Lecture 14 & 15

Some specially designed

experiments
Studies of Foaming
Slag Foaming - BOF
Slag foaming
during oxygen
blowing period.

Benefits
• Slag – metal emulsion
• Reaction area

Means
• O2 blowing
 Slag Foaming - EAF
Slag foaming
during ”flat
bath” period.
Benefits
• Thermal insulation
• Heat transfer
• Stable arcing

Means
• C + O2 injection
 Slag Foaming – Negative effects

Tapping into ladle

• Excessive foaming
during tapping.
• Prolongs tapping.
• Slag overflow.

Vaccum degassing
• Considerable gas
formation.
• Decreases productivity.
 Foaminess of slags
• Most oxides in slags are surface active.
• Strong surface active oxides: P2O5, Cr2O3, CaF2 and V2O5

Ref: Lahiri, A. K. et al; Proc

Mills Symp; Met, Slags &
Glasses: High Temp. Prop. &
Phen., IoM, London, vol. 1
(2002) pp.231-238.
 •
Foaminess
. of slags
Properties dependent on composition

Two phases

Ref: Swisher, J. H. and McCabe, C. L.;

Met. Soc. Am. Inst. Min., Met. and Petr.
Eng. Trans., vol. 230 (1964) pp.1669-75.

Single phase
 Foaming index

• Bikerman: h

us

A
• Fruehan:   const  B C E
  db
• Lahiri & Seetharaman: 
 C
 db
 Foaming index
Foam

Validity:
h uS
• ”True foams”

• Steady-state
conditions

Bubble dispersed
phase
Dynamic conditions?
 EAF slag foaming
Foaming in an EAF for stainless steelmaking

2.5 – 4.5
4
Foaming grade

Heat No
Dynamic conditions:
C + MeOx = CO + Me:Change in slag chemical comp.
 Experimental slags
Slag %Al2 %Mg %Cr2 %Mn %V2O
C/S %FeO
No O3 O O3 O 5

I 1.5 7 5 5 10 2 0

II 1.5 7 5 5 5 2 5

III 1.5 7 5 5 5 2 0

IV 1.5 7 10 5 10 2 0
 Experimental set-up

Graphite
Liquid slag crucible
Alumina sleeve

Liquid Fe-Cr

C → CO (g)
Reduction area:
Cgraphite → CO (g)
Experimental set-up

Foam
layer

Dispersed
phase
 Dynamic foaming
35
Slag II
30 Slag I
Slag III
25
Foam height (mm)

Slag IV
20

15

10

0
0 20 40 60 80 100
Time (min)
 Dynamic foaming

350 Slag I

300 Slag II
Foaming index

250 Slag III

Slag IV
200

150

100

50

0
0 20 40 60 80 100 120

Time (min)
 Foaming index vs viscosity
120

100 Slag 1
Slag 2
Foaming index  (s)

80 Slag 3
Slag 4
Slag 5
60
Slag 6

40

20

0,070 0,075 0,080 0,085 0,090 0,095 0,100 0,105 0,110 0,115 0,120

Viscosity (mPas)
Gas escape rate vs viscosity
0,000013
0,000012
Slag 1
0,000011
Slag 2
0,000010
Slag 3
Gas escape rate (m /s)

0,000009 Slag 4
3

0,000008 Slag 5
0,000007 Slag 6
0,000006
0,000005
0,000004
0,000003
0,000002
0,000001
0,000000

0,07 0,08 0,09 0,10 0,11 0,12 0,13 0,14 0,15

Viscosity (mPas)
Bubble diameter vs Foaming index

350

300
Foaming index (1/s)

250
Slag 1

Slag 2
200
Slag 3
150 Slag 5

Slag 6
100

50

0
0 0,005 0,01 0,015 0,02 0,025 0,03

Bubble diameter
Dynamic foaming
Foaming index not valid for dynamic conditions. Why?

dH
dt
0 U gen  U esc  0 

  h  const
u
Dynamic foaming
Gas escape rate (Uesc) changing - Why?

Liquid film drainage

rate
• Viscosity change

• Concentration of
surface active
element

• Bubble size
Foaming thickness vs time
 Dynamic foaming
8
dHfoam/dt (mm/min) 1
6 2
3
4
5
2

0
-1,00E-05 -5,00E-06 0,00E+00 5,00E-06 1,00E-05
-2

-4

-6

Ug-Ue (m3/min)
 Dynamic foaming - Summary
The dynamic foaming shows several interesting aspects:

• Foaminess and reaction rate (gas generation) influenced by change in

chemical composition.

