Mat. Res. Bull., V~. 19, pp. 1031-1036, 1984. Printed in the USA.

0025-5408/84 $3.00 + .00 Copy~ght (c) 1984 Pergamon Press Ltd.

A SIMPLE MINI-FURNACE FOR THERMO-MICROSCOPY AND CRYSTAL GROWTH EXPERIMENTS

Bertil Forslund and Bohdan Jelinski

Department of Inorganic Chemistry
Arrhenius Laboratory, University of Stockholm,
S-I06 91 Stockholm, Sweden

(Received May 15, 1984; Communicated by A. Magn61i)

ABSTRACT
A fairly simple and inexpensive device for the preparation of single
crystals (mm dimensions) from a melt is described. This is a mini-
furnace, permitting atmosphere control as well as continuous visual
inspection of the sample through a stereomicroscope. A method to se-
parate the crystals from the melt is also described. The device has
been used for the preparation of crystals of several ternary com-
pounds and for phase analysis studies in the ApO-V2Os-V203 systems
(~ = Rb,Cs) in the temperature range 400-800°C and the 02 pressure
range 1-10-25 atm. The oxygen activity which is crucial for these
experiments, was controlled by the use of a ZrO2(Y203) solid electro-
lyte EMF-celI.

For good characterization of properties in materials science, measure-

ments on single crystals are generally necessary or desirable. The more
sophisticated crystal growth techniques might, however, seem too elaborate and
expensive for a chemist devoting a minor part of his time to preparative work
or just having an occasional need for single crystals. This is particularly
so if high temperatures must be used.

Facing this problem in our studies of some alkali-vanadium oxide

systems (I), we have built a relatively simple and inexpensive mini-furnace.
With this device we have been able to grow single crystals, several mm:s in
length, under continuous visual control and to separate them from the melt.
The same furnace has also been used, in a slightly modified version with a
smaller sample holder, for thermo-microscopy at high temperatures to explore
phase relations in the systems.

1031
1032 B. FORSLUND, e t a l . Vol. 19, No. 8

Description of the mini-furnace

Thermal stability during high-temperature crystal growth is favoured by
a large heat capacity of the furnace. However, visual control is hampered by
large size; neither good illumination nor sufficient magnification is com-
patible with large working distances in microscopy. A small furnace makes
possible rapid cooling, which is advantageous, !.~. after separation of a
crystal from the melt or in thermo-microscopy when attempting to freeze high-
temperature equilibrium conditions for subsequent analysis at room tempera-
ture.

Considering these factors, we have designed a rather small platinum

wire wound furnace (Fig. I). The heating element (~ = 18 mm, height = 25 mm)
is contained in a water-cooled brass cylinder (~ =110 mm, height = 60 mm)
with a removable lid consisting of a transparent silica glass plate. Mostly
a silica glass bottom plate has been used. The brass cylinder was made rather
short to permit best possible visual control by means of a stereomicroscope
(max. magnif. 40x) and illumination of the sample. The top window and the
microscope lenses therefore have to be cooled by an air stream at high tempe-
ratures. An illuminator with a halogen lamp and fiber optics was used.

A thermoregulator of thyristor type controls the temperature vi___aaa

Pt-(Pt,Rh) thermocouple with its junction very close to the furnace winding.
The regulator is equipped with a motor-driven variable resistance, providing
a range of heating/cooling rates. To reach 1100°C on the sample demands
~,25 V and ~12 A. The temperature close to the specimen is read by a second
thermoeouple. For the present study most experiments were performed at
temperatures in the 400-800°C range.

Two types of sample holders have been used in the furnace:

i) For phase analyses and preparation of very small crystals (for X-ray
studies) use is made of a transparent plate of silica, mica or sapphire
(~ = 10 - 15 mm) resting on the weld of a Pt-(Pt,Rh) thermocouple housed in
a ceramic tube. The tube is inserted through a teflon ball in the furnace
wall to make it adjustable. Flexible rubber bellows prevent gas leakage.

The sample, typically I mg in weight, is placed on the ceramic plate

just above the thermocouple junction to facilitate subsequent temperature
calibration by means of reference samples fused at the same spot.

