COPPER ELECTROWINNING PROCESS

OPTIMIZATION FOR SURFACE MORPHOLOGY

AND QUALITY IMPROVIZATION

Presented By
Moganraj A/L Dhanabalan
Supervisor: Dr. Tuti Katrina bt. Abdullah
 Introduction
Production KPI
Austenitic stainless steels are commonly used materials in
High current density, modern supercritical power plants due to its excellent properties
Current efficiency, against oxidation
Specific power Disadvantages:
consumption • Limited corrosion resistance at high temperature
Copper
Electrowinning Thus, aluminide coating is introduced:
• Excellent oxidation resistance due to its ability to grow alumina
protective scales
• Applications: boiler tube steels, turbine blade & concentrated solar
Austenitic stainless power (CSP)
steel
Slurry Aluminizing

Advantages
1. easier to 2. environmentally
3. low cost
manufacture friendly process

 Performed by spraying or painting the aluminium slurry on the surface of substrate and
followed by a heat treatment process

a. Spraying b. Painting
Problem Statement
 Issues to develop a good protective coating :
1. Depletion of Al from the coating into substrate alloy
2. Mismatch of coefficient of thermal expansion (CTE)

Solutions
1. Addition of 2. 304 stainless
Al2O3 in the slurry steel is chosen as
composition the substrate

Diffusion of
aluminium also
depends on:
1. Temperature 2. Time
Objective

1 2 3
To investigate the effect heat To evaluate the surface To determine the growth

treatment temperatures and morphology, chemical kinetics, hardness, and

times on the formation of composition, and phase of corrosion behaviour of

aluminide coating with the aluminide coating. the aluminide coating.

alumina addition.
 Literature
Review
Aluminide coating Slurry aluminizing process Effect of temperature & time

 Lu et al. (2019) testified that the 

Slurry is a mixture that are consisted  Formation order: Fe2Al5 > FeAl3 >
aluminide coating formed on
of a binder and powder mixture FeAl2 > FeAl with increasing Gibbs
Super304H steel has greatly 
Kepa et al., (2020) prepared slurry free energy value
increase the oxidation resistance
composed of 57 wt.% of binder & 43  Coating thickness is increased with
when expose to high steam
wt.% of powder. temperature and time (Triani et al.
temperature  Addition of alumina minimize the 2020)
 The simple method to produce
inward diffusion of Al (Javan et al.,
aluminide coating – slurry
2019).
aluminizing

Growth kinetics Hardness

Hardness Corrosion behaviour

 Parabolic equation law:  Al-rich intermetallic compound  Corrosion resistance is improved

X² = Kt (Fe2Al5 and FeAl3): Hard and Brittle by applying aluminide coating
 Arrhenius equation:  Mudali et al., (2004) performed
 Fe-rich intermetallic compound
potentiodynamic polarization test
(FeAl and Fe3Al): Ductile
and corrosion resistance is increased
for aluminized sample
Methodology -
Process Flow

Figure 1: Overall process

flow of the project
Methodology - Sample Preparation

25ml H₂O 14.67g Al

2.78g
PVA
6.29g Al₂O₃ Slurry

Heated to 85℃ Cooled down to room

temperature

Slurry
Samples placed in crucible

Put the crucible into the furnace Samples

 Heat Treatment Process

Temperature
● 600, 630, 650, 680 and 700℃

Time
● 4, 6, 8 and 10 hours

Figure 2: Heat treatment profile of aluminide coated sample at 600, 630,

650, 680 and 700℃ for 4, 6, 8 and 10 hours
Results and Discussion
 SEM Morphology – for 10 hours
(a) (b)

Al + Al2O3 Al + Al2O3  A thin layer of aluminide is

formed at 600℃ and 630℃.

Substrate Substrate  The low temperature is not

600℃ 630℃ able to induce any solid-
state diffusion.
(c) (d) (e)
 Continuous and uniform
Coating Coating Coating aluminide layer is formed at
650, 680 and 700℃.