• Mismatch between gas generation and gas escape rate.

• Theory on effect of bubble size on gas escape rate not observed.

• Cold modelling of dynamic foaming in agreement.

• Traditional foaming index not applicable.

CaCO3 addition in EAF
 Work outline: slag foaming

Heat effect
of slag
foaming

Calculations Lab measurements Industrial trials

Thermocalc Heat Kinetic studying 100-ton EAF

HS Chemistry measurement and modeling at Belarusian
Literature data Steel Works
New-developed X-ray imaging
setup system
 Introduction. EAF optimization: slagformers supply

CO2 Slag

Decomposition Calcination Lime/

energy furnace Burned EAF
dolomite
Slag
Slag foaming Beneficial for
energy saving
CO2
Limestone/
Additional
Dolomite Decomposition oxidizer for
energy dephosphorization
etc.
 Laboratory experiment design
Furnace tube
Metal cone to Samples: a) – spherical limestone, b) – plain
shield the tc. limestone, c) – plain dolomite, d) – iron tablets

slag a)

b) c) d)
4 5
Slag composition:
CaO - 31 %; SiO2 - 31 %;
MgO - 7 %; Al2O3 - 6 %;
Iron crucible Thermocouples PID thermocouple FeO - 25 %.
(Ar envir.)
 Heat effect estimation (an example at 1400 oC)

S1 S2 -S1

n 2 2t
2 RT0 
(1)
n
nr
T  T0 
r

n 1 n
sin
R
e R2

Typical temperature profile after samples addition:

1 - pure iron tablets + natural carbonate; 2 – only pure iron tablets; 3 – model curve
 Heat effect determinations results
Calculated and measured heat effects of dolomite and limestone decomposition:
Measured heat of
Calculated Measured heat of
carbonates
dolomite carbonates
decomposition, %
Substance T, K decompositi decomposition,
from calculated
on energy, kJ/kg
values
kJ/kg
Min Max From To
Dolomite 1623 3146.6 1731.9 2187.6 55.0 69.5
1673 3213.7 1801.6 2370.5 56.1 73.8
1723 3281.5 492.7 689.8 15.0 21.0
Limestone 1623 3251.7 2005.3 2278.8 61.7 70.1
1673 3318.9 1896.4 2180.9 57.1 65.7
1723 3386.9 492.7 689.8 14.5 20.4

Calculation results:
Dolomite energy demand, J/g Limestone energy demand, J/g
Source of
Products Products
calculations Hr298 Total Hr1127 Total
heating heating
Thermocalc - - 3203.3 - - 3225.0
HS Chemistry - - 3168,7 - - 3193,9
1059.9
Calculations based
1545.4 1568.3 3213.7 1569.1 + 3318.9
on literature data
689.9
 Slag foaming kinetics: experiment design

Silica rod

Guiding tube Paper container

with carbonate

tube furnace

X-ray source X-ray camera Image processing

Computer
Alumina crucible
with slag

3
2
1
 Slag foaming kinetics: “shell” model
(Q  Qtr ) Cp2 – slag heat capacity, J/kgK; 2 – slag density, kg/m3; Vf.l. – the
T  dec volume of foaming layer, m3; Qdec and Qtr – the amounts of energy
Cp2  2V f .l . consumed for carbonate decomposition and transferred from the
bottom layer respectively; S – the slag surface area, m2; K2 – slag
S thermal conductivity, W/mK; Tbw – slag temperature at the bottom
Qtr  K 2 (Tbw  T f .l . )(t 2  t1 ) and at the walls, K; t2-t1 – time interval duration, s; h – the depth of
h bottom layer, m; Tsurf – the surface temperature of CaO/CaCO3
granule, K; R – sphere diameter, m; P – estimated porosity (which is
admittedly approximate);  – a pore shape factor, which was taken as
Qsl  4RK 2 (T f .l .  Tsurf )(t 2  t1 ) 2/3 for randomly dispersed cylindrical pores; b – bulk density of the
material; e – density, determined experimentally.
TABLE WITH INITIAL DATA / DRAWING?
4K CaO
eff
(Tsurf  Tdec )(t 2  t1 )
Qsp 
1 1
(  )
r R

Qsl = Qsp = Qdec

model
1 P
eff
K CaO  K CaO
1  P

b  e
P
b
 Industrial verification: data processing
Step 1: normalization of the heats by energy consumption

Preconditio Energy effect for 1

Parameter Delta unit
n value (pav) delta unit (Qi), kJ
Tap temperature 1931 K +1K 1980
Heat duration 55.9 min + 1 min 5472
Slagformers 33.1 kg/ton + 1 kg/ton 3600

Step 2: heat filtration by the time of carbonates addition.

tQ – average dimensionless time of carbonate addition,. It was calculated for each heat. Then heats were divided into 2 group:

1st – with early addition of carbonates (tQ < 33 %) 2nd – with later addition (tQ > 50 %).

