Metallothermic Processes

(Self-propagating High-temperature
Synthesis Method)
Prof. Dr. Onuralp Ycel
Istanbul Technical University,
Department of Metallurgical & Materials Engineering,
Maslak, Istanbul, 34469, Turkey
1

 Specific heat;

Main Reaction Parameters for

SHS and Metallothermic Reactions

determining the heat evolved during the reaction and to estimate if the temperature
achieved is sufficient to smelt the metal and the slag and to separate them due to the
different density.
calculated by dividing the enthalpy of the reaction at 25C by the sum of the
molecular weights (MW) of the reaction products.
MeIO + MeII MeI + MeIIO
GR =GMeIIO GMeIO < 0
Specific heat < 2250 J/g, insufficient to melt the charge and to separate metal/slag
Specific heat > 4500 J/g, violent reaction and may even be explosive.
Specific heat : 2250 4500 J/g, a controlled and self-sustaining metallothermic
reaction
Spesific Heat = H 298 K / MWProduct
6

Main Reaction Parameters for

SHS and Metallothermic Reactions
Adiabatic combustion temperature (Tad);
It is suggested that a combustion reaction will self-propagate when Tad is higher than
1527 C

Adiabatic Temperature, C

Adiabatic Temperature, C

Without Al2O3

Al addition, mole

Mg addition, mole

Simulation of Tad change in Aluminothermic and Magnesiothermic Reactions

A Metal Joining applications in Istanbul Metro

In our laboratories, we have studied:

Some metals (V, Cr, B)

Alloys and ferroalloys (FeB, FeV, FeW, FeCr,

FeMn, FeMnSi, FeMo, CrNi, AlTiB)

Some advanced ceramics (TiB2, B4C, WxBy)

The process parameters of each production study

and thermochemical considerations were also
discussed.

Selection of Reductant Materials

Reductant/
Product

Melting Point, Boiling Point, -H298 ,

C
C
kJ/mol O

Metal price, Density,

$/kg
g/cm3

Al

660.4

2519

2,72

2,7

Mg

649

1088

3,28

1,74

Ca

839

1484

N/A

1,54

Si

1410

2355

2,65

2,33

Al2O3

2050

558.1

3,96

CaO

2570

634.7

3,34

MgO

2825

601.6

3,58

SiO2

1720

303.6

2,60
10

11

12

Aluminothermic Reduction
FeTiO3(s) + 2Al(s) = [Fe Ti](l) + Al2O3(slag)
3TiO2(slag) + 2Al(s) = 3TiO(slag) + Al2O3(slag)
3TiO + 2Al = 3Ti + Al2O3

3TiO + 2Al = 3Ti[Fe] + Al2O3

Aluminothermic ilmenite reduction of 20-25 % Ti alloy produced by the
addition of magnetite is done in a way.

3Fe3O4 + 8Al = 9Fe + 4Al2O3

FeTiO3 + 2Al = [Fe Ti](l) + 2Al2O3
3SiO2(slag) + 4Al = 3[Si](l) + 2Al2O3(slag)
MoO3 + Al Mo + Al2O3
14.12.2016

13

Silicothermic Reduction
2MgO + Si = 2Mg(g) + SiO2
2Mg(g) + O2(g) 2MgO(s)
10CaO + 5Si 2CaSi2 + Ca2SiO4 + 6CaO
10MgO + 2CaSi2 +6CaO 10Mg(g) + 5Ca2SiO4
10(CaO.MgO) + 5Si 10Mg(g) + 5Ca2SiO4

14.12.2016

14

Reduction of Uranium Compounds

3UO3 + Ca U3O8 + CaO
U3O8 + Ca 3UO2 + CaO

UO2 + Ca U(l) + CaO

UF4(s) + 2Ca(s) 2CaF2(l) + U(l)

H = 156 kcal/mol

Application in Uranium Metallurgy

UO2 + Mg(g) 2MgO + U(l)

14.12.2016

15

Reduction of Uranium Tetrafluoride

UF4 + 2Mg U + 2MgF2

H = -8,4kcal/mol

Niederschlag Process
Me1X + Me2 = Me1 + Me2X
Sb2S3 + 3Fe(s) = 2Sb(l) + 3FeS(k)
Very high grade (over 50% Sb) or pure crudum (Sb2S3) is reacted with iron.
Deoxidation in Iron and Steel Metallurgy
3FeO(metal) + 2Al = 3Fe(metal) + Al2O3(s,l)
Cementation
Me1n+ + Me02(s) = Me01(s) + Me2n+
Cu+2 + Fe0(s) = Cu0(s) + Fe+2

