.
Such a directional stress field might lower the surface free
energy of large crystals.
As mentioned previously, the refractive energies of
water and transition metals in silicates are not well known.
A systematic study of hydrous silicate indices of refraction
vs. composition would enable more meaningful applications
of the rule of Gladstone and Dale.
The present study by no means has considered all possible end-member micas.
Rather, it demonstrates the vast
number of synthetic micas, of both end-member and intermediate compositions, that may be produced with relative
ease.
Future studies on the effects of cation substi-
tutions on the physical properties of dioctahedral micas
and fluor-trioctahedral micas would enhance our present
understanding of the sheet silicate structure.
Indeed,
the method of cation substitution in silicate minerals can
provide useful information about virtually every silicate
structure.
-65Referencep
Barnes, H.L, and W.G. Ernst (1963) Xdeality and ionization in
hydrothermal fluids:
The system MgO-H20-NaoH'. Amer. Jour.
Sci., 261, 129-150..
Burnham, C.W. and E.W. Radoslovich (1964) Crystal structures
of coexisting muscovite and paragonite.
Carnegie Inst.
Wash. Yearb., 63, 232-236.
Burns, R.G. (1970) Mineralogical Applications of Crystal
Field Theory.
England,
Cambridge University Press, Cambridge,
2 2 4 p.
Carman, J.H. (1969) The study of the system NaAlSiQ-Mg 2 SiO 4 SiO2 - H20 from 200 to 5000 bars and 800 0 C to 1100 0 C and
its petrologic applications.
Ph.D. Thesis, Penn. State
Univ. 290p.
Crowley, M.S. and R. Roy (1960) The effect of formation pressure on sheet structures - a possible case of Al-Si
ordering.
Geochim. Cosmochim. Acta, 18, 94-100.
DeVries, R.C. and R. Roy (1958) The influence of ionic substitution on the stability of micas and chlorites.
Geol.,
Econ.
53, 958-965.
Donnay, G., J.D.H. Donnay and H. Takeda (1964) Trioctahedral
one-layer micas. 3r.
Prediction of the structure from
composition and cell dimensions.
Acta Cryst., 17, 1371--
1381.
Edison, T.A. (1916) U.S. Patent #1,167,484.
Chem. Abstracts,
10, 725.
Eugster, H.P. (1957) Heterogeneous-reactions involving
-66oxidation and reduction at high preppures and temperatures.
J. Chem. Phyp., 26, 1160.
Eugster, H.P. and J. Munoz (1966) Ammonium micap:
sources of atmospheric ammonia and nitrogen.
Popsible
Science,
151, 683-686.
Eugster, H.P. and D.R. Wones (1962) Stability relations of
the ferruginous biotite, annite.
J. Petrol., 3, 82-125.
Eugster, H.P. and T.L. Wright (1960) Synthetic hydrous boron
micas.
U.S. Geol. Survey PP400, B441-B442.
Figlarz, M. and F. Vincent (1968) Sur la deshydmtation de
l'hydroxyde .de cobalt Co(0H)2.
C.R. Acad. Sc. Paris,
266, 376-378.
Foster, M.D. (1960) Interpretation of the composition of
Trioctahedral micas.
U.S. Geol. Survey PP 354-B, 11-46.
Franzini, M. (1963) On the crystal structure of biotite.
Zeit. Krist., 119, 297-309.
Franzini, M. (1969) The A and B mica layers. Contrib. Mineral.
Petrol., 21, 203-224.
Frondel, C. and J. Ito (1966) Hendricksite, a new species of
mica.
Amer. Mineral. 51, 1107-1123.'
Gladstone, J.H. and T.P. Dale (1864) Researches on the refraction, dispersion, and sensitiveness of liquids.
Phil.
Trans. Roy. Soc. London, 153, 337-348.
Given, N. (1967) The crystal structure of 2M, phengite and
2M muscovite.
Carnegie Inst. Wash Yearb. 66, 487-492.
Hatch, R.A., R.A. Humphrey, W. Eitel and J.E. Comeforo (1957)
Synthetic mica investigations. IX.
Review of progess
-67from 1947-1955,
Jaffe,
U.S. Bureau of Minep, Rept. Inv. 5337.
H.W. (1956) Application of the rule of Gladptone
and Dale to minerals.
Amer. Mineral., 41, 757-777.
Jakob, J. (1925) Beitrage zur chemischen konstitution der
glimmer. I. Mitteilung:
die schwedischen manganophylle.
Zeit. Krist., 61, 155.
