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CHAPTER

II.

PREPARATTON OF THE SAMPLE


2.1

Methods o:( arowl.ng crystals.


Large high quality crystals of various

~re

of great

imrort~nce

as materials for technological and

industrial purposes and their use in


seems to be boundless,

suh~t~nces

~olid

state physics

Hence there has recently been a

renewal of interest in the methods of growing crystals and


this brilnch of sci.ence is more actively cultivated than ever
in its history.

A survey of the general methocls of growing

si.ngle crystals ie given helow which is followed by the


description of the rr.ethorls used in the present case.
(A)

Crystallization from melt :


This procedure is sui table for _growing single

crystals of metals, certain organic comoounds with low


melting point and that of inorganic compound like LiF, CaF

2
Super cooling of mol ten metal etc. is regula ted

NaN0

etc.
3
carefully leading to growth of single crystals.

Following methods are based on this principle.


( i)

Tammanns Method

( ii)

Method of Obreimov and Schubnikov ( 1924)

...

Method of Bridgman ( 1925)

( iv)

Method of Kapitza (1928)

( llJ. )

( v)
(vi)

Method of Czochralski ( 1918)


Method of Nacken (l915)

(vii)

Method of Kyropoulos ( 1926-30)

(viii)

Method of Stober ( 1925, 1945)

-(R)

Crystnllizatinn from v?oour :


Th i_ s

techniau~

is suit? ble for certa i11 metals

like Silicon, Silicon carbide, Silver, Gold, Copper, Nickel


etc., organic comnounds and sulph1des like Cd8, ZnS, etc.
Crystills grown from their own vaoour are small, hence
certain variations are made to obtain comparatively larger
crystals viz.
(i)

Condensatlcn of other metal


Potassium sealE>d in a thermostatically controlled

glass tuhe i.s condensed on a sHver wire to ohtain crystals


.of

pota~-sium.

(ii)

'Nhisker grov.rth
This technique of Sears (!953, !955) have been

applied by Melmed and Gomer ( !961) to grow thi.n crystals of


numerous metals for use i.n field emission misroscopes.
(iii)

Growth by haHde reduction


This technique gained prominence during early,

days of lamp industry.

de Lodyguine (1893) deposited tungsten

on to hot carbon filaments in a mixture of hydrogen and


tungsten hexachlori.de by the reaction
WC1

(iv)
(v)

+ 3H 2 = 6HC1 + W

Growth by decomoosltion of a volatile vapour.


Dynamic method
Frerich ilnd co-workers produced a chemically

purified grade of CdS. Cadmium metal is heated in a small


procelain boat inside a auilrtz tube to about 800- !000 C.
TI1e cadmium vapour formed in the boat is carried by a slow
stream of hydrogen in' - contact with a slow stream of H 2 S

furn~ce

that flows into the

through a quartz tube.

The

r,.oction occurs forrrdng CdS.


(vi)

Static method
This was devised hy Reynolds and Czyzak (1950)

nnd was first apolied to ZnS.

Chemically pure ZnS powder was

distributed over a length of approximately~ in. in a ouartz


tube,

TIJis charge

Ji'lS

resistance furnace.

olaced i_n the centre of a hori.zcntal

The ou:utz tube was then filled with a

H2 S atmosphere 'Jnd sealed.

A slightly positive pressure was

mai.nt1linPd at the growth temperature of ll50C. for a period


of about 48 to 96 hrs.

Crystals formed di.rectly on the

powder charge in the, shape of hexagonal prisms.


(vii)

Growth by pyrolytic decomposiUon.

The pyrolytic breakdown of Sii4


has been investiSii4 (g) ~ Si (S} + 4I(g)
gated by several authors (Me Carty ,1959; Herrick and Krieble,
1960) for the purpose of preparing transistor - grade polycrystalline silicon.
(viii)

Hydrogen Reduction Process


The hydrogen reduction of trichlorosHane has

found w5 de applica t i_on in the com'T1erc ial f<'lbrication of


transistor structure.
The eauation Sil-!Cl 3 (g) + H 2 (g)~Si(S) + 3H.Cl(g)
I'\"'

dE>scribes the p:ut of the reacti.on that results silicon


f\

deposition.
( ix)

Growth by subl i.mat ion.