14.12.2016

16

High Carbon Ferro Chromium Production

17

LC FeCr Production
Perrin Prosesi
25-27 % Cr2O3
7-8 % FeO
2-3 % SiO2
45-48 % CaO

~70 % Cr
>1.5 %Si
0.05-0.02 %C

40-45 % Si
45-40 %Cr
0.05-0.02 %C

8-10 %
Cr2O3

20-25 % Si
60-55 %Cr
0.05-0.03 %C

18

19

20

21

22

23

24

25

26

Production of LC Ferrochromium by the Perrin Process

Perrin Process based on a silicothermic reduction of a chrome ore - lime melt
(rich slag) with a ferrosilicon-chromium (Fe-Si-Cr) alloy by using two ladle
steps. In the first step, basically, the Fe-Si-Cr alloy produced in a submerged
arc furnace is cast into a ladle and reacted with a molten intermediate slag
taken from the second ladle to produce intermediate alloy and waste slag.
Meanwhile, in the second step, the rich slag produced in an open arc furnace
is cast into a basic-lined ladle together with crushed intermediate Fe-Si-Cr
alloy taken from the first ladle to form LC ferrochromium and intermediate
slag.

27

28

The optimum quantity of intermediate Fe-Si-Cr alloy (60 wt% Cr, 20 wt %Si, 19.95 wt%
Fe and 0.05 wt% C) to reduce 100 g of molten rich slag (27 wt% Cr2O3, 48 wt% CaO, 10
wt% FeO, 6 wt% MgO, 6 wt% Al2O3, and 3 wt% SiO2) was estimated simulating the
process conditions of the second ladle with Equilib module of FactSage 6.0. The liquid
phases occurring in the reaction process were selected as Fe-liquid (FSstel database,
includes Fe, C, Cr, Al Si, Mg and O) and as ASlag-liq (FTOxid database, includes Al2O3,
SiO2, CaO, FeO, Fe2O3, MgO, CrO,Cr2O3), whereas all gas and stoichiometric solid phases
were taken from the Fact53 database.
The reaction of the process was assumed as adiabatic (H=0) and the initial reaction
temperature was selected as 1700 C. The adiabatic condition was searched for using the
temperature while adding a variable amount <A> of Fe-Si-Cr with <A> in the range
between 0 and 100 g.
Figure 3 shows that as the quantity of intermediate Fe-Si-Cr alloy added to the molten rich
slag increases, the degree of simultaneous reduction of Cr3+ to Cr2+ in the slag and a
subsequent transfer of Cr to the alloy phase increases.

29

31.25 g

Simulation result of effect of intermediate Fe-Si-Cr alloy on Perrin Process

for the production of LC ferrochromium
30

As the amounts of CaO and Al2O3 remain unchanged in the slag, SiO2 content
increases with increasing intermediate Fe-Si-Cr addition due to the oxidation of
silicon. The addition of the intermediate Fe-Cr-Si to the molten rich slag should be
limited to a level that does not increase the Si content in the molten LC FeCr alloy
higher than that of desirable specification limits (<1.5 wt % Si). For example, the
results of the calculation showed that in order to obtain an alloy with % 70 Cr
content, the amount of intermediate Fe-Si-Cr should be selected as 31.25 g and the
adiabatic temperature of the process then was found to be 2395 C.

The output substances of calculated LC FeCr alloy with 70% Cr

31

32

Self Propagating High Temperature Synthesis (SHS),

Metallothermic Reduction Applications
Greenand
Smelting
Solidification
Solidification
Combustion
Combustion
mixture
Phase
Seperation
and
cooling
and
cooling

Slag
Slag

FeCr
FeCr
Liquid SlagAlloy
Alloy
Liquid Metal

Metals, alloys, ferroalloys

Organic and inorganic
Advanced ceramics,
compounds,
Intermetallics,
Polymers
Oxygen free single crystals
Welding and metal joining
In these processes, after initiation, reaction becomes self-sustaining and propagates in the
reactant mixture.
A high amount of heat which is generated during the process accelerates the reaction rate and
thus it makes the process highly productive and economically feasible for different
33
production scales.

Enthalpies of reactions and Specific heat of the products related with the
experiments
H298, kJ

Specific
heat, J/g

Equation
No

Cr2O3 + 2 Al 2Cr + Al2O3

-535.573

-2600.45

(1)

Cr2O3 + 2 Al + CaO 2 Cr + CaO.Al2O3

-551.514

-2104.75

(2)

Cr2FeO4 + 8/3Al Fe + 2Cr + 4/3Al2O3

-775.016

-2620.17

(3)

Cr2FeO4 + 8/3Al+4/3CaO Fe+2Cr + 4/3CaO.Al2O3

-796.265

-2148.81

(4)

CrO3 + 2Al Cr + Al2O3

-1085.748

-7052.24

(5)

CrO3 + 2Al + CaO Cr + CaO.Al2O3

-1101.689

-5245.21

(6)

NaClO3+2Al NaCl+Al2O3

-1728.661

-10776.9

(7)