Klingsberg, C. and R. Roy (1957) Synthesis, stability and
polytypism of mickel and gallium phlogopite.
Amer.
Mineral., 42, 629-634.
Larsen, E.S. and H. Berman (1934) The microscopic determination of the nonopaque minerals.
U.S. Geol. Surv. Bull.,
848, 266 p.
McCauley, J.W. (1968) Crystal structures of the micas KMg 3AlSi30 2 0 F 2 and BaLiMg 2AlSi 3Oo
1 0 F2 .
Ph.D. Thesis, Penn.
State Univ., 180p.
Neumann, H. (1949) Notes on the mineralogy and geochemistry
of zinc.
Mineral. Mag., 28, 575-581.
Pistorius, C.W.F.T. (1962) Thermal decomposition of the hydroxides of cobalt and nickel to 100 kilobars.
Zeit.
fur P. Chem., 34, 287-294.
Prewitt, C.T. (1971) Private Communication.
Radoslovich, E.W. (1960) The structure of muscovite, KAl 2 (Si3Al)O0,(OH) 2 . Acta Cryst., 13, 919-932.
Radoslovich, E.W. (1962) The cell dimensions and symmetray
of layer lattice silicates. II.
Regression relations.
Amer. Mineral., 47, 617-636.
Radoslovich, E.W. and K. Norrish (1962)The cell dimensions
-68and symmetry of layer lattice pil4catep. I.
tural considerations.
Some struc-
Amer. Mineral., 47, 599-616.
Schairer, J.F. and N.L. Bowen (1955) The pyptem K 20-AI 2 0 3 Si0 2 . Amer. Jour. Sci., 253, 681-746.
Seifert, F. and W. Schreyer (1971) Synthesip and stability of
micas in the system K 2 0-MgO-SiO 2 - H20 and the relations to
phlogopite.
Contrib. Mineral. Petrol., 30, 196-215.
Shannon, R.D. and C.T. Prewitt (1970) Revised values of
effective ionic radii. Acta Cryst., 26, 1046-1048.
Shaw, H. (1963) The four-phase curve sanidine-quartz-liquidgas between 500 and 4000 bars.
Amer. Mineral., 48, 883-
896.
Smith, J.V. {'ed.]
(1967) X-ray Powder Data File.
American
Society for Testing and Materials, Philadelphia, Pa.
Smith, J.V. and H.S. Yoder (1956) Experimental and theoretical
studies of the mica polymorphs.
Mineral. Mag., 31, 209-
235.
Steinfink, H. (1962) Crystal structure of a trioctahedral
mica:
phlogopite.
Amer. Mineral., 47, 886-896.
Stubicon, V. and R. Roy (1962) Boron substitution in synthetic micas and clays.
Amer. Mineral. 47, 1166-1173.
Takeda, H. and C.W. Burnham (1969) Fluor-polylithionite:
2
A lithium mica with nearly hexagonal (Si2 s0)
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Mineral.
Jour., 6, 102-109.
Takeda, H. and N. Morimoto (1970) Crystal chemistry of rockforming minerals. I.
Structural studies of micas.
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-69Tuttle, O.F. (1949) Two pressure vesppels for splicate-water
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Geol. Soc. Amer. Bull., 60, 1727-1729.
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Wise, W.S. and H.P. Eugster (1964) Celadonite:
thermal stability and occurrence.
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Wones, D.R. (1963a) Phase equilibria of "ferriannite,"
KFe
3
Fe 3
0 10 (OH)2 . Amer. Jour. Sci., 261, 581-596.
Wones, D.R. (1963b) Physical properties of synthetic biotites on the join phlogopite-annite.
Amer. Mineral., 48,
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Wones, D.R. (1967) A low pressure investigation of the stability of phlogopite.
Geochim. Cosmochim. Acta, 31,
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Stability and
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Experiment, theory and application.
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-70-.
APPENDTX A--The stability of hydrou§ trioctahedral
micap and their related hydroxidep.
Introduction
It has been demonstrated that mica stability is closely
related to the ionic radius of the octahedral cation.
Rado-
slovich (1963) and others have noted that the octahedral
layer of trioctahedral micas possesses a structure analagous
to that of brucite--Mg(OH) 2 . Therefore, in conjunction with
studies on the physical properties of hydrous trioctahedral
micas, stability relations of nickel and cobalt micas and
hydroxides are now being determined.
While this work is
not finalized, a preliminary report follows.
Several studies on the stabilities of hydrous trioctahedral micas and their related hydroxides have been presented by previous investigators.
