J. Sustain. Metall.

(2017) 3:251–264
DOI 10.1007/s40831-016-0075-3

RESEARCH ARTICLE

Sustainable Recycling of Ferrous Metallic Scrap Using Powder

Metallurgy Process
K. K. Rane1 • P. P. Date1

Published online: 5 August 2016

Ó The Minerals, Metals & Materials Society (TMS) 2016

Abstract Powder metallurgy (PM) process can be used for L18 outcomes. This was confirmed by analytical prediction
transforming the oxidized ferrous metallic scrap to usable as well as confirmatory experiments.
products. The present study establishes an optimized PM-
based recycling process to obtain considerably higher Keywords Powder metallurgy  Recycling  Carbothermic
physical and mechanical properties of products (cylindrical reduction  Sintering
samples in the present work). To this end, seven parameters
including a source of metallic scrap, the quantity of car- Abbreviations
bothermic reducing agent, and PM process parameters PM Powder metallurgy
were used to build a Taguchi L18 orthogonal array. In situ FS Forging scale
reduced and sintered samples made under these 18 condi- GS Grinding sludge
tions were characterized for physical, mechanical, and GRA Gray relational analysis
microstructural characteristics. The gray relational analysis GRG/!i Gray relational grade
(GRA) approach was used to arrive at the most optimal S/N Signal-to-noise ratio
parametric setting. The grinding sludge as a source of scrap f i(k) Gray relation coefficient
material led to the highest sintered density, hardness, and
mechanical strength under these conditions: compaction Units
pressure of 900 MPa, a sintering temperature of 1150 °C, G Grams
stoichiometrically added graphite (for carbothermic Cm Centimeter
reduction), 90 min of sintering time, and ratio of heating- MPa Mega Pascal
to-cooling rate of 5/7. This analysis also corroborated with
the earlier findings that simultaneous reduction of metal
oxides and densification occur in the sintering operation. Introduction
This newly established PM-based recycling process with
GRA-optimized parametric settings improves the product Steel recycling, generally used to produce secondary
characteristics of interest by approximately 14 % com- steels, involves processing of primary metallic scrap
pared to those of the initial optimal setting obtained from available as chips, scales, dust, etc. Molten steel in
electric arc furnaces is refined using a variety of advanced
melt treatments [1–4]. The resulting ingots, available for
subsequent processing, show properties comparable to
The contributing editor for this article was Sharif Jahanshahi. those made from virgin sources [5]. This is, however,
energy-intensive and requires consumables/fluxes for
& K. K. Rane refinement, purification and subsequent processing such as
kkrane@iitb.ac.in rolling, casting, forming, and heat treatment [6–8]. This
1
Department of Mechanical Engineering, Indian Institute of process is economical when chunks of a scrap of similar
Technology, Bombay, India grades are available [9].