FeO + 2/3Al Fe+1/3Al2O3

-291.155

-3241.03

(8)

Reaction

Since some oxides in the chromite concentrate such as Al2O3, SiO2, MgO etc. may decrease the
reaction heat during aluminothermic process, in the same cases, additives such as sodium
chlorate (NaClO3) and chromic acid (CrO3) may be used to increase the reaction heat as shown
in Eq 5 and 7.
When CaO and CaF2 are added to the charge to decrease the melting point of the slag, the heat of
the reaction is still sufficient to advance the reaction.
34

FERROBORON
H298
kJ

Specific heat
J/g

B2O3 + 2 Al + 2 Fe 2FeB + Al2O3

- 402

2310

B2O3 + 4 Al + Fe2O3 2 FeB + 2 Al2O3

- 1255

4140

Reaction

35

FERROVANADIUM
Reaction

H298
kJ

Specific heat
J/g

V2O5 + 11.8 Al + 0.9 Fe2O3 Fe1.8V6 + 5.9 Al2O3

- 4860

4800

36

FERROTUNGSTEN
H298, kJ

Specific
heat, J/g

WO3 + 2 Al W + Al2O3

- 832

2912

1.5 Fe2O3 + 7 Al + 2 WO3 Fe3W2 + 3.5 Al2O3

- 2973

3332

1.5 Fe2O3 + 7 Al + 2 WO3 + 7 CaO Fe3W2 + 3.5

Ca2Al2O5

- 3017

1.5 SiO2 + 2 Al 1.5 Si + Al2O3

- 309

2144

KClO3 + 2 Al KCl + Al2O3

- 1501

8503

Reaction

100

90

70

90

W
Fe
Recovery

70
60
50
40
30

80

60

70

50

60

40

50

W
Fe
Recovery

30

40
30

20

20

20
10
90

100

110

Stoichiometric Al, %

120

0
130

10

10

0
80

90

100

110

120

130

Stoichiometric Al, %

37

calcine 26 wt.% W

Calcine 40 wt.% W (KClO3/Calcine ratio: 20 %).

Recovery of W, %

80

65
60
55
50
45
40
35
30
80

80

W, Fe in alloy, wt. %

80
75
70

100

Recovery of W , %

W, Fe in alloy, wt. %

90
85

2348

Ferroniobium
The refractory metals Nb, V, Ti, Mo, and W, when used in steelmaking, are
produced via aluminothermic reduction in the form of a ferroalloy.
This is done for two main reasons:
the alloy has a lower melting point, being close to one of the eutectics of the
binary system
the energy of the iron oxide (hematite) released during the reduction process is
necessary to melt the bulk of the mixture autothermically and to permit good
metal-slag separation.
Approxiamately 85-90 % of total niobium production is used in the steel industry
in the form of iron niobium alloy (ferroniobium) containing 40-70 % niobium.
Ferroniobium is usually produced by aluminothermic reduction of niobium oxide
ores with the addition of iron oxides if the niobium ore used contains insufficient
iron.
The starting materials are mainly columbites and pyrochlore concentrates.

38

Traditional Production of Ferroniobium

The traditional method of producing ferroniobium from pyrochlore concentrate was by

batch aluminothermic reduction. A typical batch was composed of the following:
Pyrochlore concentrate : 18000 kg
Hematite: 4000 kg
Aluminium powder: 6000 kg
Fluorspar: 750 kg
Lime: 500 kg
Each batch produced approximately 11 t of ferroniobium containing 66 % niobium. The
plant was capable of firing six batches per day, giving an annual capacity of 22,8 kt per
year operating 345 days. The yield was around 96 %.
The reaction gives 10000 kg
of ferroniobium of composition:
and 20000 kg of slag containing:

39

Traditional Production of Ferroniobium

The reactor consisted of a steel cylinder lined with one layer of magnesia bricks,
3,8 m in diameter and 1,8 m in height. Six of these cylinders were positioned over
concave pits, lined with lime and fluorspar, prepared on a sand bed.
Externally, the reactor base was sealed with sand, and the mixture that had been
stored in the steel containers was charged to the reactors.
The reaction was initiated with magnesium turnings, and the total reaction time
was about 20 minutes. During the reaction in open air, an enormous volume of
fumes, mainly alumina, came from the reactor.
Metal and slag are readily separated by gravity. The metal settled in the concave
pits in the sand bed, and the slag floated above the metal and was contained by the
reactor. It was then tapped into a nearby pit when the reactor had been raised from
the sand bed with an overhead crane.
Some 16 hours after the reaction had been completed, the slag was removed from
the sand bed and transferred to a 35 t dump truck and hauled to a disposal area.
The ferroniobium 'button' was kept in the sand bed for about 6 hours until it
solidified, and was then also removed from the sand bed. Af ter 12 more hours of
40
cooling in air, the ferroniobium was crushed in a jaw crusher, sampled, and stored.