Brucite--Mg(OH) 2 sta-
bilities have been examined by several authors, the most
frequently cited being that of Barnes and Ernst (1963).
The hydroxide stabilities of cobalt and nickel have been
determined by Pistorius (1962) for pressures from 5 to 100
kilobars.
Van My (1964) and Figlarz and Vincent (1968) pro-
vide additional data on these stabilitiep.
previously (see Table One),
AS mentioned
several authors have examined
stabilities of hydrous trioctahedral micas of the form
+2
The most important of these studiep are,
KR32AlSi3010(OH)2.
2
+
for Mg , Yoder and Eugster (1954) and Wones (1967); for
Fe+ 2 , Eugster and Wones (1962) and Wones, Burns & Carroll
(1971); and for Ni + 2 , Klingsberg and Roy (1957).
Experiments and Data
All stability experiments were performed in standard
hydrothermal pressure apparatus as previously described.
A
partial list of synthesis experiments and resulting stability
points thus far completed may be found in Table A-1.
quenching of pure CoO, Co(OH) 2'
Slow
NiO and Ni(OH) 2 from stability
curve temperatures and pressures revealed no development of
other phases.
It is therefore assumed that no anomalous
phase development took place in fast-quenching of these stability determination experiments.
In order to determine thermodynamic properties of the
hydroxides and oxides of cobalt and nickel, the unit cell
volumes of these substances have been redetermined (see
Table A-2).
While volume and cell parameters of CoO,
Co(OH) 2 and NiO are in close agreement with those reported
in the ASTM File (Smith (ed.), 1967), those of Ni(OH) 2 are
somewhat lower than ASTM values.
Future work will consider
this discrepancy more carefully, and determinations of the
cell parameters of Ni(OH) 2 formed at a range of temperatures
will be performed.
Preliminary Conclusions
Data of Pistorius (1962) and of this ptudy agree that
Co(OH) 2 and Ni(OH) 2 dehydrate at much lower temperatures
than Mg(OH) 2 , but are certainly more stable than Fe(OH) 2
-72r
TABLE A-l--Stability Experiments
a.
CoO + R2 0
co
Co(QH) 2
Cobalt Hydroxide Dehydration:
Reactants
Products
208
CoO
200
214
2000
240
Co (OH) 2
CoO
CoO + Co(OH)
CoO
2000
244
Co (OH)
Pressure
(bars)
Temperature
200
(Oc)
(..
Stability Points:
Duration
(hrs.)
CoO + Co(OH)
2
2
CoO
2
(200 ± 2 bars, 211 ± 3 0C)
(2000
±
242 ± 2 C)
20 brs,
(5 ±1 kbars, 258 ±10 0C)
b.
(15 ±1 kbars,
297 ± 5 C)
(27 ±1.5 kbs,
308
(50 ±2.5 kbs,
315 ± 50C)
Nickel Hydroxide Dehydration:
Ni(OH)2
+
10 C)
NiO + H20.
Reactants
Products
265
NiO
200
270
Ni (OH) 2
NiO + Ni(OH)
NiO
2000
275
NiO
Ni (OH)
2000
280
2000
285
Pressure
(bars)
Temperature
(0C)
200
Stability Points:
Duration
(hrs.)
Ni(OH)
48
2
(200 ±2 bars,
(2000 ±20 brs,
1(5± 1 kbars,
268 ± 3 0C)
280 ± 5 C)
295 ± 50C)*
(16 ±1 kbars, 325 ±100C)
(31.5 ±1.5 kb, 330 ±15 0C)
(50 ± 2.5 kb, 338 ±12 0 C)
(100 ± 5 kb, 345 ± 50C)
,--Data of PistoriuP (1962)
2
NiO + Ni(OH)
Ni(OH) 2
NiO
2
2
-73r
Table A-l--Continued
c.
Cobalt Mica Dehydration;
KCo 3 A1Si 3 Q 1 0 (QH)2
CoQ + Co 2 SiO 4 + KA1Si 2 06
Pressure
(bars)
Temperature
(°C)
Duration
100
790
48B
Gel
100
795
48
Gel
Reactants
Products
(hrs.)
Co Mica
Co Mica,
CoO,
Co2SiO
CO2 si0 44 &
Leucite
100
802
32
205
825
46
Gel
Co Mica
205
880
39
Gel
CoO, Co 2 SiO 4 ,
Co Mica
CoO, Co 2 SiO 4 ,
& Leucite
& Leucite
300
875
Stability Points:
48
Gel
CoO, Co2SiO41
& Leucite
(100 ±1 bars, 796 ±6 0 C)
(205 ±2 bars, 850 ±200C)
-74-
Table A-2--Cell parameterp and
dspacing
hkl
for the Oxidep and Hydroxidep
of Cobalt and Nickel
a.