This arrangement is preferentially used for phase analysis work, as

excellent visual control is achieved with such small samples. Observations
in transmitted light can also be performed by illuminating the sample through
the bottom silica window.

By slightly tilting the ceramic plate any creep tendency of a partly

fused sample can be counterbalanced, and the exact positioning of the sample
relative to the furnace is facilitated by the narrow depth of field of the
microscope. Crystals can be separated from the liquid at any temperature by
means of a piece of porous ceramics, attached to a simple manipulator, which
can be brought in contact with the partly fused sample to absorb the melt.

ii) For studies of larger volumes of material metal (Pt,Au) and ceramic
(SiO2, AI203) crucibles are used. These are about 5-13 rmn in height and 5-10
mm in diameter and placed in contact with a P~(pt, I~) thermocouple as in i).
Typical charge weights are 50-300 mg.
Vol. 19, No. 8 MINI-FURNACE 1033

~ MICROSCOPE

gos preh..ter-------~ I~;,~' liLsuotloo

silica glosswindow.--~7/ \orifice/¢o..,or.fO-r'"g SeOl
se

.,.,, I teflon ball

r~rUbber bellows

itovacuum
Ji V ~ cooling water

leads g.u /
silica glasswindow-`--/ 0
L 11 2
i
3
i
4
i
5cm
l

ALTERNATIVE ~ a t o r
SAMPLEHOLDER somple--,.~.
~pie¢e of porousceramics

~.~,,/ \plate holder (Pt}

FIG. I.
Schematic drawing of the mini-furnace with two sample holder arrangements.
Current leads to the furnace are not drawn, neither are the illuminator or
the thermo-couple for furnace control (close to the Pt-winding). An alumina
plate with a 5 mm orifice resting on top of the furnace is shown in the fig.
It can be used with the small crucible (0.1 ml) to improve thermal stability.

( ~ valve furnace __solid buffer (Ni*Ni0}

m P''==I~ rnixtu re
;z; . w ,,-,,',-,-,--~} - /,-way m croscope

II I\ tl--JI °"''°

FIG. 2.
Schematic diagram of the experimental set-up for crystal growth and phase anal?
sis studies at controlled oxygen partial pressures. The CO/CO 2 gas mixture is
stabilized by passing through the furnace (400-600°C) with Ni/NiO solid buffer
mixture before entering the sample space of the mini-furnace. By means of the 4-
way stopcocks either the gas entering or that leaving the furnace can be passed
through the zirconia EMF cell for measurement of the oxygen partial pressure.
1034 B. FORSLUND, e t a l . Vol. 19, No. 8

To separate a solid phase or pick up a single crystal from the melt, a

movable silica capillary tube, connected to a vacuum pump, is used in this
case rather than a piece of porous ceramics, which cannot absorb such large
amounts of melt fast enough. When the crystal has grown to sufficient size
the preheated tip of the silica tube is introduced into the melt close to the
crystal, the vacuum pump is run momentarily to suck up the melt, and the
crystal will remain attached to the capillary tube which is then moved to a
cooler part of the furnace compartment.

For both kinds of sample holder temperature calibration was performed

with several substances, e.g. K2Cr207 (Merck "p.a.", m.p. 398°C) in oxygen
atmosphere and NaCI ( M e r c ~ p . a . '' m.p. 801°C). The calibrations with sodium
chloride were carried out in both oxygen and argon atmospheres. A slight in-
crease (+ 3° ) of the calibration temperature in reduced atmospheres compared
with oxygen was noted, probably caused by a change in thermal conductivity
of the gas surrounding the crucible.

The horizontal temperature gradient was ascertained by heating these

reference materials at a slow rate and observing the temperatures for partial
and complete fusion. With a solid sample resting on a 0.1 mm thick mica
plate the gradient is about 2°/mm at 400°C and 4°/mm at 800°C. In the case
of crucible sample holders, the differences between partial and complete fu-
sion were found to be 6 ° at 400°C and 10° at 800°C over a 75 mg charge in a
small Pt-crucible (0.1 ml). Over a 500 mg charge in a 1-ml crucible the
corresponding values were 8 ° and 12° , respectively. In almost completely
fused samples these temperature gradients are probably reduced by convection.