Traditional Production of Ferroniobium

41

Autothermic Semi-continuous Process

The original ferroniobium plant in Araxa was designed in the early 1960's and its
capacity was gradually increased, basically by enlarging the reactor size.
Despite offering a high yield and smaIl investment costs, the operational and
environmental conditions demanded a new engineering concept, incorporating
modem materials handling, more safety, and fume control.
Studies carried out indicated that the 'fed reaction process' is the best alternative.
In this process, the reaction occurs in a fixed vessel during mixture feeding. This
enclosed controlled reaction, occurring in different cycles of a single reactor,
makes it easier to treat the fumes generated. After the batch feeding has been
completed, the slag is tapped through the upper hole, allowing water granulation,
and afterwards the metal is tapped through the bottom hole, allowing casting.
In order to save on the aluminium powder, which is used to reduce the hematite,
the use of an electric furnace as an external source of energy was considered,
which would permit the replacement of the hematite by scrap iron.

42

Autothermic Semi-continuous Process

43

Autothermic Semi-continuous Process

Studies, including some exploratory tests at Mintek, a South African research
organization, and several meetings with manufacturers of electrical furnaces, led
to the following conclusions.
Investment in an electric pilot fumace would be of the same magnitude as that
in an industrial fumace.
Most of the pending questions such as metal-slag separa-tion and tapping, slag
granulation, and refractory life are common to both options.
As a consequence of these conclusions, it was decided to conduct a series of pilot
tests on the autothermic 'fed reaction process'. A pilot plant with a fixed reactor of
1,6 m in internal diameter and 1,7 m in height was set up in May 1989, and a
modus operandi was gradually developed during that year by use of the present
autothermic mixture.
Based on the data generated during the pilot phase, it was decided to design an
industrial facility with a reactor con-figuration that would, if necessary in the
future, accept an external heat source to optimize the aluminium saving.

44

Process Flow Diagram of the Autothermic Semi-Continuous Process

45

FERROMANGANESE & SILICOMANGANESE

Products

Process

Mn Recovery, Energy Consumption, Coke,

%
(kWh/t)
(kg/t)
EAF
60-75
2600-2800
350
HC FeMn
BF
80-85
2000
SiMn
EAF
70-80
3500-4200
850-1000
LC FeMn
EAF
60-85
1600-1900
Metallothermic
63-85
Metallic Mn Electrometallurgy
70-87
9000
Reactions
Mn2O3 + 2Al = 2Mn + Al2O3
Mn3O4 + 2.667Al = 3Mn + 1.333Al2O3
Mn2O3 + Fe2O3 + 4Al = 2FeMn + 2Al2O3
2.5Mn2O3 + 3SiO2 + 9Al = Mn5Si3 + 4.5Al2O3
Mn2O3 + 1.5Si = 2Mn + 1.5 SiO2
Mn3O4 + 2Si = 3Mn + 2 SiO2
Mn2O3 + Fe2O3 + 3Si = 2FeMn + 3 SiO2
Mn2O3 + Fe2O3 + 4Al + CaO = 2FeMn + CaO.2Al2O3
1.5 Mn2O3 + Fe2O3 + 3 Al + 1.5 Si + 1.5 CaO = 2Fe+ 3Mn + 1.5 CaO.Al2O3. SiO2
KClO3 + 2Al = KCl(g) + Al2O3

-H298 , Specific Heat,

(kJ)
718.4
845.3
1569.4
2614.8
409.4
433.9
951.5
1609.6
1735.1
1500.8

(J/g)
3391
2810
3688
3197
2057
1522
2367
3342
2874
8502
46

Mn, Fe in alloy, wt.%

80
70
60
50

Mn
Fe
Si
Al

14
12
10
8
6

40
30
20

4
10
2
0
0
50 60 70 80 90 100 110 120 130 140

20

80

18

70

16

60

14

50

12

(Mn)

10

Recovery

40
30

8
6

20

10

Recovery of Mn, %

20
18
16

Mn in slag, wt. %

90

Al, Si in alloy, wt. %

FERROMANGANESE

0
50 60 70 80 90 100 110 120 130 140
Stoichiometric Al, %

Stoichiometric Al, %

Mn in alloy, wt. %

70
60

Mn
Si
Fe
Al

50
40
30
20
10
0
0

0.1

0.2
0.3
Si / Al, wt.

0.4

0.5

20

100
90
80
70
60
50
40
30
20
10
0

18
Mn in slag, wt. %

22
20
18
16
14
12
10
8
6
4
2
0

Si, Al, Fe in alloy, wt. %

80

16
14
12
10
8

(Mn)
Recovery

6
4
2
0

0.1

0.2
0.3
Si / Al, wt.