Oxides:
CoO
This StudNiO
hkl
This Study
ASTM File
This Study
ASTM File
111
ill
2.4599
2.460
2.410
200
2.1295
2.130
2.4108
2.0881
220
1.5059
1.5062
1.4766
1.476
311
1.2840
1.2846
1.2596
1.259
222
1.2298
1.2298
1.2059
1.206
a
4.2595
4.260
4.17665
4.1769
77.281
77.31
72.859
72.872
(A )'
Vol.
b.
3
(A)
2.088
Hydroxides:
hkl
This Study
001
4.654
100
ASTM File
Ni (OH) 2
This Study
ASTM File
4.638
4.605
2.755
4.66
2.76
2.706
2.707
101
2.368
2.38
2.336
2.334
102
1.78
1.60
1.758
1.754
110
1.776
1.594
1.563
1.563
ill
1.506
1.51
1.481
1.480
103
1.352
1.36
a
3.182
4.653
3.179
4.649
3.125
3.126
4.628
4.608
(Ao)
c (A 0 )
Vol.
(A
)
3
40.795
40.688
Brucite--Mg(OH) 2 :
39.15
a = 3.147 A
b = 4.769 A
3
Vol = 40.9026 A
38.97
-75-
Furthermore,
which is metastable at laboratory condition§.
Co(OH) 2 has a slightly lower thermal ptability than Ni(OH) 2 .
This relative pequence of ptabilitiep:
Fe(OH) 2
<
Co(OH) 2
<
Ni(OH) 2 < Mg(OH) 2 , is identical to the order of stabilities
+2
.+2
+2
+2
micas. Therefore, we may
seen in Fe
,
Co
, N+
and Mg
conclude that the factors which control the qualitative (if
not quantitative) aspects of hydroxide stabilities may also
strongly influence trioctahedral mica stabilities.
Ionic radii, crystal field stabilization, and oxidation
potential of the octahedral cation are all known to affect
the pressure-temperature stability of micas.
Furthermore,
octahedral cations affect the dehydration products of micas.
While nickel and cobalt phlogopite react to form monoxide
plus olivine plus leucite, Mg-phlogopite reacts to form
kalsilite plus olivine plus leucite, and annite dehydrates
to sanidine and magnetite!
Clearly, the differences in
AVrx n for the decomposition of these four micas will affect
the pressure stabilities.
Accuratedeterminations of a vari-
ety of mica dehydrations will aid in our understanding of
these controls on the stability of micas.
APPENDIX B--Selected computer d-spacing
output for synthetic micas.
On the following pages are computer output d-spacings
for the micas listed below:
Formulae
Run Number
KMg 3 AlSi 3 0 1 0 (OH)2
Ml
Ni 3
M7b
Cu 3
M49
Co 3
Ml14
Zn 3
Ml01
Mn 3
M91
KMg 3 B Si
3010
(OH)
2
Ga
Fe+
Ml08
M109
3
KMg 3 AlGe 3 0 1 0 (OH)2
Mll
M68
.r--
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-87VITA
The author was born in Rockville Center, Long Island,
New York on November 1, 1948.
He graduated with high honors
from Ridgewood High School, Ridgewood, New Jersey where he
concentrated in science and music.
He entered the Massachu-
setts Institute of Technology in September of 1966, and subsequently enrolled in the five-year Masters degree program
in the Department of Earth and Planetary Sciences.
In addition to his scientific studies, the author has
studied trumpet privately for four years with AndreCome of
the Boston Symphony Orchestra.
He has been principle trum-
pet of the M. I. T. Symphony Orchestra for five years, and
has appeared as soloist with the M. I. T. Concert Band, Symphony Orchestra, and many other groups in more than a dozen
states.
Among the author's academic awards are the Harvard
Alumni Award (1965), the New Jersey Science Teachers' Award
(1966), Outstanding Musician--New York State Music Festival
(1966), and the Phi Sigma Kappa Foundation Award (1968).
He
is a member of Sigma Xi, Phi Lambda Upsilon, and Baton honorary societies.
Professional experience includes summer work with Isotopes, Inc. of Westwood, New Jersey (1968) and as field
assistant for the United States Geological Survey (1970).
Next year the author will continue hip studies at Harvard
University, and will receive for a second year a National
Science Foundation Fellowship.
-88-
The author was married to Margaret Joan Hndle on August
9,
1969,