In crystal growth to synthesize or grow a crystal of material having high melting point

we have to melt the sample the sample start solidifying to form a crystal. Achieving higher
temperature for melting samples can be done using furnace. My main objective in this project is
making furnace for Bridgman setup, profiling the furnace and testing the furnace by
synthesizing a crystal.

I will discuss briefly about the Bridgman technique and the setup below

Bridgeman Technique:

The Bridgman method is widely used for growing single crystals. It’s a directional solidification
process. Its schematic is given below

Bridgman Schematic

This method involves following steps

 Sealing the sample inside the ampoule

 Melting the sample
 Then the sample is made to pass through pass through the temperature gradient region.

Furnace should be able to go above the melting point of sample and it should have a proper
temperature profile so that the sample can be made to pass through the temperature gradient
region where solidification takes place. The required temperature profile with ampoule position
inside the furnace is given below
This temperature profile is very important in growing crystals. The sample is sealed in an
ampoule (the ampoule is conical shape at the bottom and the sample sits at this point) and it is
kept at the region inside the furnace where it has a highest temperature which is at the middle
region for uniformly wounded furnaces. When it is kept at that point if the temperature is
sufficient for melting then material starts melting and it is kept there for some time so that the
material melts completely. Then it is made to pass through the temperature gradient region at
a constant and very slow velocities so that the temperature at the tip decreases very slowly and
the sample at the tip starts crystallizing and also acts like a seed crystal and grows as single
crystal.

We can find furnace profiling theoretically using the following equations

(1)

Where T(x) is temperature at position x

σ is Stephens constant

ε is emissivity of the Muffle

q Is total input power density

D is diameter of the Muffle

L Is the length of the muffle

Te is temperature of the environment

At the middle of the furnace x=L/2 if we fix the temperature to be 1273K

T(x) = T (L/2) =1273K

D=4cm

L=35cm

Te =300K

We can calculate input power q

q=3063.19 W/cm2

Now plugging above value in the equation for T(x) we can find temperature profiling

1000

900

800

700

600
0 5 10 15 20 25 30 35

This is theoretical found graph along x axis we have position in cm and along y axis we
temperature in oC
Here I will be mentioning about the materials used to make a cylindrical furnace which will be
used in Bridgman setup and I will describe the procedure that I have followed

Materials used for furnace:

In making furnace I have used the following materials

Cylindrical Tube

The furnace was made of Cylindrical Muffle of recrystalized Alumina whose thermal conductivity
depends on the temperature of hot region as

K (T )  5.5  34.5  e( 0.0033(T  273))

W/mK (2)

35

30

25

20

15

10 T

400 600 800 1000 1200

Graph.1 this graph shows how the thermal conductivity of material is varying with temperature

Heating Element:

Heating element used is Kanthal A1 which has a melting point of 1500OC. Resistivity of 1.45Ωm.

Insulating Material:

Refractory Cement used to coat the muffle which can with stand for temperatures of about 1200 oC.
Sodium meta-silicate acts as a binder for the cement.

Cylindrical tube made of stainless steel of dimensions 35cm length and radius 8cm.

Glass wool used as insulation in between muffle and cylindrical tube.

Procedure for winding the furnace:

The furnace is meant to be a part of the Modified horizontal Bridgman crystal growth setup.

According to the requirement the length of the furnace is fixed as 30 cm. A cylindrical
recrystalized Alumina muffle of length 35cm and Inner diameter 40mm and outer diameter
45mm. The required resistance of the heating element was 18 ohm. Kanthal A1 wire with a
resistivity of 1.45Ωm is used as heating element.

Number of windings is 60 and a separation of 5mm is maintained between them and wire is
wounded on muffle in workshop. After winding the heating elements tightly to the alumina
muffle wire is fixed to the muffle with the help of a mixture of refractory cement and sodium
meta-silicate solution. Here sodium meta-silicate acts as a binder for the refractory cement. The
mixture is cemented uniformly on the muffle and baked at a temperature of 150 o C with the
help of a heater. The system is allowed to set in room temperature for 7 days in isolation
without any mechanical shock. The outer covering is made out of stainless steel with a length
35 cm and radius 8cm. Glass wool was used as the insulation material .the muffle was inserted
in the cylindrical stainless steel covering and fixed in the slots. Two holes were made on the
upper and lower caps so that the muffle was coaxial to the outer covering. This step was done
with extreme care as it can affect the profile of the furnace crucially .After fixing the bottom cap
and the muffle the space in between the muffle and the stainless steel covering was filled
uniformly with layers of glass wool. The ends of the heating element to be connected to the
thyristor output were taken out through two holes on the top cap. The leads of the heating
elements are filled with separate alumina beads so that the two leads should not touch each
other. The current input terminals are electrically insulated from the stainless steel cover by
placing cement block in between. A hole was made at the midpoint of the curved surface .the
thermocouple for temperature controlling was inserted through this hole. After making all
necessary arrangements the furnace was mounted on the Bridgman setup. The furnace was
aligned on the platform of Bridgman setup with the help of four screws on the platform and 6
screws on the main frame. The alignment was done with extreme care so that the furnace
should not touch the quartz tube passing co-axially through the furnace .after alignment the
furnace was translated in both forward and backward direction to make sure that translation is
smooth without any jerks and friction.
Measurement:

After making the furnace, it was fired once for calibration purpose. The input current is supplied
to the furnace through a thyristor (TE10A).the thyristor was controlled by Euritherm 2416
temperature controller and an R type thermocouple. Both the thyristor and controller were
interfaced to the computer using RS232 port. During the test firing an external thermocouple
was inserted inside the furnace for calibration. After calibration profiling was done. The
profiling was done as follows. The thermocouple was kept coaxially at one of the faces of the
furnace .this position is designated as position 0.the program is rum for once and temperature
is measured as a function of time. It takes a while for temperature to stabilize at each position.
This is shown in the first graph. Accordingly the measurement was done throughout the length
of the furnace. All the graphs are plotted together. The steady temperature for each position is
measured in this manner. The steady state temperature values are given in the graph.2. The
profile matched with the required temperature profile. The dynamic which is while furnace is in
motion are given in graph.4

(a) (b)
470 7cm

800 6cm

465 1 cm
5cm
700
4cm

460
T (0C)

T (0C)

3cm
600
2cm
455 500
1cm

450 400 0

Time (a.u)
Time (a.u.)
 (c) (d)

14 cm 21 cm
960 13 cm
995 20 cm
19 cm
12 cm
940 990 18 cm

11 cm 17 cm
920 985

T (0C)
10 cm
T (0C)

900 980 16 cm
9 cm

880 975
15 cm
8 cm
860 970

Time (a.u.) Time (a.u.)

(e) (f)

1000 900 29 cm
22cm
23cm 30 cm
990
24cm 850
31 cm
980
25cm 800 32 cm
970
T (0C)

26cm 750
T (0C)

960 33 cm

950 27cm
700
34 cm
940 650

930 28cm 600 35 cm

Time (a.u.) Time (a.u.)

Graph.2

Temperature vs. Time at different position

Profiling different position vs. Mean temperature

Position of the thermocouple in furnace in cm Mean temperature in oC

0 381
1 468
2 551
3 624
4 672
5 715
6 786
7 838
8 860
9 890
10 910
11 922
12 941
13 954
14 963
15 972
16 979
17 986
18 990
19 993
20 995
21 995
22 993
23 989
24 983
25 975
26 963
27 949
28 927
29 906
30 874
31 837
32 795
33 733
34 670
35 590
 -5 0 5 10 15 20 25 30 35 40

1000 1000

900 900

800 800
tem perature ( C )
0

700 700

600 600

500 500

400 400

300 300
-5 0 5 10 15 20 25 30 35 40

Position (cm )

Graph 3.Furnace profiling for static case

 20 22 24 26 28 30 32

1000 1000

980 980
Tem p ( C )

960 960
o

940 940

920 920

900 900
20 22 24 26 28 30 32

Position (cm )

Graph.4 for dynamic case

After getting the profile a trial run has been made for sample of Fe 1.1Te of 5gms by the following
procedure

First the sample of 5gm is taken in an ampoule according to the stochiometric ratios as given below

Mass (Fe) = Fe1.1/ (Molecular Weight (Fe) X 1.1+Molecular Weight (Te))

Mass (Te) = Te/ (Molecular Weight (Fe) X 1.1+Molecular Weight (Te))

Then it is sealed after evacuating up to 10 -6 Pascal’s and sealed with another ampoule after evacuating
to 10-6 Pascal’s.

Then it is mounted inside the furnace in the middle of axial line. Then controller has been set for about
56hrs as given below

Target Temp.-790oC at a ramp rate of 100oC/hr, annealed for about 22hrs, cooled at a rate of 5 oC/hr up
to 700oC, cooled further to 300oC at the rate of 25oC/hr, further cooled to room temperature at the rate
of 100oC/hr. And the sample has taken out. It was a single crystal Laue and XRD has been taken for this
sample which confirmed that it is a single crystal. Growth of single crystal confirms that the furnace is
having proper profiling which is need for crystal growth.
Single Crystal XRD
Observations:

 Graph 1 shows that the how thermal conductivity of the muffle is varying with temperature at
higher temperature exponential term is approaching zero so at higher temperatures K is 5.5
W/mK. Which says at higher temperature thermal conductivity is reducing almost six times
which means it conducts very low heat compared to the lower temperature cases so achieving
higher temperature is very difficuct.
 Theoretically calculated and experimentally found graphs are almost matching each other.

References:

1. Modeling temperature distribution in cylindrical crystal growth furnaces P.S. Dutta, H.L Bhat
and Vikram Kumar

2. Mechanical and Physical properties of engineering alumina ceramics.