0.4

0.5

Recovery of Mn, %

SILICOMANGANESE

47

FERROMOLYBDENUM
MoO3 + 2 Al Mo + Al2O3
Fe2O3 + 2 Al 2 Fe + Al2O3

H = 915.0 kJ
H = 847.8 kJ

To estimate SHS reaction process:

Released Energy per g Product: 4433.65 J

Purity %

Fe2O3

96.5

Al

96.0

MoO3

98.0

FeMo Metals

Slags

EPMA

ICP Spektrometer

Mo %

Fe %

62 69

27 32

Si %

Al %

XRD

Cu %

1.5 2.1 0.5 1.1 0.4 1.0

Cr %

Ni %

C%

S%

< 0.2

< 0.2

< 0.1

< 0.05
48

July 2009

49

WO3 + 2 Al W + Al2O3

H0298 = -832 kJ

1.5 Fe2O3 + 2 WO3 + 7 Al Fe3W2 + 3.5 Al2O3

H0298 = -2973 kJ

1.5 Fe2O3 + 2 WO3 + 7 Al + 7 CaO Fe3W2 + 3.5 Ca2 Al2O

H0298 = -3017 kJ

1.5 SiO2 + 2 Al 1.5 Si + Al2O3

H0298 = -309 kJ

KClO3 + 2 Al KCl (g) + Al2O3

H0298 = -1501 kJ

50

51

52

53

Ak emas

Magnetiyotermik Redksiyonla
Titanyum retiminde Kullanlan
Kroll Tipi Bir Reaktrn
ematik Yaps

54

55

56

MAGNESIUM

Mg Metal

G-T diagram for oxide formation indicates that MgO reduction with silicon is only possible
beyond ; 2140 C at 1 bar and 1312 C at 1mbar
57

2 MgO.CaO + Si = 2 Mg (g) + Ca2SiO4

2 MgO.CaO + FeSi = 2 Mg (g) + Ca2SiO4 + Fe

2 MgO.CaO + 2 Al = 2 Mg (g) + Ca2Al2O4

58

59

* Pidgeon Prosesi

Patent No: US5.658.367

(1997)
60

Dolomitin Redksiyonu
Biriketler redklenme
ileminin yapld retort
bataryalarna arj edilirler.
Frn ii scaklk 12001250Cdir.
Vakum pompalaryla retort
ii basn 0.13-0.06 mbar
seviyelerine getirilmektedir.
Retortlarn frn dndaki
ucunda bulunan
kondansrlerde magnezyum
buhar birikerek younlar ve
ta ekilli Mg tanecikleri
olarak adlandrlan dendiritik
yap haline dnr.
61

1- Furnace, 2-Stainless steel retort, 3Briquetted charge, 4-Mg condensation

section, 5-Cooling water in and out, 6Vacuum connection, 7-Vacuum pump,
8-Digital
pressure
gauge,
9PtRh30/PtRh6 thermocouple, 10-Ice
water box, 11-Temperature measuring
unit.

Mg
Metal

Fe

Na

Al

Ca

Si

Mn

0.60

0.005

0.05

0.006

0.009

0.01

62

63

Crown Magnesium

64

65

66

Magnatherm Prosesi
Reaksiyon 5.7 m yksekliinde,
4.3 m apnda olan silindirik
reaktrde gerekletirilir.
Sistem atmosferik basnta iken
Kalsine dolomit, Kalsine boksit
ve FeSi hammadde silolarna
doldurulur.
Sistem vakuma alndktan sonra
hammaddeler reaktre verilir.
Bir nceki safhadan kalan
curufla temas edildikten sonra
reaksiyon meydana gelir
(1600C).
Oluan magnezyum buhar
650Cde tutulan kondansre
difze olduktan sonra su
soutmal pota ierisinde sv
halde birikir.
Reaktr proses evriminin
ortasnda ve sonunda olmak
zere iki kere boaltlr. 67

Self-propagating high-temperature
synthesis (SHS)

Self-propagating High-temperature synthesis (SHS) means the

synthesis of compounds (or materials) in a wave of chemical
reaction (combustion) that propagates over starting reactive
mixture owing to Layer-by-layer heat transfer.
68

69

izelge 2. Oluabilecek reaksiyonlar, entalpileri ve aa kan birim slar.

Reaksiyonlar

- H298 ,(kJ)

Birim s,(J/g)

1.5 TiO2 + 2 Al = 1.5 Ti + Al2O3

258.1

1485.2

B2O3 + 2Al = 2B + Al2O3

403.3

3263.7

TiO2 + B2O3+ 3.3 Al= TiB2+1.6 Al2O3

899.8

3757.1

2TiO2 + B2O3+ 4.6 Al= 2TiB+ 2.3 Al2O3

1067.5

3004.5

KClO3 + 2Al = KCl(g) + Al2O3

1500.8

8502.7

70

TiB2 contains 31.10 wt. % B and 68.90 wt. % Ti.