In this method crystals grow from the vapour

created by the decomposition of a suitable compound,

26.

(x)

Growth by gaseous cracking.


SiC etc. are sometimes grown by this method.

Growth consists of bringing Si and C bearing vapours together


at high temperature.
(xi)

Epitaxial Growth.
Hergenrother et al. (1960) have shown that SiC

etc. can be grown from vapour onto a seed crystal at low


pressures.
(C)

This method is commonly called epitaxial growth.


Growth of single crystals by Electrolysis.
von Schwarz ( 1915) showed that quite large

crystals of copper can be grown by electrolysis of a solution


of copper sulphate strongly acidified with sulphuric acid.
van Liempt (1925, 1927) enlarged the 'Pintsch'
wires by electrolysis in a bath of molten sodium or lithium
tungstate.
(D)

Precipitation of Crystals from solution :


A wide variety of crystals are grown by this

method. Crystals grown from solutions usually have well


defined faces as compared with those grown from melts etc.
Growth is favoured because concentration of compounds and
their mobility can be very high, in the solutions. Compounds
that decompose when heated or become unstable at their melting
points or tend to form glasses when tried to cool from their
melts can be grown as crystals by this method.

The most

critical factor in this method is supersaturation.

It can be

controlled either by changing temperature of the solution or


by removal of the solvent by evaporation.

The following

three method5 nre used in general


J,

The temperature of the saturated solution is

raised or lowered depending on the stgn of temperature coefficient of solubility,


2.

A temperature gradient is estahlished in the

solution resulting in continuous dissolution of excess


nutrient in one zone and continuous extraction by growing
crystal in the other zone,
3,

A solution contained in one vessel at one constant

temperature is continuously saturated and then pumped in to


a second vessel containing the seed crystal at another
temperature,
Inducing

suoersat~~t~y

on a laboratily scale.

evaporation is most practical

The orincipal advantage is that the

rate is very easy to eontrol simply by adjusting size and


number of holes in the lid of the container.

Evaporat-ion at

constant temoerature avoids the danger of cracks induced by


thermal strains and single temperature is easy to control
with inexpensive equi,ments.
For salts .r6th normal solubility curves temperature
lowering is a pnctical method of inrlucing supersaturation
but the necessary temoerah;re contro11 ers are ex;:>ensive for
l8boratory use.

Recirculation is another method for

inducin~

supersaturathn :oncJ is efficient on a large scale but it is


often impractical in the laboratory.

This scheme uses a

solution make-up tank ( at a temoerature slightly higher


than the growing tank) that provi<ll"s a cont5.nuous source of
new material.

The solution is filtered throu9h a holding

tank to ensure comnlete soluti0n of the nuclei.

In the

labotatory, however, control of +emoerab1re changes In small


tubing and pumos cause difficulties with sponteneous nucleation.

~-

comroon lahoratnry

v~rsion

of th;_s techniaue is

convection current tr;omsfer between the two verti.cill limbs of


an H - cell,

Diffusion of new material through the horizontal

connector is slow since the connector is full and the amount


of suoersaturatlon developed is also low.

This too is diffi-

cult to control at an efficient rate.


Following are descri.bed a few methods based on the
ahove principles which are capable of giving reasonable big
cryshls of sufficient uniformity and purity on the laboratory
scale.
WULFF*S

ROT/>.TING

CYLINDER

METI-JOD

~
I
I

'\

'

~ ' ~ 'lui!!'.

,,,,t,[hc.t"" , . . . ,

----

---~~----""'

Wulff ( 1901) mounted his crystal on a holder placed on


the axis of a rotating glass cylinder holding about half
litre of solution.

Ey a chord and pulley the cylinder could

be rotated slowly.

The required supersaturation was obtained

by slow cooling.

In his later oaper (1912) a double cylinder

was used and the whole was placed in a large vessel of water

which could hE> controllrd hy a thermoregulator.