 Further discussion is
Substrate Substrate Substrate
discontinued for heat
650℃ 680℃ 700℃
treatment temperature at
Figure 3: SEM image of cross-section aluminide coating heat treated at (a) 600℃, (b) 630℃, (c) 600℃ and 630℃.
650℃, (d) 680℃ and (e) 700℃ for 10 hours
 SEM Morphology - at 680℃
(a) (b)

Coating Coating

 The aluminide coating formed

was discontinuous and non
Substrate Substrate
uniform at 4 hours.
4h 6h

 The aluminide layer became

(c) (d)
continuous and more uniform
Coating Coating when durations increased
from 6 to 10 hours.

Substrate Substrate
10
8h h

Figure 4: SEM image of cross-section aluminide coating heat treated

at 680℃ for (a) 4 hours, (b) 6 hours, (c) 8 hours and (d) 10 hours
EDX Analysis - (680℃, 10h)
Table 1: EDX chemical composition of spectrum 1, 2, 3 and 4 for sample
heat treated at 680℃ for 10 hours
Outer layer Inner layer Element Spectrum 1 Spectrum 2 Spectrum 3 Spectrum 4
at.% at.% at.% at.%
1 C 38.60 35.09 37.73 40.79
Coating
2 Al 42.26 45.36 33.19 2.99
3 Cr 3.71 3.44 4.40 10.59
Fe 15.22 16.11 19.08 42.58
IDZ Ni 0.20 - 5.59 3.05
Substrate 4 Total 100.00 100.00 100.00 100.00

 The outer layer and inner layer were enriched with aluminium
concentrations, implying that Al-rich intermetallic compounds,
Figure 5: SEM image of cross-section aluminide FeAl3 were formed.
coating with EDX spectrum 1, 2, 3 and 4 heat  A thin light grey layer in the interdiffusion zone (IDZ) was
treated at 680℃ for 10 hours confirmed as FeAl phase.
XRD Analysis – at 680℃
 FeAl3 were detected in all sample
regardless the heat treatment time.

 FeAl only detected at 10 hours

aluminizing time which is observed in
the interdiffusion zone (IDZ).

 FeAl phase is not detected in other

samples might due to the shielding
effect of the outer coating layer
prevented the X-ray from reaching to
the inner layer to detect the FeAl phase
(Reza Bateni et al., 2009).

Figure 6: XRD pattern of sample after heat treatment at 680 ℃

for (i) 4 hours, (ii) 6 hours, (iii) 8 hours, and (iv) 10 hours
Effect of alumina addition on aluminide
coating formation
(a) (b)  Aluminide coating for sample with
entirely Al is continuous and
uniform
Coating
Coating Thickness
Thickness  Coating thickness
IDZ
 Total thickness
FeAl
- entirely aluminium than 7Fe:3Al2O3
IDZ  FeAl
FeAl -7Fe:3Al2O3 than entirely aluminium

Figure 7: (a) SEM image of cross-section of sample with entirely Al slurry  Addition of alumina filler helped
composition, and (b) SEM image of cross-section of sample with 7Al : 3Al 2O3 slurry to retard the inward diffusion of
composition heat treated at 680℃ for 4 hours Al and promoting the growth of
Table 2: Coating thickness and thickness of FeAl layer of sample with entirely FeAl layer.
Al and 7Al : 3Al2O3 slurry composition heat treated at 680 ℃ for 4 hours
Sample Coating Thickness of
Thickness (μm) FeAl (μm)
Entirely Al 93.48 1.1364
7Al : 3Al2O3 28.88 2.4760
Aluminide Coating Thickness
 There is an increasing trend with
increasing heat treatment duration
and temperature.

 The maximum coating thickness is

obtained when durations is 10 hours
at all temperatures.

 The minimum coating thickness is

obtained when durations is 4 hours
at all temperatures.