71

The Reduction and Formation

Reactions in B2O3-Mg-TiO2 System

3TiO2 + Mg Ti3O5 + MgO

2Ti3O5 + 7Mg 3Ti2O + 7MgO
Ti2O + Mg 2Ti + MgO
B2O3 + 3Mg 2B + 3MgO
B2O3 + 4Mg MgB2 + 3MgO
Ti + 2B TiB2
Ti + MgB2 TiB2 + Mg
B2O3 + 3MgO 3MgO.B2O3
2MgO +TiO2 2MgO.TiO2

72

Experimental Setup of the Metallothermic

Reduction Experiments
1. Power supply
2. Electric cable
3. Reaction crucible
4. MgO lining
5. Charge material
6. CrNi resistance wire
7. Stainless steel cover
8. Metal tube
9. Plastic gas hose
10. Flow meter
11. Regulator
12. Argon tube

73

Metallothermic Reduction Experiments

74

Theoritical Study
Spesific Heat (J/g)
Adiabatic Temperature (C)

Simulation of SHS products

composition change with addition of C

B4C

ZrB2

TiB2

WxBy

3820.6

3051.8

3947.7

3482.8

2323

2120

2979

2150

Simulation of Tad change with Mg addition

75

Experimental Procedure
B2O3 + 0.5 C + 3 Mg 0.5 B4C + 3 MgO
ZrO2 + B2O3 + 5 Mg ZrB2 + 5 MgO
TiO2 + B2O3 + 5 Mg TiB2 + 5 MgO
a WO3 + b B2O3 + c Mg WxBy + z MgO
B2O3+ 3 Mg + C

Raw
Materials
Mg
H3BO3
B2O3
C
ZrO2
TiO2
CaWO4
WO3

Purity,
wt %
99.7
99.5
97.0
98.0
99.0
98.8
98.0
99.8

Particle
Size, m
< 150
< 53
< 106
< 75
< 106
< 106

Mg

76

Metallothermic Process
B2O3 + 0.5 C + 3 Mg 0.5 B4C + 3 MgO
B2O3 (1 2 mole) C (0.5 1.1 mole)
Mg (2.5 3.5 mol)

ZrO2 + B2O3 + 5 Mg ZrB2+ 5 MgO

B2O3 (1 3 mole) Mg (5 7 mole)

TiO2 + B2O3 + 5Mg TiB2 +5MgO

1. Power Supply
2. Electricity Cable
3. Crucible
4. SHS Mixture

B2O3 (100 110 % sto.) Mg (90 110 % sto.)

5. W heating wire
6. Steel Cover
7. Argon Gas

WO3 + B2O3 + Mg WxBy + MgO

B2O3 (5 8 mole) Mg (0.6 3 mole)

ZrB2

B4C

TiB2

77

Leaching Process
Since the SHS product is a mixed solid of
B4C, or ZrB2, or TiB2, or WxBy with (MgO+Mg3B2O6)
MgO was leached out from the SHS product by HCl acid leaching process

In the leaching step,

MgO + 2HCl = Mg2+ + 2Cl + H2O

the SHS product was leached by HCl solution

-

S/L ratio,
Leaching temperature
Leaching Time
HCl Concentration
1.
2.
3.
4.
5.
6.

The temperature variations were

monitored
Water was added gradually when
loss of water was observed after
obtaining highest solution
temperature values.
Filter cakes were obtained by S/L
separation method.

400C contact thermometer

Magnetic Mixer
Hot-plate
Magnet
Beaker
Acid solution

Leaching Step

Filtering Step
78

SHS Process Results B4C

XRD analysis of the SHS product

(100 % stoic. Mg, C and B2O3 addition)
MgO(), Mg3B2O6 (), B4C ()
Possible
Reactions

B2O3 + 0,5C + 3Mg = 0,5B4C + 3MgO

B2O3 + 3MgO = 3MgO.B2O3
79

B2O3 + 0,5 C + 3 Mg 0,5 B4C + 3 MgO

no clear structural changes between these products

XRD analysis of SHS products obtained by

different stoic. C
additions and 100% stoic. Mg and B2O3.

MgO(),
Mg3B2O6 (),
B4C ()

XRD analysis of SHS products obtained

by different stoic. Mg additions and 160
% stoic. C & 100% stoic. B2O3.