Q i
carb
 micarb
tQ  i 1
 100 %
Qtot  mtot
carb

mi mi mi mi mi

Scrap melting Liquid bath

Dolomite and limestone influence on the energy demand per
liquid steel ton

litestone, tQ < 33 %; dolomite, tQ < 33 %;

limestone, tQ > 50 %; dolomite, tQ > 50 %

 Conclusions:

 A newly developed thermal analysis technique was introduced

for studying heat effects of carbonate additions.

Decomposition energy for dolomite and limestone is in the range

56-79 % of theoretical values, which is attributed to the energy
saving effect of slag foaming.

 The energy impacts for limestone and raw dolomite additions in

100-ton EAF were found to be 2255 and 2264 kJ/kg respectively,
which is 70 % of the theoretical values.
 Direct Alloying

Mo additions in EAF
 Background: Mo alloying in EAF

Fe-Mo alloy

Tsub=795oC
Gas
MoO3 MoO3
Steel
90 %  steel
C 7.6 %  dust
MxOy 2.4 %  slag

CaO/MgO/FeO

Alloying mixture
36
(stabylized Mo)
 Steel alloying with Mo in Uddeholms AB

1) MoO3
Pros: lower cost of Mo sources
Cons: yield of Mo is appr. 90 %

Dust and gas (7.6 %)

Output of
MoO3 Slag phase (2,4 %)
Steel phase (90 %)

2) Fe-Mo alloy
Pros: Better Mo yield and process control
Cons: High cost of Fe-Mo material

37
 The idea to increase Mo yield in EAF
- Compound formation

CaMoO4, MgMoO4, Fe2MoO4 replace MoO3 ?

38
The thermodynamic stability of different compounds

50

0
0 500 1000 1500 2000 2500
-50 CaMoO4
MgMoO4
-100 FeMoO4

-150

-200

39
 Work outline

Steel
alloying
with Mo

Calculations HT XRD TGA GC Steel alloying trials

Stabilities 16 g scale
In-situ formation C-FeOx-MoO3
MoO3 0.5 kg scale C-CaO-MoO3
Fe2MoO4 Decomposition C-MoO3
FeMoO4 3 t scale
MgMoO4
Reduction by C
CaMoO4 60 t scale C-FeOx-MoO3

40
 Work Strategy

Plant
Application
65ton EAF

Pilot trials
(5 ton test at Uddeholms)

Experimental studies
(0.5 kg induction furnace test)

Fundamental experiments (mg and gram scale lab )

Teoretical calculations

41
 TGA investigations (50 mg scale)

1-MoO3 (x0,02); 2-CaO+MoO3; 3-MgO+MoO3

SETARAM TGA 92

42
10 gram Lab test

Temperature profiles of the experimental heats

43
Charging sequence for a crucible
 Induction furnace test (0.5 kg)

Induction furnace Crucibles (Al2O3)

44
 Industrial experiments (3 ton)

Scrap Mixture

Induction furnace
Mixture addition

Scrap addition

45
 Industrial tests (65 ton EAF)

The mixture for Mo alloying

C Si Mn P S Cr Ni Mo V Al
0,38 1 0,39 0,01 0,004 5,1 0,09 1,44 0,9 0,017

46
 Test results (lab and 3 ton induction furnace)

The ranges of Mo yield, %

Experiment
M1 M2 M3
scale
FeOx+MoO3+C MoO3+C CaO+MoO3+C
95.0 – 97.4 91.3 – 98.5 88.6 – 96.7
16 g
(96.2) (93.3) (92.0)
97.7 – 98.2 76.6 – 86.7
0.5 kg 93.0
(98.0) (81.7)
89.2 – 97.8 92.6 – 92.8
3 ton 92.4
(95.8) (92.7)

