Phase transitions and

exsolution phenomena in
pyroxenes
 Cleavage in the pyroxenes

001

010
100

110
110
Optical micrograph showing two cleavages at 90o
Exsolution lamellae in pyroxenes
Because exsolution takes place by the solid state diffusion of ions
through the structure, it is very slow and so the two phases generally
exist on a microscopic scale

0.1mm
Basic structure and chemistry of
pyroxenes XYZ2O6

Pyroxene endmembers :

i) enstatite Mg2Si2O6 (or

simply MgSiO3)
ii) ferrosilite Fe2Si2O6 (or
simply FeSiO3)
iii) diopside CaMgSi2O6
iv) hedenbergite CaFeSi2O6
v) jadeite NaAlSi2O6
vi) Ca-Tschermak
CaAl(AlSi)O6
Pyroxene chain - ‘I-beams’
The structure of pyroxenes :
Two opposing chains connected by a chain of octahedra : I-beam

I-beam
Pyroxene structure from ‘I-beams’
Clinopyroxene and orthopyroxene structures
How does the silicate chain fit to the octahedral chain?

QuickTime™ and a
Graphics decompressor
are needed to see this picture.
How can the silicate chain fit to the octahedral chain?

Diopside chain Pigeonite chain

High - low pigeonite
 Table 1 C2/c Pbca P21/c
Size and
Small Small Small
coordinatio
[6] [6] [6]
n

M
Shape Regular Regular Regular
1
Small cations such as Small cations such as Small cations such as
Cations
Mg, Fe2+, Al Mg, Fe2+, Al Mg, Fe2+, Al

Large Small Small

Size
[8] [6]-[7] [7]

M
Shape Irregular Irregular Irregular
2
Only small cations such Small amount of Ca is
Large cations such as
Cations as Mg and Fe2+ tolerated. Mainly Mg
Na, Ca
Very little Ca! and Fe2+
Pyroxene solid solutions
P-T relations of enstatite MgSiO3
Augite- pigeonite phase diagram (pseudo-binary)
Behaviour of pyroxenes during cooling
Behaviour of pyroxenes during cooling
Behaviour of pyroxenes during cooling
 a

c AUG
9.8Å
106o

Accommodation of strain 9.7Å 9.7Å

within exsolution lamellae 110 o

110 o
PIG

9.9o

9.8Å
AUG
(001)
106 o

(a)
a

c
9.8Å
AUG
106 o

9.8Å
PIG
110 o

(001)
9.8Å
AUG
106o

(b)
a

c
9.8Å
AUG
106o

7.9 o
9.9Å
(001)
110o

PIG

9.8Å
AUG
106o

(c)
Accommodation of strain in exsolution lamellae
The growth of exsolution lamellae
The growth of exsolution lamellae : experiments
Twinning in clinopyroxene
Pigeonite to orthopyroxene
transformation

1. Formation of a twinned crystal of

clinopyroxene (pigeonite)
2. Exsolution of augite from
pigeonite
3. Transformation of pigeonite to
orthopyroxene
4. Exsolution of augite from
orthopyroxene
Na-bearing pyroxenes
Jadeite : NaAlSi2O6
Aegerine : NaFe3+Si2O6
The solid solution : Jadeite - Diopside

NaAlSi2O6 - CaMgSi2O6
Cation ordering in omphacite
Cation ordering in omphacite
Phase transitions and exsolution in
the alkali feldspars
Phase transitions in the feldspars

There are three types of behaviour which take place in the feldspar structure on
cooling:
At high temperatures:
(i) at high temperatures the feldspar structure is expanded and can contain Na,
K and Ca in the large M-sites.

(ii) at high temperatures the Al and Si are randomly distributed in the T-sites

(iii) at high temperatures there are extensive solid solutions in the alkali
feldspars and in the plagioclase feldspars.

In this ideal high-T state, feldspars are monoclinic.