Mixture

XRD Identified Phases

Mixture

XRD Identified Phases

100 % sto. C

MgO, Mg3B2O6, B4C

100 % sto. Mg

MgO, Mg3B2O6, B4C

160 % sto. C

MgO, Mg3B2O6, B4C

105 % sto. Mg

MgO, Mg3B2O6, B4C

200 % sto. C

MgO, Mg3B2O6, B4C

110 % sto. Mg

MgO, Mg3B2O6, B4C

80

SHS Process Results ZrB2

ZrO2 + X B2O3 + 6 Mg

Initial Molar Ratios

(ZrO2/B2O3/Mg)

XRD Identified Phases

1/1/6

ZrB2, MgO, ZrO2, (Zr, Mg)O2, Zr3O

1/2/6

ZrB2, MgO, (Zr, Mg)O2, Mg3B2O6

1/2,5/6

ZrB2, MgO, (Zr, Mg)O2, Mg3B2O6, Mg2B2O5

1/3/6

ZrB2, MgO, Mg3B2O6, Mg2B2O5

81

SHS Process Results TiB2

TiO2 + X B2O3 + Y Mg

XRD analysis of SHS products obtained by

different stoic. Mg additions and % 100 stoic.
B2O3

XRD analysis of SHS products obtained by

different stoic. Mg additions and % 110 stoic.
B2O3

:TiB2 :MgO : Mg3B2O6 :Mg2TiO4

82

SHS Process Results WxBy

WO3 + 8 Mg + X B2O3

XRD analysis of SHS products obtained by

different stoic. B2O3 additions with WO3

W, W2B, WB, W2B5,

MgO, Mg3B2O6, + Mg

CaWO4 + 8 Mg + X B2O3

XRD analysis of SHS products obtained by

different stoic. B2O3 additions with CaWO4

W, W2B, WB, W2B5, MgO,

Mg3B2O6, * CaO, Ca3(BO3)2
83

Leaching Process Results

Effect of HCl concentrations on
solution temperature.

B4C SHS product obtained by 100% stoic. C and Mg

Temperature, K

340
330

9.3 M HCl
7.4 M HCl

320

5.6 M HCl
3.7 M HCl

310

Maximum increase in temperatures were

detected within the first 3 minutes.

2.6 M HCl

300
0 M HCl

290
0

10

15

20

Time, min.

25

30

TiB2 SHS product obtained by

100% stoic. B2O3 and Mg
84

Leaching Process Results B4C

1/5 S/L ratio, 8,11 M HCl,

room temperature Effect of L. Time

85

Leaching Process Results ZrB2

1/20 S/L ratio, 80C, 60 min.

Effect of HCl Conc.

86

Leaching Process Results TiB2

1/5 S/L ratio, 30 min. Room temperature

Effect of HCl Conc.

87

Leaching Process Results WxBy

1/10 S/L ratio,

2.85 M HCl,
Room temperature
Effect of Leaching Time.

W2B,
WB,
W 2 B5 ,
MgO,
Mg3B2O6,
Ca3(BO3)2

88

Leaching Process Results

at optimum leaching conditions
B4C = 1/10 S/L ratio, 8,93 M HCl, 60 minutes, 80 C
MgTotal (wt. %)

Fe (wt. %)

CTotal (wt. %)

0.49

0.085

15.298

ZrB2 = 1/20 S/L ratio, 1,88 M HCl, 60 minutes, 80 C

BET analysis
Leached SHS product: 2,20 m2/g

Commercial ZrB2 particle: 1,04m2/g

TiB2 = 1/5 S/L ratio, 9,3 M HCl, 30 minutes, 25 C

FCT Systeme GmbH FAST
(Field Assisted Sintering Technique)
Graphite Crucible
Inner diameter 40 mm
Under Vacuum
50 MPa pressure
2100C
2 minutes sintering time

Density
(g/cm3)

Relative D.
%

Commercial
TiB2

4.22

93.4

Leached
SHS Product

4.44

98.2

WxBy = 1/10 S/L ratio, 5.7 M HCl, 60 minutes, 80 C

89

(: B4C, : ZrB2, : TiB2, : MgO, : Mg3B2O6, : Mg2B2O5)

TiB2

TiB2

ZrB2

ZrB2

B4C

B4C

Commercial

Leached

Unleached powders
90

SEM micrographs of
a) unleached B4C
b) leached B4C

c) unleached ZrB2
d) leached ZrB2

e) unleached TiB2
f) leached TiB2

(a)

(c)

(e)

(b)

(d)

(f)

91

WxBy

W2B,
WB,
W2B5

unleached
W xBy

leached
W xBy

92

Bir metal, kendi oksidinden daha negatif deerli serbest enerjiye sahip oksit
oluturan bir element tarafndan indirgenebilir.
Tm oksitlerin artan scaklkla kararll azalr. Baz nemli metallerin, artan
serbest enerji deerlerine gre sralan yledir: CaO, MgO, Al2O3, ZrO2,
TiO2, SiO2, Cr2O3, FeO, MoO3 vs. gsterilen bu oksitlerin her birinin metalik
hali, sadaki oksidi redkler ve bu redkleme reaksiyonu sonrasnda s aa
kar. Redkleyici olarak Ca metali kullanld zaman ilemin ad
kalsiyotermik,
Mg kullanldnda magnezyotermik,
Al kullanldnda aluminotermik,
Si kullanldnda Silikotermik redksiyon adn alr.