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252
The powder metallurgy process having four stages (pul-
verization of scrap, mixing, compaction to the shape of the
final product, and sintering) on the other hand offers the
following advantages for recycling. Different varieties of
metallic scrap may be shaped directly to the product
geometry through compaction and in situ solid-state reduc-
tion was followed by densification during sintering [10].
Recycling via the PM method has been reported earlier for
cast iron, ultra-high-strength steel, low-carbon steels, alloy
steels, etc., available in the form of chips or oxide scales [11].
Metallic scrap obtained from the foundry, forging, machine
shops, etc., are usually found in an oxidized state. Methods
like ball milling, target jet milling, and high-energy ball
milling are used for pulverization of this scrap. The powder
so obtained is irregular in shape and size [12].
Reduction of powdered metallic scrap is achieved by
carbothermic reduction (by mixing with solid particulate
reducing agents like charcoal, coke, coal, and char fines)
with scrap powder before compaction [13, 14]. Alternately,
the reduction may also be achieved by gaseous means
during sintering in a reducing atmosphere (like H2, NH3,
CH4, or CO). Compacted samples from scrap powder have
higher green strength due to mechanical interlocking of
irregular-shaped particles [15, 16].
PM products, after sintering, must possess adequate
density and mechanical properties to withstand in-service
conditions. Material parameters like chemical composition,
particle size, and process parameters like compaction pres-
sure, sintering time, and temperature together determine the
product quality in the PM process. Higher compaction
pressure and sintering temperature both improve density and
mechanical properties such as tensile/compressive strength
and hardness as reported earlier [17–20]. Optimization of the
processing parameters enables significant improvement in
the properties of the product as proven elsewhere while
recycling nonferrous metallic scrap [21–24].
The present work integrates in situ carbothermic
reduction of iron oxide and net shape manufacturing using
powder metallurgy for recycling of ferrous metallic scrap.
This work brings out the effect of material and PM process
parameters on density and mechanical properties using the
inferences of Taguchi L18 experiments followed by gray
relational analysis (GRA) to enhance multiple properties
concurrently [25]. This was followed by confirmatory
experiments performed under optimal conditions derived
from the GRA multiobjective optimization approach.
Experimental Details
For the present study, metallic scrap as (a) forging scale
(FS) and (b) grinding sludge (GS), and both mixtures of
different varieties of iron oxide were used. FS formed
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J. Sustain. Metall. (2017) 3:251–264
during hot forging was sourced from a forge shop. These
are brittle and have layers of iron oxide, like Fe2O3, Fe3O4,
and FeO. These scales are currently recycled during the
secondary steel-making process by melting in electric arc
furnaces [2]. GS consists of moisture, oxidized micron-
sized metallic chips/particles and residues of organic
matter like filter paper, oil, etc. GS is usually used in a
landfill but recent developments in separation techniques
have enabled recycling through a secondary steel-making
process. In the present work, GS was treated in a specially
designed drying–roasting unit to remove moisture and to
convert oil and paper/organic residues to carbon [26]. The
obtained dry and agglomerated sludge was initially ground
in a mixer grinder to form a powder.
Forging scrap and GS were further ground by ball mil-
ling for 5 min at 200 rpm to get powder of about 5–10 lm
particle size and 5–5.7 g/cm3 true density. The chemical
compositions of pulverized powders are given in Table 1.
Particle size and shape distributions as seen under an
electron microscope are presented in Fig. 1. It was
observed that powder particles of FS as well as GS after
roasting and ball milling have irregular shapes and sizes
(Fig. 1a, b). Particles of FS were finer and more homoge-
neously distributed in size than the GS particles.
The chemical analysis of pulverized FS and GS deter-
mined by EDX and confirmed through XRF analysis is
given in Table 1. As expected, the major constituents of
both the scrap powders were iron (Fe) and oxygen (O),
contributing over 90 % of the sample weight. Carbon
(C) was present as a minor element (\10 %) in both the
powder samples. The presence of alloying elements (wt%)
such as 1.26 % Cr, 0.36 % Si, and 0.35 % Al in the FS
powder and 0.42 % Mn, 0.57 % Si, and 0.39 % Al in the
GS were also confirmed. The presence of oxygen as a
major constituent in elemental analysis verified that the
iron oxides in the pulverized scrap were in the form of
hematite (Fe2O3), magnetite (Fe3O4), and wustite (FeO).
Graphite powder was mixed with powdered scrap in
different proportions for carbothermic reduction. This
mixture was compacted to the cylindrical shape of 10-mm
diameter (green samples) under different compaction
pressures. Sintering was performed in vacuum furnace
maintained at 1 Torr vacuum before starting the cycle. The
initially attained level of vacuum was sufficient to maintain
a nonoxidizing atmosphere throughout the sintering cycle.
Table 1 Chemical compositions of pulverized scrap material
Materials Elements
C O Al Si Mn Cr Fe
FS 6.32 18.37 0.03 0.36 – 1.26 73.65
GS 4.37 18.16 0.02 0.87 1.02 – 75.57
J. Sustain. Metall. (2017) 3:251–264
Fig. 1 SEM images of scrap powder obtained after ball milling of a forging scale and b grinding sludge
Inert gas (like N2 and Ar) was not used during sintering
because the gaseous mixture of CO and CO2 generated
during reduction reaction served as a reducing atmosphere
for sintering and had to be retained [27]. Otherwise, the
CO–CO2 mixture would get flushed away with the stream
of Ar or N2 inert gases. The plan of experiments for
studying powder recycling via the PM technique is illus-
trated in Fig. 2.
Design of Experiments
Taguchi orthogonal array was used to study the effect of
seven control parameters (Table 2) on the physical and
mechanical properties after sintering. Among seven
parameters, one parameter (scrap materials) was consid-
ered at 2 levels and the remaining six factors were at 3
levels. The source of scrap material was chosen as a control
parameter to represent the variation in raw material prop-
erties and chemical compositions, specifically the propor-
tion of Fe3O4, Fe2O3, and FeO.
The XRD analysis determined the presence of Fe2O3 (66
wt%), Fe3O4 (34 wt%), and negligible portion or absence
of FeO in FS. The analysis also confirmed the presence of
Fe3O4 (96.5 wt%), FeO (2 wt%), Fe(CO)5 (1.5 wt%), and
negligible portion or absence of Fe2O3 in GS.
The stoichiometric need of carbon for carbothermic
reduction of the various forms of iron oxide is calculated
based on the following reduction reactions:
6 Fe2 O3 þ C ¼ 4 Fe3 O4 þ CO2
2 Fe3 O4 þ C ¼ 6 FeO þ CO2
FeO þ C ¼ Fe þ CO2
From the above, the total stoichiometric carbon required
for reduction per gram of FS powder was calculated as
0.1322 g and that for GS powder was 0.0985 g. Usually,
the reaction does not reach completion, i.e., total
253
conversion is not possible. This is because of several
practical issues like inadequate (limited) surface contact
between iron oxide and carbon, the lower yield of reducing
agents/presence of impurities, and uneven mixing. Hence,
the reducing agent is needed in quantities higher than the
stoichiometric amount. Therefore, three mixtures from the
scrap powder were prepared to contain the selected car-
bothermic reducing agent, i.e., graphite in 100, 150, and
200 % of stoichiometric proportion for obtaining a com-
plete reduction reaction [28].
In the compaction stage, compaction pressure and
compact volume are the control parameters. The diameter
of cylindrical compact remains constant same as that of the
uniaxial compaction die. Thus, in order to study the effect
of volume of compact, three different weights of powder
mixtures were compacted. The volume of the compact may
cause a significant impact on powder packing and friction
with varying compaction pressure and in sintering process
by affecting thermal and mass transport. Sintering tem-
perature and time are the controllable parameters in the
sintering process, which affect significantly the physical
and mechanical properties of the sintered products. Heating
rate during the sintering cycle governs the thermal gradient
across the compact thereby affecting the densification and
properties after sintering. Therefore, the ratio of heating-to-
cooling rate (constant for all sintering cycles) was chosen
as a control parameter. Mixed design L18 orthogonal array
was used for the above-mentioned experimental studies.
The control parameters and their respective levels are
ð1Þ shown in Table 2.
ð2Þ Factors ‘‘A’’ and ‘‘B’’ are the material parameters, ‘‘C’’
and ‘‘D’’ are the compaction parameters, and rest of the
ð3Þ
parameters (‘‘E,’’ ‘‘F,’’ and ‘‘G’’) come from the sintering
process. The experimental settings of selected parameters
for each experiment with their respective levels are for-
mulated as per Taguchi L18 orthogonal array as given in
Table 8 of Appendix.
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Fig. 2 Experimental flow of ferrous metallic waste recycling using PM-based approach