JOHNSEN'S

f\OT!ITING

r----J

CRYST~L

METHOD (!9.15)

r'---~

This is a vari.aHon of the above method.


llizing vessel

of capacity

The crysta-

200 ml. open to atmosphere to

allow supersaturation by evaporat"i.on, is clamped in a large


tank of 'Nater controlled by a thermostat.
pulley

speed.

This red holds a disc

A rod

A wi.th

at the top can he geared to rotate at any desired


D

the seed crystal can be cemented.

at the lower end to whi.ch


The spurious crystals

which form on the surface drop down to the bottom and do not
affect the growing cr'/Stnl.
Kruger

and

Finke

Method

Krtrger and Finke ( 19 JO) connec~ed two wl.de verti.cal


(..fig. 23)
tuhes A
A
in the abovt" shown manner by two tubes T1 &
1

The bag

r2

A c0ntatns a few crystals for supply to the solution

in A TI1e temperature can be raised by a heater at the


1
bottom of A1 A cnntalns a stirrer which draws concentrated
2
solution through r from A and drives it back through A2 <!nd
2
1
T1 C is a water cooler which supersaturate s the current
K near the h~se of A2
the t
The drawback in this method was~the undesired crystals

reachinq the seerl crystal

clogged up in the connector tubes Tl'

r2

The arrangement was later modified by Valeton (1915) who


placed P.

A2 in sep:nate thermostats as shown below. After


1
both thermostats have been matntai.ned at the same temperatures

for some hours, a small m1antity of under saturated solution


is added to A2 , the seed crystal is introduced and then the
temperature of the thermostat surrounding A is gradually
2
lo"'ered, to about 5 C below that of A
1
Hostetter (1919) used the same method and found that
the

be~t

temperature difference was from

.30 to .5 0

31
;

Walker and Kohman ( 1948) gave an account of the modern


plant which is adapted for commercial production,
Crystallization occurs in one tank of a three- tank
system,

The solution is saturated in a second tank at

slightly higher temperature, by being vigorously stirred in


contact with an excess of small crystals.

The saturated

solution flows through a filter due to gravity to the third


tank where it is heated to a temperature slightly above the
saturation point.

This unsaturated solution can be pumped

through a heated pipe line to the bottom of the crystallizer.


Though the temperature of solution is above the saturation
temperature when it enters the crystallizer, it rapidly cools
to the crystallizer temperature, somewhat below the saturation
temperature and the crystals grow uniformly and perfectly
under these conditions.
2.2

Crystallization of anhydrous and hydrated Cupric


Sulpb.ates.
Etard (1878) crystallized the anhydrous cupric sulphate,

CuS~

from a saturated solution of the pentahydrate in boiling

sulphuric acid,

Schwalbe (1898) obtained the same by cooling

a saturated solution of the pentahydrate with solid carbon dioxide and Poulenc (1894) obtained it from a solution of cupric
fluoride in concentrated sulphuric acid.
Graham (1835) obtained the monohydrate by heating the
pentahydrate in

vacuum at

38 -

vide infra.

Hodgkinson

and Co-workers (1899) b.eated the pentahydrate a week at 98,


.

Taylor ( 1904 ) heated the pentahydrate to 100

in a current

of dry air for a week and Krafft (1907) 60 hrs. over sulphuric
acid in vacuum.
Etard ( 1887) obtained the trihydrate by heating a
saturated solution of cupric sulphate in a sealed tube at
108 - 110 for 48

hours.

de Bruyn (1892) found that crystals of trihydrated salt


separated out from methyl alcohal on addition of water or by
raising its temperature.
Cross (1881) obtained the monohydrate by boiling the
pentahydrate with absolute

alco~ol,

Dietz and co-workers (1900) obtained the anneahydrate


at very low temperature which transformed into the hexahydrated
salt at

- 20.3 0 ,

de Boisbaudran (1867) obtained the hexahydrated and


heptahydrated salt by adding a small crystal of' NiS(\ 6H
and

2 to a supersaturated solution of' copper

Fes~.7H o

sulphate.

Metastable crystals isomorphous with these salts

separated but soon they change into the pentahydrate,


2.).