93

Bir metalotermik reaksiyonda, reaksiyon entalpisi aa kan snn

belirlenerek ilem esnasnda metal ve curufun ergitilmesi ve younluk
farklar yardmyla birbirlerinden iyice ayrlmalar iin yeterli scakln
oluup olumadnn belirlenmesinde kullanlan nemli bir gstergedir.
Reaksiyon entalpisi reaksiyon rnlerinin molekler arlklarnn
toplamna blnerek arj veya rnn gram bana retilecek s
hesaplanabilmektedir. Eer bu deer 4500 J/g dan daha bykse
reaksiyon patlayclardaki kadar iddetlidir. 2250 J/g dan daha dk
deerlerde ise aa kan s ergitme ve metal-curuf ayrm iin yeterli
olmamaktadr. 2250 ile 4500 J/g arasndaki s deerlerinde ise
metalotermik reaksiyon kontroll ve kendiliinden devam eden bir seyir
gsterir.

94

Eer s veren reaksiyon ile yeterli s salanamyor ise arj bir

n stmaya tabi tutulabilir ve/veya reaksiyona CrO3, KClO3,
NaClO3 gibi s vereci maddeler ilave edilebilir. Dier bir
alternatifte, retim iin elektrik ark frnlarnn kullanlmasdr.
Baarl bir aluminotermik proses iin, dk ergime
scaklna ve yksek akkanla sahip bir curuf gelitirmek
gereklidir. Bu ilem kire, flourspar ve kuarsit gibi curuflatrclar
kullanlarak salanabilir. Kire ilavesinin faydal etkisi yksek
aluminal curuflann likds scakln hzla drmesidir. Ar
curuflatrc ilavelerinde ise bu inert maddeler termal gereksinimi
arttrarak reaksiyonun yava ilerlemesine ve curuf scaklnn
artmasna neden olurlar.

95

Aluminotermik redksiyon yksek reaksiyon hz ile karakterize edilir ve

aluminotermik redksiyonun hz kontrol metal oksit ve aluminyumun
deiik tane boyutlarndan etkilenir. Kaba partikll aluminyum ieren
arj, ince partiklllere nazaran daha dk reaksiyon hzna sahiptir ve
yetersiz metal/curuf ayrmna sebep olur, curuf ve metalin ergime
scaklklarna glkle ulalr. nce aluminyum taneleri ise ksa bir
zaman periyodunda yksek scaklk piki verirler. Bunun anlam ksa bir
sre sv kalan yksek akkanlkl bir curuftur. Bu nedenle bir
aluminotermik proses iin aluminyumun tane boyutu ok nemli bir
parametredir.
Aluminotermik redksiyondan sonra herhangi bir ilem grmeden
satlan ferroalamlar iin alamdaki aluminyum ierii, elikte
istenmeyen bir emprite olduundan snrldr. Alamn Al/metal
orannn artmas alamn younluunu drr ve curufta kalma
ansnn ykselmesine sebep olur.
96

REFERENCES
Ycel,O., nar,F., Addemir,O., Tekin,A., The Preparation of Ferroboron and
Ferrovanadium by Aluminothermic Reduction, High Temperature Materials and
Processes, Vol. 15, Nos.1-2, 103-109,1996.
O. Ycel, F. nar, . Gzkaman, Aluminothermic Production of Al-Ti-B Pre-alloys,
10th Int. Metalllurgy and Materials Cong., UCTEA, Chamber of Metallurgical
Engineers, stanbul, TURKEY, 24-28 May, 2000.
O. Ycel, F. nar, A.O. Keskin, Metalothermic Production of Manganese Alloys,
10th Int. Metalllurgy and Materials Cong., UCTEA, Chamber of Metallurgical
Engineers, stanbul, TURKEY, 24-28 May, 2000.
O. Ycel, A. zelebi, Reduction Smelting Of Bursa-Uluda Tungsten Concentrates
By The Aluminothermic Process, Scandinavian J. of Metallurgy, 29, 3: 108, 2000.
O. Ycel, F. inar, Production of Aluminum-Titanium-Boron Master Alloy by
Aluminothermic Process, High Temp. Mater&Proc., 20, 2,2001.
O. Ycel, A.O. Keskin, F. . ahin, Metallothermic Reduction Of Tavas Manganese
Ore, INFACON 9, Proceedings of the 9th International Ferroalloys Congress, 230,
Quebec City, 2001.
Demircan U., Derin B., Ycel O., Synthesis of TiB2 Powder by PyroHydrometallurgical Process, XII. International Materials Research Congress, August
22-26, 2004, Cancun-Mexico
Ycel O., Yiit S., Derin B. Production of Magnesium Metal from Turkish Calcined
Dolomite using Vacuum Silicothermic Reduction Method International Conference on
Magnesium, September 2024, 2004 , Beijing, China.

97