Phase transitions in the feldspars

(iv) at lower temperatures there is a tendency for the structure to distort

by a displacive transition. This tendency depends on the size of the cation
in the M-site. K is large and prevents the distortion, Na and Ca are smaller
and so the structure distorts to triclinic.

(v) there is also a strong tendency for Al and Si to become ordered as the
temperature is reduced. This is to avoid Al in adjacent tetrahedra (the
aluminium avoidance rule or Loewenstein’s Rule).

(vi) at lower temperatures the extent of solid solution decreases i.e.

exsolution processes
K - Feldspars

sanidine KAlSi3O8
orthoclase
microcline

rasrs
sdpsap
efledl
lailif
klak
AAl

Plagioclase feldspars
NaAlSi3O8 CaAl2Si2O8
albite anorthite
Phase transitions in K-feldspar, KAlSi3O8

1. At high temperature the structure is monoclinic with Al,Si disordered. This

is called sanidine.
2. As the temperature decreases Al tends to go into one of the T1 sites. This
reduces the symmetry to triclinic.
This has an important consequence :
Transformation twinning
c c
b Diad b
axis
The 2 equivalent orientations of
(a) Mirror (b) Triclinic the triclinic unit cell can form
plane cell
twin domains, either related by a
c mirror plane (albite twin) or by a
c c b diad axis (pericline twin).
b b b
c
When both possibilities
(c) Albite (d) Pericline
exist in a single crystal
twin twin then there are two twin
planes at right angles
Phase transitions in K-feldspar, KAlSi3O8

Fully Al,Si ordered K-feldspar is called microcline.

Microcline has characteristic cross-hatched twinning, seen in a polarizing
microscope :

This characteristic microstructure is due to the existence of both albite and pericline
twinning in the crystal which has transformed from the high temperature disordered
monoclinic structure.
 KAlSi3O8
Sanidine Microcline
Orthoclase : an intermediate
Monoclinic stage between sanidine and Triclinic
Al,Si disordered microcline. It is monoclinic on Al,Si ordered
average, but in an electron
Found in volcanic microscope it looks like Found in plutonic
(fast cooled) microcline i.e. very fine twins (slowly cooled)
rocks rocks

Found in rocks with intermediate

cooling rate
Na - Feldspars

sanidine KAlSi3O8
orthoclase
microcline

rasrs
sdpsap
efledl
lailif
klak
AAl

Plagioclase feldspars
NaAlSi3O8 CaAl2Si2O8
albite anorthite
Phase transitions in Na-feldspar, NaAlSi3O8

1. At very high temperature the structure is monoclinic with Al,Si

disordered. This is called monalbite.
But on cooling below about 1000oC monalbite undergoes a displacive
transition to triclinic symmetry because the Na is too small to stop the
structure from distorting. This triclinic albite is called high albite.
In most rocks albite grows as high albite because the temperature is
below that where albite is monoclinic.
2. As the temperature decreases Al, Si begin to order. There is no
twinning associated with this because high albite is already triclinic and
cannot reduce its symmetry further.

Albite with ordered Al,Si is called low albite. It has no transformation

twinning.
Alkali - Feldspars

sanidine KAlSi3O8
orthoclase
microcline

rs ras
sdpsap
efldel
lai lfi
lklak
AA

Plagioclase feldspars
NaAlSi3O8 CaAl2Si2O8
albite anorthite
The alkali feldspar phase diagram

1000 The disordered solid

Disordered solid solution can only exist at
M solution
high temperatures.
800
T solvus Below the solvus the solid
High
Ab solution breaks down to 2
600 Al,Si orde phases - one Na-rich, the
Low ri ng M
Ab other K-rich.
T
400 This exsolution process
Na-feldspar + K-feldspar results in a 2-phase
intergrowth, called perthite
“Perthite”
200

0 20 40 60 80 100
Na-Feldspar Composition K-Feldspar
The alkali feldspar phase diagram
Perthite microstructure - an
intergrowth of Na-feldspar
and K-feldspar
Cross-hatched twinning
Na-feldspar in K-feldspar

te
whi