Crystallization of the Pentahydrated Salt

cuso4 5H2o It is evident from the above account that the anhydrous
cupric sulphate and the hydrated sulphates other than the
pentahydrate are not obtained under

ordinary conditions from

a saturated solution at or near the room temperature.

It is

only the pentahydrated sulphate which can be easily crystallized


from solution at or near the room temperature.
For the present study two methods of' growing single

33
crystals from the solution were tried :
and

1.

Sealed Jar Method

2.

Evaporation Method.

The principles of these methods are illustrated


below :

r..

'

'
'

'
--.._

];

. v_/ c
~

"'0

'!;

..rv
tc.J

'

C)

're.....,p~"~""t"'rL.

\b'

'lcmp<r<'l.tu re

- ---

. ---

Fig. 2S(a) Sealed Jar Method (b) Evaporation Method.


In Fig. 2.5'( a) the portion

A' represents

saturation

of the solution at the growing temperature, 'B'- heating of


the solution above the growing temperature preparatory
dissolving more salt in it,

C1

to

dissolving additional salt

in the solution at the higher temperature, 'D' - cooling the


solution to the growing temperature after

i~

has been seeded

and 'E'- represents allowing the crystal to withdraw material


from the solution at the growing temperature.
In Fig. 2.S(b) 'A' represents saturating the solution

at the

growing temperature, 'B'- heating the

solution so

that it can be seeded while it is unsaturated, 'C'- cooling


the solution to the growing temperature after it has been

34
''

seeded

and 'D'- represents allowing the solution to evaporate

at constant temperature, becoming supersaturated while the


crystal grows.
For either of these methods it is necessary to

prepare

the saturated solution which requires a knowledge of the


solubility of the salt.

In general the data on solubility of

any salt given by different workers seldom agree because of


the errors in the determination of the correct volume of

the

solvent due to evaporation.


Solubility of Copper Sulphate has been studied by
A. Etard (1872), Gruner and Brandes (1826); Trevor (1891) and
Cohen (1907).
The best representative values for solubility
expressed in 100 gms. of water are
6oo
14<>0
40
100

4o.o

28.5

180

80.2

75.4

75.4

According to Etard ( 1872) the solubility S at 0


referred to the anhydrous salt can be represented by -

s
s
s

=
=

11.6 + 0.2614 0 between

&

26.5 + 0.3700 0

&

:: 45 0 -

029 3 0

"
"

The following data on the solubility of the


pentahydrated copper sulphate

is taken from the,International

Critical Tables and are based on the works of Schiff (1859),


Guthrie (1875), Etard (1894), de Coppet (1897), Cohen &
Crommelin (1903), Schreine makers (1909), Foote (1919) etc.

.. TABLE- 2

------------------,----------------------,-----------;---,------,
II Temperature
! 0 ! 10 !: 20 Il 30 Il 4o lI 50!I 60 i' 10 i 80 lI 90!J 100 JI
in C
1

r~~~~~~~~~~--t ---l---r---r---r--r--~---t --~---~--- ~------ 1

I
, i
I

L100

gms

pe
c. c. of

1'

C\IIC\11'
1 1:', 0
, C\1 , ..:t
1"1 I .....,': co
0

i 0:.

I co'

'I "'

1:'-

1:'-

l \()

I '
t

I 1"1a- :'"'I
-o

,...

..:t

!
I
I

lj
.,.~,:r.'
I 't3 1 ~
~ , :i , ~ i S R I a> 'b'
~
I
L~~:~.:_c ______ j_ ___ j ____ j_ ___ j____ i __ l __ j ___ j_ __ j ___ j_~_j__: ___ J

~
1~

In the present case the solubility of the salt was


found to agree more closely with the values quoted above rather
than with .those obtained by calculations from the above three
equations of Etard.
2.4

Preparation of the Saturated Solution 585.0 gms of the salt (supplied by E.Merck) were

dissolved in 5'00 c.c. of distilled water and the solution was


boiled for

5 minutes.

This hot solution was then allowed to

cool up to the room temperature slowly.