47
 65 ton test results

Steel sample analysis results for the 4 heats:

Heat No.
Element Sample No.
62864 62865 62870 62871
1 1.57 1.56 1.55 1.50
Mo
2 1.44 1.45 1.39 1.39
1 0.18 0.15 0.09 0.16
C
2 0.28 0.33 0.25 0.27

Sample No. 1 – steel sample before addition of ferroalloys

Sample No. 2 – steel sample after addition of ferroalloys

The Mo content for the first sample is in the range of 1.5-1.57%,

while that for the reference heats is only 1.41-1.47%

48
 Mo yield -summary
Mo yield, %
Experiment scale
Patented MoO3 mixture MoO3
16 g 85-97.4 (96.2)
0.5 kg 97.7-98.2 (98.0)
3 ton induction
89.2-97.8 (95.8)
furnace

65 ton EAF 97.5-99.5 (98.5) 90.0

For a 65 ton EAF with steel grade contained 2% Mo, the

saving from Mo is 23 000 Kr / heat saving!

( if Mo price = 38 $ /kg)
49
 NEW PLANT TRIALS
II. Practical-Test
Charging Amounts per heat (65t)

Heat id Carbon Millscale

64145 2500 900 1400

64147 2500 900 1400

The mixture for Mo alloying

NEW PLANT TRIALS
 Test results
Experimental Mo Yield, %
scale
Pre-Study - 90-95% (Av)
Practical Test 95-98 (Av)
Theoretical test 95-99 (Av)
Modified test Oct. or Nov. 2011

Mo yield has 3-5% increse!!!

The iron yield is also increased some 1.9%

 Ecnomic gain from the project

MoO3 consumption ( 2010 Sep. to 2011 Aug) :1028.25 ton/year.

Mo saving: 1028.25*60%*5%=30.84 ton

SEK saving: 7.65 million SEK

Mould flux experiments
 Introduction

Powder

Mould
layer
Sintered layer

Liquid pool

Solidified layer(s)
Liquid layer

Liquid steel

Solid steel shell

 Flux design requirements

1. Thermal requirement
• Solid layer thermal release (glassy/crystalline)
• Opacity

2. Flux bed & liquid pool requirements

• Bed insulation
• Pool depth (melting rate)
• Pool physical properties
 Strategy
1. Determine physical properties
• Data for modelling of properties
• Properties input in mould simulation
models

2. Study the flux bed melting

• Bed structure
• Melting behaviour
 Strategy (contd.)

Plant trials
Material and data collection

Laboratory characterisation
DSC Measurement
Thermal diffusivity
Surface tension
Melting simulations
 Two casting powders
Flux A Flux B
%SiO2 28.8 32.7
%CaO + MgO 37.8 30.6
%Al2O3 6.5 4.7
%MnO + Fe2O3 4.1 1.3
%Na2O 7.2 11.3

CaO / SiO2 1.27 0.88

%F 5.9 9.4
%CFree 1.5 4.5
 Two different fluxes
Flux A (Plant A) Flux B (Plant B)

• Stainless steel • Low carbon, low

slab casting alloyed slab casting
• Non-peritectic
• Peritectic grade grade
• Soft cooling • High thermal
release

Glassy slag layer

• Crystalline slag
layer
 Plant trials

3/5
2/5

Sample
position
 Plant trials
Plant A Plant B
• 1429 x 205 mm
• 1445/1525 x 220 mm
• 1500°C in tundish
• 1532°C in tundish
• 0.85 m/min
• 1.35 m/min
• 4 x 5 kg starting powder
• 4 x 5 kg starting
• Flux consumption powder
 1.0 kg/min, or
 0.36 kg/m2 • Flux consumption
 1.45 kg/min, or
 0.31 kg/m2
 Plant trials
1st heat 2nd heat
35 SiO2

30 CaO

25
Weight percent

20

15
Na2O
10 Al2O3
F
5 MnO
MgO
0 Fe2O3
0 20 40 60 80 100 120
Time since start of casting sequence [min]
 Laboratory study

Flux A Flux B
Apparent thermal 3.72 ∙ 10-7 4.02 ∙ 10- m2/s
7
diffusivity

Surface tension 1150 910 mNm

DSC apparatus: Netzsch STA 449C (available at KTH)

Atmosphere
Measurements
Ar, Air, N2, CO, CO2, SO2, H2 etc.
Phase transformation temp.
Mixing: possible
Flow rate: controllable cp etc.
Gas cleaning system: available of slag, alloy, etc.
Po2: controllable by mixing CO and CO2 at ~1400oC / at ~ 1600oC
Min. Po2<10-21atm
 Specific heat capacity

Use Differential Scanning Calorimetry (DSC) method!