Figure 8: Coating thickness of sample after heat treatment at

650℃, 680℃ and 700℃ for 4, 6, 8 and 10 hours
respectively
 Growth kinetic of aluminide coating
1650 -3.3
1541.3476 0.00102 0.00103 0.00104 0.00105 0.00106 0.00107 0.00108 0.00109
1550 -3.5 -3.57198570264244
Square of Coating Thickness (μm²)

1450 -3.7
f(x) = − 25827.8532205505 x + 22.9842354067099
1350 f(x) = 0.0281353333333333 x + 394.938
-3.9
1250 1202.7024 -4.09835258361964

ln K (μm²/s)
-4.1
1150
f(x) = 0.0165674444444444 x + 573.6754 -4.3
1050 1020.1636
972.1924
1007.4276 936.36 -4.5
950 882.09
f(x) = 0.0067412920.5156
x + 708.46916
850 834.0544 908.4196 -4.7
886.8484
781.7616
750 -4.9
10800 15800 20800 25800 30800 35800 40800 -5.00564775258522
-5.1
Time (s)
650℃ Linear (650℃ ) 1/T (K⁻¹)
680℃ Linear (680℃ )
Figure 9: Square of coating thickness of sample after heat treatment at Figure 10: ln K of the sample as a function of the inverse of the
650℃, 680℃ and 700℃ for 4, 6, 8 and 10 hours respectively temperature at 650℃, 680℃ and 700℃ respectively

 The activation energy (Q) was calculated to be 214.630 kJ/mol based on the slope in Figure 10.
 The high value of activation energy achieved can be attributed to the formation of FeAl3 and
FeAl phase.
 Nano Hardness Test
Layer 5
Layer 4
Layer 3

FeAl3 + Cr
FeAl
FeAl
diffusion
zone Layer 2

Layer 1
Substrate
Figure 12: Depth of penetration of 5 layer for sample after
heat treatment at 700℃ for 8 hours

Table 3: Maximum depth, hardness and reduced modulus of layer 1, 2,

Figure 11: SEM cross section image with label layer 1, 2,
3, 4 and 5 for sample after heat treatment at 700 ℃ for 8 hours
3, 4 and 5 of sample heat treated at 700 ℃ for 8 hours
Layer Maximum Hardness Reduced
 From Figure 12, the depth of penetration is decreasing from layer 1 depth (nm) (GPa) Modulus (GPa)
until layer 5 with same load applied. 1 829.3565 3.2461 225.4908
 Layer 4 and layer 5 which contained FeAl3 had the comparable high 2 584.9718 7.2738 238.1601
hardness value and low maximum depth of penetration value. 3 528.3063 9.4079 227.1563
 The hardness is decreased from layer 4 to layer 3, further supported 4 454.3797 14.0663 238.0590
the formation of FeAl phase in the layer 3. 5 455.8154 14.3847 229.2504
 Corrosion Test
Table 4: Corrosion potential, corrosion current and corrosion rate for sample
heat treated at 650℃, 680℃ and 700℃ for 8 hours and 10 hours respectively
Sample Ecorr (V) Icorr (μA) Corrosion
Temperature Time rate
(℃) (hours) (mm/year)

650 8 -1.0284 21.2610 0.2184

10 -1.2146 14.9140 0.1532
680 8 -1.0522 9.1196 0.0937
10 -0.6688 7.8516 0.0806
700 8 -0.7023 2.7247 0.0464
10 -0.6709 1.6438 0.0280
 Corrosion rate is decreased with increasing
heat treatment temperature and time.
 The lower the corrosion rate, the higher the
Figure 13: Tafel plot for sample heat treated at 650 ℃,
resistance of aluminide coated sample against
680℃ and 700℃ for 8 hours and 10 hours corrosion.
Conclusion
 Aluminide coating was successfully developed on the
sample that were heat treated at 650℃, 680℃, and 700℃
for all the durations.
 Based on EDX, XRD and nano hardness analysis, the
aluminide layer formed has an outer layer of FeAl3 phase
and an inner layer of FeAl phase.
 Aluminide coating thickness was increased with aluminizing
temperature and time.
 The activation energy for the coating containing FeAl3 and
FeAl phases was calculated to be 214.630 kJ/mol.
 The addition of Al2O3 had resulted in reducing the inward
diffusion of Al and promoting the growth of FeAl layer.
 The corrosion rate of the aluminide layer decreased as the
aluminizing temperature and time increased.
Thank
You
QNA SESSION