This was done by

transferring the solution in a vessel of capacity 1000 ml,


and immersing the same in a bath of water at 100C in another
vessel containing approximately 10 litres of the hot water.
Since the water rises and falls in temperature more slowly than
the surrounding air, the bath acts as a 'thermal ballast'
reducing the temperature fluctuations

of the immersed solution.

A fragment of the crystal was suspended in the above


solution and the container was sealed to check evaporation.
letting the crystal fragment remain for about three days,

B.r
the

solution deposits its excess solid and the bottom in the form of
crystals, ( These crystals are twinned together irregularly and
are not single crystals.)

When these crystals stopped growing the solution had


reached its saturation point.

The clear solution was then

poured off into another container.

This was the saturated

solution.

2.5

Preparation of the Supersaturated Solution :

When the saturated solution was prepared in the manner


described above, it was heated to

5o 0 c

and freshly powdered

copper sulphate was added to it at the rate of 6.7 gms. par


100 ml. of the saturated solution.

This was throughly

dissolved and then the solution was allowed to cool up to


3QC.

The mouth of the containing vessel was sealed during

cooling so that no spontaneous growth of a large number of


tiny crystals on the surface could take place.
2.6

Preparation of seed crystals:

The saturated solution was poured on to four dishes,


each of them was then covered w1 th a bell jar as shown
the following figure,(fig 2.G).

!.-'
\

,
The bell jars were slightly tilted in order to

in

J'l
37

provide ventilation for evaporation to take place at a


sufficient rate.

The saturated solution thus gradually

supersaturated itself due to withdrawl

of solvent by

evaporation and after a couple of days tiny crystals of


dimension 2 mm3 or less were obtained at the bottom of
the dishes.

The solutions in the dishes were then decanted

off and the seed crystals were gently washed with distilled
water, dried with blotting papers and were

preserved in

dessicators which contained water in small amount.

This

saved the crystals from dehydration.


After a few crystals were grown by the methods
described below a few of them were cut in directions
parallel to various pinacoidal faces.

These sections

ware also used as the seed crystals in the

latter

experiments.
2.7

Mounting of the seedsIn earlier experiments the tiny seeds were glued to

thin glass rods when it was found that the solution creeped
on the supporting rods itself.

The same thing happened when

cotton or silk threads were used.


parachute thread was then used.

A single strand from the


No creeping took place in

this case but occasionally the solution creeped in this


thread also.

Later on it was found that creeping could be

completely checked if the strands were washed in running


stream of distilled water for a minute or two.
2.8

Minimising creep
Spurious

iD the walls of the container :

crystals forming at the surface of the

solution ( or growing up along the sides of the container )

... ,
j(,

proved to be another serious problem.

This was particularly

noticed during growth by evaporation,

When tile spurious

crystals gained sufficient size they fell at tile bottom as

well as on tile growing crystals and started growth in random


directions,

This was prevented to a good extent by taking

taller containing vessel and filling it only half with the


solution.
2. 9

Growth by evaporation -

As shown in figure 2. 7 a the apparatus consists of a


rectangular glass vessel

A' of dimension 15'" x 811 x 8 11

provided with a thick cover plate of wood 'B'.

'B' has slots.

of the size of the walls of the container wi tb depth about ,,


one and a half em.

In these slots rubber pads are inserted

as shown in fig, 2.7C.

To the cover plate, are attached

eight copper rods of diameter 0,4 em.

The ends of these rods

have boles for tying the fibres carrying seed crystals.


To control evaporation

a number of holes are dril.led

in the cover plate and each is fitted with a rubber

cork.

Fig. 2. 7( f) the
complete apparatus
with solution &
growing seeds.

Fig. 2.? h A photograph of the apparatus


for crystallization by controlled coolin
method. This method was not followed
later since it repeated gave crystals
with greenish white inclusions perhaps
that of hydroxide of cooper. The growing solution through thoroughly filtered
at first appeared to be full of suspended impurity somewhat gelatenous in
nature.

.. 39.

After preparing the saturated solution as described


before, it was transferred to the container to fill it
half its volume,

only

Eight seeds were mounted at the ends of the

supporting rods by tying them in the manner shown in fig, 2."7 b,


The vessel was then immersed in a water bath containing about
10 litres

of water at the temperature of the solution,

The

growing seeds were left undisturbed for a week,


At the end of the week crystals

of dimention

approximately 2 em. in length were obtained,

Five out of the

eight crystals were quite transparent and single.