DSC:
The temperature difference is controlling the electrical
power to the sample and reference in order to keep them at
the same temperature.

The peak area directly corresponds to the heat consumed

or produced by the sample.
 Laboratory study
0 200 400 600 800 1000 1200 1400
15
10
DSC (Mould flux A)

5 Flux A
0
-5
-10
-15
-20
15
10
DSC (Mould flux B)

5 Flux B
0
-5
-10
-15
-20
0 200 400 600 800 1000 1200 1400
Temperature [°C]
 Laboratory study
Summary of initial mesurements

Flux A Flux B
Carbon, amount Low High
Carbon, type High Temp Low Temp

Melting interval 1000-1140°C 1030-1145°C

Basicity High Low

Flouride Low High

Phys properties Uncertain effect

More information required!

 Property Studies

Flux A Flux B

Softening 1000 1030

point (°C)
Melting point 1110 1085
(°C)
Flowing point 1140 1145
(°C)
 Laboratory study – Melting

Flux powder Al2O3 lining &

bed insulation
Flux sintered layer

Slag pool
Induction coil

Liquid steel Al2O3 cast

 Laboratory study – Melting

En
d
 Results

Flux A 1 cm Flux B

Platinum
markers

Powder
bed
Powder
bed Gas
generation
Mould flux

Sintered layer
Liquid
steel Mushy
Liquid slag zone
pool Liquid slag
pool
 Results
0 200 400 600 800 1000

Distance from liquid steel surface [cm]

4 Flux A
3
3

2 2
1

3
4 2 Flux B
3
1
2

0
0 200 400 600 800 1000
Time [s]
 Results

40
Flux B
Powder sink rate [cm/hrs] 35

30

25

20

15

10
0,1 0,2 0,3 0,4 0,5
Liquid slag pool depth [cm]
 Industrial implications
• Knowledge of mould flux melting in
general

• Characterisation of bed structure

during mould flux design with respect
to

 Number of layers
 Thickness of layers
 Gas generation
 Metal entrapment
 Slag entrapment
 What do we learn?

• Effect of starting powder

• Product data sheet information limited
• ”Normal” physical properties insufficient
• New melting test method developed
• Up to four layers in flux bed
• Liquid pool thickness controls melting
rate
• Possible impact on CC-process operation
and mould flux design

More studies needed...

The main problems are:
Longitudinal crack caused by
unevenness of cooling in the mould.
Sticking type breakout caused by
insufficient lubrication between the
mould and the shell.
 Slag Film Rupturing

Role of mould flux in continuous casting:

Lubricant
Preventing reoxidation of steel
Removal of non-metallic particles

 High speed casting causes high shear stress of liquid flux film
and the surface of solid flux film also.
 The break out of the slag film is a problem for lubrication
and heat transfer.

 The rupture mechanism of the slag films still have been poorly
understood.
 It is very important to understand a rupture
phenomenon of solid slag films.
 Strategy
 Development of apparatus to measure rupture
(tensile) strength of mould flux film.

 Measuring the rupture strength of the mould

flux film.

 Find out the correlation between strength and

structure of slags.

 Find out a suitable mould flux.

 Apparatus

Regulator DC Stepping liner drive

power supply

Thermo couple, T1

Specimen
40%Rh-Pt heating element Steel bed

Copper cooling block

Cooling water
Transducer

Thermo couple, T2 Stepping liner drive

Thermo couple, T3
PC
 Pt/Rh
heater
Specimen

Cooling bed

10mm
 Calculation of the stress

 ：Stress
Ft Ft ：Tension force measurement
  As：Cross section of the solid flux film
As after experiment

Liquid flux film

Solid flux film, ds

1mm

Cross section of sample (after experiment)

Chemical composition of the mould fluxes

(mass %)
Flux A Flux C Flux D
SiO2 34.2 25.5 32.7
CaO 29.4 22.7 28.8
Al2O3 3.92 12 4.7
MgO 1.01 0.97 1.77
TiO2 0.1 0.46 0.11
Fe 2O3 1.09 2.86 1.24
MnO 0.05 0.04 <0.10
Na2O 12.8 2.62 11.3
K2O 0.37 1.43 0.31
F 7.95 4.42 9.4
CFree 3.6 17.7 -
CO2 7.9 9.4 -
C total 5.74 20.3 6.6
H2O 0.69 - 0.3
Basicity (CaO/SiO 2) 0.89 0.93 0.88
Basicity (CaO+MgO/SiO 2+Al2O3) 0.8 0.63 0.82
 Sample preparation