Operation of the mini-furnace with controlled oxygen pressures

Experiments on transition-metal oxide systems demand a careful, conti-

nuous measurement and control of the oxygen activity in the gaseous environ-
ment of the sample, since the total composition of the charge will depend on
the oxygen pressure as well as on the temperature. Therefore a ZrO2(Y203)
solid electrolyte cell was used to monitor the oxygen activity in the gas
flow through the furnace.

To generate atmosphere~ with different well-defined partial pressures

of oxygen in the range 1-10 -~ atm (105 - 10 Pa), oxygen and argon from bombs
were simply mixed by means of a needle valve. Oxygen pressures lower than
10-4 arm were achieved by mixing CO and C02, dried by bubbling through con-
centrated sulphuric acid. For the purpose of stabilization, this gaseous buf-
fer mixture was passed through a separate furnace charged with a solid Ni/NiO
mixture defining an oxygen activity which depends on the furnace temperature.
For a description of this "double buffer" technique see (2). In order to fa-
cilitate the equilibration at the sample site, the gaseous buffer was pre-
heated with a Pt-wire winding around the gas inlet of the mini-furnace.

Fig. 2 schematically shows the set-up and flow diagram for the crystal
growth experiments at controlled oxygen partial pressures.

Table i presents crystal growth parameters for 4 mixed-valence Cs-V-

oxides prepared in the mini-furance (I). The strategy of these experiments
was the following: An initial mixture of CsVO 3 and V205 was almost completely
fused in the selected atmosphere, so as to leave only a small solid residue
of the desired phase, identified by microscopic inspection. When equilibrium
Vol. 19, No. 8 MINI-FURNACE 1035

(or at least steady state conditions) had been reached, necessary adjustments
of PO2 and temperature were made, and crystal growth was started by slow de-
crease of the temperature at a controlled rate. If the chosen crystal seed
turned out to be of insufficient quality, the procedure was repeated after
complete fusion. AT in Table I is the total temperature decrease from the
starting temperature (T) until the crystal was separated from the melt.

Fig. 3 shows the result of one of these experiments; a crystal of the

compound CSxV307 ( x ~ 0 . 3 ) sticking to the suction capillary after being
picked up f-fom the--mother liquor at about 650°C and Po2~-~ 10-16 atm (10-11pa).

FIG. 3.
A crystal of CSxV307 ( ~ 0 . 3 ) sticking to the tip of a silica
capillary after--suction of the mother liquor from a Pt-crucible
at 650°C. PO 2 ~ I 0 -16 atm. Crystal size ~ 3 x 0.5 x 0.3 mm.
1036 B. FORSLUND, et al. Vol. 19, No. 8

TABLE I

Growth Crystal
Compound ~ (°C) po 2 (atm) -AT. (o) time (h) size (ram)

CsV205 678 2.0 • 10 - 1 5 13 4x2x0.2

600 1.7 • 10- 1 9 3 4x3xO.1
Cs2V5013
CSxV307 650 1.6 • 10-16 7 5x0.5x0.3
(_x-~ 0.3)
C0.3V205 610 1 " 10 - 4 10 5x0.2xO. 2

Crystal growth parameters for four mixed-valence Cs - V - oxides prepared

in the mini-furnace under atmosphere control. AT is the total temperature
decrease during growth. T is the starting temperature.

Agknowled~ements

The authors wish to express their sincere gratitude to Dr. Karl-Axel

Wilhelmi for many helpful Suggestions.

We are also indebted to Professor Arne Magn~li and Professor Lars Kihl-
borg for critical reading of the manuscript and to Dr. Sven Westman for re-
vising the English of the text. Mrs. Ruth Wilhelmi has given invaluable help
with the editing of the manuscript, which is highly appreciated.

References

I, B. Forslund, Chemica Scripta. To be published.

2. S. Berglund, Chemica Scripta 18(2), 73 (1981).