The three

crystals had some air inclusion hence gave milky appearance


at the centres.
The process was repeated a number of times.

In the above method when seed crystals were suspended


at different heights from the bottom it was found that for the
first three days all the seeds grew approximately with the same
rate but afterwards the one near the free surface continued to
grow while those near the bottom started dissolving . When the
vessel containing growing solution was taken out from the
external bath and was examined in light from a frosted bulb
cone.
the~currents were seen to have a flow concentration from the
smaller crystals near the bottom to the larger ones near the
surface.
These concentration currents were also useful in
determining whether a solution
saturated.

is super saturated or under

'.

l
! '

'.',
..

~b)

~ {11.,1

-----------

If saturated, they descend from the crystal


( fig, 2.'i! a ) and the solution is unsaturated, if they
ascend

the solution is supe~saturated, ( Fig~- S b)

Another interesting observation in this method was


(fig

~-'II)

the formation of flat spiral! shades right on the surface


"

the solution around every thread carrying the seed.

The

seed crystals thus grew under a self protected condition.

o~

"

.,,
2.10

Tne sealed bottle method-

---:---~l
RubbH
Cork
l'opp<:l'

\.hre

.Sdk

Fibre

( 't

(b)

(a)
~~. 110 , ..,
I'

1J(r

K.ibra t:'lf
wtrtt

Cr

<15)

In tnis method the saturated solution was first


prepared and then it was made supersaturated by adding
more salt at a higher temperature as described before.
This was cooled to a temperature slightly higher (2-3C)
than the room temperature.

The solution was then transf-

erred to the conical flasks and freshly washed


were suspended in them.

crystals

Two methods were used for mount-

ing the seeds as shown in figure 2.

'' and 2.

"

r~
.

"'

'" .

'l -

The seed is suspended by a silk fibre tied to a


pin inserted in a rubber cork or is suspended from the upper
end of a cobra made from copper wire.

In the latter case the

cobra is kept entirely immersed in the solution.


The flasks containing the growing solution were
then immersed in

th~

water baths containing water at the same

temperature as that of the growing solution.


After about a week or sometimes more than a week,
flaw less, inclusionless and transparent single crystals were
taken out from the growing vessels.

The size of the crystals

were of dimensions 1 - 2 ems. in length.


2.11

Effect of rate of stirring on the size and


tran spar en ce

of the crystal -

rr---,

As shown in fig.

2.1~

fed from a voltage stabilizer unit.

an electrical stirrer was


Its vanes were kept

immersed in the growing solution first below the growing seed


then above it.

In each case three trials were made with

the

stirring rates 20 r.p.m., 4o r.p.m. and 60 r.p.m. respectively.

'!-

It was observed that when the vanes were below the


level of the growing seed, the formation of spurious crystals
on the surface of the solution were minimised when the stirring rate was raised from 20 r.p.m. to 4o r.p.m. and were
totally absent when the rate of stirring wa.s raised to 60 r.
p. m.

Size of the crystals after the completion of ey_ual

%for

periods of time (5 days) was found to vary by about 15


an increase of 20 r. p. m.

The size

d~minished

with increas-

ing r.p.m. but the milky inclusions (due to air) were minimised.
It made no difference whether the vanes are kept below or above
the growing seed.
Work on similar lines has been done by Matuserich
( 1960 ) on the same substance.

But the difference was that

he studied the effect of the addition of Ni, As and Fe on the


size and purity of the crystal with different rates of stirring of the growing solution.
In the present case the two studies were made
s-eparately.
2.12

NiS~, FeS~,

Effect of the addition of

and

CoS~-

When crystals were grown with the addition of 2 gms.,

gms., and 10 gms.,

NiS~

per 100 gms. of the saturated

solution by evaporation method the size of the crystals


increased by about

5 %,

10

%and

20

%respectively.

It was also noticed that the crystals had a tendency


to flatten along the face (100).
be

The crystals were

found to

more tran spar~11~- wi tl_!_Jncreas:i,.ng. quanti ~~___of~~.