Step 1. Premelting and Quenching

 Induction furnace: 1473K, 10min, Ar atmosphere.
 Graphite crucible
 Quench

Step 2. Casting by graphite mould

 Crash
 Induction furnace: 1423K, 10min, Ar atmosphere.
 Graphite mold: 3mm in depth, 4mm in width and 70mm
in length.
 A typical result of Stress-Elongation curve

5000
Flux C
4000 MAX
1423K
Stress,  /kPa

3000

2000

1000

0
0 1 2 3 4
Elongation,e /mm
 Flux A Flux C
5000 5000
1423K

Max Stress, Max / kPa

Max Stress,Max / kPa

1423K
4000 4000
1473K

3000 3000

2000 2000

1000 1000

0 0
0 0.5 1 1.5 2 2.5
0.0 0.5 1.0 1.5 2.0 2.5
Thickness, t /mm
Thickness, t /mm

C
Flux D M
5000
Flux A
1423K Flux A
Max Stress, Max / kPa

4000 M

Relative Intensity
3000 Flux B
Flux B

C
2000
Flux C
Flux C
1000
C

M
0
Flux D
Flux D
0.0 0.5 1.0 1.5 2.0 2.5
Thickness,ds /mm 400 600 800 1000 1200

-1
Wave
Raman number
shift / cm/-1cm
RAMAN SPECTROSCOPY MEASUREMENTS

Hokkaido Univ.
Raman Spectra Results

Raman spectra of SiO2-Al2O3-SiO2- CaF2 =14.3mol%

CaF2 as a function of CaF2 content.

Peak position of 1000cm-1 shifts to CaF2 =10.9mol%

lower frequency with increasing the

CaF2 content

CaF2 =8.39mol%

Relative intensity
The structure changes from chain to
monomer CaF2 =4.95mol%

The addition of CaF2 leads to the CaF2 =2.46mol%

depolymerization of silicate network

owing to the formation of Si-F bonds
CaF2 =0mol%

1200 1000 800 600 400

-1
Raman Shift [cm ]
 Compressive Strength

Thermocouple

Al2O3 tube
Quartz tube (f =12mm)

IR Furnace

Pt cover
f =6.5mm Slag

Al2O3 tube
(stand)

Load cell PC
Data acquisition
 Stress relaxation pattern

I II III IV
Force

Time
Stress relaxation test of synthetic slags at 1673K. (a)
time: 0-200sec., (b) time: 0-40sec.
3.5

3 (a)
2.5 C/S=0.94, C/A=1.89
C/S=0.94, C/A=0.81

Force, F / N
2 C/S=0.94, C/A=1.89, 6mass%CaF2
C/S=0.49, C/A=1.89
1.5

0.5

0
0 50 100 150 200
Time, t / s

0.06
C/S=0.94, C/A=1.89
C/S=0.94, C/A=0.81 (b)
0.05
C/S=0.94, C/A=1.89, 6mass%CaF2
0.04 C/S=0.49, C/A=1.89
Force. F / N

0.03

0.02

0.01

0
0 5 10 15 20 25 30 35 40
Time, t / s
 Some Conclusions
• The residual stress after a compression was
increased with increasing of Al2O3 content
and with decreasing of CaF2 content.

• The relaxation behavior was changed

drastically with increasing of temperature for
some molten slags.
 VISUALIZATION OF
IRON OXIDE REDUCTION
 Pellet reduction studies
PC-monitor

Al2O3 reaction
tube

Al2O3 crucible

X-ray source
Detector
 Product Analysis - SEM

Graphite base

Pellet in graphite bed

Gaseous reduction
 The Experimental Sequence

• Olivine pellets from LKAB, KPBO/KPBA

• CO-CO2-SO2-Ar gas mixtures used for reduction
• Isothermal as well as ramp experiments used
• Three sets of experiments
1. Without the presence of elemental carbon
2. Pellets packed in graphite powder
3. Pellets placed on a graphite plate
 Isothermal Experiments

• Temperature range: 900 – 1200oC

• No visible reaction

• Pellets neither melted nor changed in color

• Shows domains of 50 % O and 30-40 % Fe.