Sulphate of iron and cobalt had 11 ttle or no effect

on the rate of growth or on transparence

of the

crystals.

2. 13

Effect of passing intermittent .A. C. and D, c.


current through the growing solution -

. In Fig, 2. ~3

'A' is a copper vessel containing

growing solution and 'R' is a copper rod which rests on


card board disc and supports the seed,
ated to allow evaporation,

Tile disc is perfor-

A bell transformer was used to

supply A. C. voltage,
de..,.,c;\ly

An alternat:ing. current of 4 mA/cm 2 was passed for


/'

6 hrs, daily at regular intervals of half an hour for five


days.

It was found that (i) no spiral growth took

place

on the supporting rod (ii) size of the crystal was not much
different than that without passing current and (iii) milky
inclusions ( of air ) were absent.
When the experiment was repeated in the same manner
with D. c. current of the same magnitude it was noticed that
( i) No spurious growth occured on the surface of the solution (ii) The crystal was somewhat more transparent and
(iii) The size of the crystal was approximately larger by
about 10 %.

.. 2.14

Arrangement for cutting the crystal lt'or the measurement of electrical conductivity in

the solid state and dielectric constant and to study their


directional dependence it was necessary to prepare sections
of the crystal in various crystallographic directions.

The

crystal being fragile it is not possible to cut it by

even

thinest wheel saws.

But it is soluble in water hence cutt-

ing of the crystal by wet thread is possible.


is however very tedious and extremely slow.

This method
The following

arrangement proved to be quicker and more convenient.

l4.tL

r }""")'3(>rnent f'Jr cuttrnc,; cry.s1al .

Fig. 2.14(b) The


Crystal mounted on
goniometer is under
the process of cutting.

As shown in Fig. 2.14(a) and (b) a wooden fly wheel


Wis coupled to a motor and is rotated at a speed of

r.p.m.

To this fly wheel is attached a shaft S which in its tum is


attached to a rod A.

With the rotation of the fly wheel the

rod A moves forwards and backwards.

The other end of A tnus

drives a string a b which is kept taut by a spring

The

string is made to pass through two diametrically opposite


holes in a vessel

containing a paste of very fine corundum

powder made with water.


dropped on the string.

Water from a burette B is occasionally


The corundum impregnated string cuts

the crystal at a sufficiently rapid rate.

The crystal is

cemented to the head of a goniometer G and can be set in any


desired direction.

All of the above parts are rigidly fixed

on to a heavy table.
The sections of the crystal thus obtained are then
ground first on a wet cotton pad then on ground glass surface.
Photographs of the above arrangement and that of the crystal
sections are given below.

lj '

Preparing samples cut perpendicular to the axial direutionsl


(i)

The face 010 of the ccystal makes an angle of 9744'

w1 th the b-arls,Awedge was cut from a single crystal of good

size ( appr<)ximately 1.'5 em or more in height ) w1 th one of


its faces being the face 010 itself. The wedge angle 1vas first
roughly

ahosen tobe 10.The face other than 010 was ground

till it made an angle of go with the face 010.This could be


measured with the help of a contact goniometer.Now the sample
was embedded in wax and was mounted on the prism table of a
spectrometer and the wed2e angle was measured to an accuracy
of 1'. The sample \vas then repeatedly ground and the vredge
was measured every time till an angle of 744 1 was obtained.
Having obtained this 1vedge the face kno-wn to be 010 1vas ground
so that it became parallel to the cut face This sample was
then perpendicular to the b-axis.
(ii)

The face 100 makes an angle of 7234 1 wlth the a-S]{is.

A wedge was cut in a similar manner as described above with


one of its faces being the face 100 itself.The vmdge angle
was accurately adjusted to be 1726 1 with th~ help of the spectrometer.The face 100 vras then ground till it became paralle-l to
the cut face.This was then the sample perpendicular to the
a-axis.
(iii)

All the faces of the crystal are parallel to the c-axi:J.

Hence a transverse cross-section of the crystal served as a


sample cut perpendicular to the c-axis.

'.10

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