Impurities Ca, Mg and Si dispersed.
 Isothermal Experiments
Temperature 1300oC, CO/CO2 ratio: 13:1

Final
Start
 Isothermal Experiments
Temperature 1350oC, CO/CO2 ratio: 13:1

Start After 16 min

 Isothermal Experiments

Temperature 1350oC,CO/CO2 ratio: 1:1

Start After 30 min

 Ramp Experiments

Temperature ramp,CO/CO2 ratio: 8:1

Start 1421 oC
 Ramp Experiments

a b c

d e
Reductions on a temperature ramp with 3CO:CO2, graphite bed
(a) before reduction, (b) at 1453 C after133 min of reduction,
(c) at 1536 C after150 min, (d) at 1552 C after154 min,
and (e) at 1555 C after155 min.
 Ramp Experiments

b
a

c d
Temperature ramp reduction on a graphite substrate at 3CO:CO2—
(a) at 800 C before reduction; (b) at 1425 C after 123 min.;
(c) at 1485 C after 135 min.; (d) at 1489 C after 136.5
 Ramp Experiments

b b
a

d
c

Temperature ramp reduction on a graphite substrate at 3CO:CO2--(

a) at 800 C before reduction; (b) at 1428 C after 127 min.;
b) (c) at 1426 C after 127.5 min.; (d) at 1425 C after 128 min
 CONCLUSIONS
• Isothermal reductionexperiments show
incomplete reduction with the formation
of a molten slag.

• Ramp experiments with and without

contact with carbon have significant
differences in their behaviour during
reduction.
 CONCLUSIONS (contd.)

• Significant differences were noticed in

the pellets embedded in graphite and
those placed on graphite plate.

• Slag formation and consequent reduction

most robably through metal phase were
noticed.
Nitrogenation of
Fe-Nd magnets
Experimental

Balance

Pt wire
Auxiliary gas outlet Graphite furnace
Control module

Sample

Iron disks

Ti disks

Gas inlet Thermocouple

To vacuum pump
NITROGENATION AS A FUNCTION OF TIME
AT DIFFERENT TEMPERATURES

Pure N2, Flow rate: 95 ml/min.

0,020

0,015

1173 K; 100%N2; 95ml/min

(m)/m

0,010
1273 K; 100%N2; 95ml/min

1373 K; 100%N2; 95ml/min

0,005
1473 K; 100%N2; 95ml/min

0,000
0 10000 20000 30000 40000 50000 60000
Time, sec
 Temperature Effect of Nitrogenation
50%Ar-50%N2, 99 ml/min.
0,020

0,015
(m)/m

0,010 1173 K; 50%N2-50%Ar; 99ml/min

1273 K; 50%N2-50%Ar; 99ml/min

1373 K; 50%N2-50%Ar; 99ml/min

0,005
1473 K; 50%N2-50%Ar; 99ml/min

0,000
0 10000 20000 30000 40000 50000 60000

Time, sec
EFFECT OF PN2 ON NITROGENATION
T = 1473 K, Flow rate: 76-99 ml/min

0,020

0,015
(m)/m

0,010 1473 K; 25%N2-75%Ar; 76ml/min

1473 K; 50%N2-50%Ar; 99ml/min

0,005
1473 K; 100%N2; 95ml/min

0,000
0 10000 20000 30000 40000 50000 60000
Time, sec
HEAT CAPACITIES OF NITROGENATED ALLOYS

1.0
33.33 hrs nitrogenation at 1473 K 100%N 75%N , 25%Ar
2 2

0.8
25%N -75%Ar 50%N /50%Ar
2 2
Cp, J/g.K

0.6

Experimental curver
0.4
Fitted function

0.2
300 400 500 600 700 800

Temperature, K
The magnetization curve of a Nd2Fe17Nx sample
nitrogenated at 300 K

200
T=300K
150 Max field=4T
Nd Fe N (100% N , 33.33 hrs)
2 17 x 2
100

50
M, emu/g

-50

-100

-150

-200
-40000 -20000 0 20000 40000

H, G
 Other experiments
• Oxidation of slags containing FeO and MnO to
produce nanoferrites.

• Single step synthesis of Ni-W-C cemented

carbides by fluidized beds.

• Decarburization of Cr-containing steel melts

by CO2
Thank you!