Table 2 Control parameters with respective levels and mechanical properties such as sintered density, hard-
S. No. Factors Levels ness, and compressive strength. Three samples were tested
for every experimental condition. Each sample was pre-
1 2 3
pared for testing by polishing the surface to eliminate the
1 A: Scrap material source FS GS – effect of the porous layer (often having a layer of carbon
2 B: Graphite addition (% excess) 0 50 100 deposited on it) formed on the surface during sintering. The
3 C: Compaction pressure (MPa) 600 900 1200 sintered density of the cylindrical samples was measured
4 D: Compact weight (g) 2 3 4 using Archimedes’ principle. For measuring mass in air
5 E: Sintering temperature (oC) 1050 1150 1250 and water, a mass balance (Make: Citizon; Accuracy:
6 F: Sintering time (min) 30 60 90 ±0.001 g) was used. Different techniques of hardness
7 G: Ratio of heating-to-cooling rate 3/7 5/7 7/7 measurements (Microhardness, Rockwell B and C scale)
were used and found to be not suitable for measurement of
hardness after sintering due to large range scatter in the
Experimental Measurements and Analysis measured hardness values of samples. Rockwell superficial
Procedure hardness measuring technique (Rockwell T scale) was
found to be satisfactory for hardness measurements,
The samples obtained after completing above-mentioned wherein the test piece is indented for 20 s by a hardened
L18 experiments were characterized by various physical steel ball indenter [D = 1/1600 (1.56 mm)] under a minor

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J. Sustain. Metall. (2017) 3:251–264 255

load of 3 kg and a major load of 12 kg. Hardness was Table 4 Signal-to-noise ratios of individual properties (sintered
measured for each sample three times at different locations density (p), hardness (q), and maximum compressive strength(r))
and average values were reported. Exp. No Sample description S/N ratios for individual properties
A compression test was carried out on the cylindrical
p q r
samples using Universal Testing Machine (Make: Shi-
madzu; Model: AG5000ZG) to measure the compressive 1 FS1 12.1334 15.02588 29.07834
strength (MPa) of the sintered samples. The outcomes of 2 FS2 13.7443 22.37223 42.4529
these experiments are given in Table 3. 3 FS3 13.4030 19.38643 54.42054
The effect of process parameters on sintered density, 4 FS4 13.3544 22.10179 40.06104
hardness and maximum compressive strength was deter- 5 FS5 12.4485 24.58518 35.98488
mined using Taguchi experimental analysis procedure. S/N 6 FS6 12.4089 15.28202 33.36709
ratio, ‘‘Larger is better’’ criterion was followed as given in 7 FS7 10.8208 16.11459 37.03268
relation 4: 8 FS8 13.0701 16.79409 42.73395
" !# 9 FS9 10.9468 12.31961 25.54359
S 1 X n
1 10 GS1 14.8100 32.74905 52.88379
¼ 10 log10 ; ð4Þ
N n i¼1 y2i 11 GS2 14.9621 32.50399 51.88381
12 GS3 15.2839 30.43379 55.82927
where yi is the response value of ith experiment, i the ex-
13 GS4 12.2536 24.73209 41.82898
periment number and n is the number of experiments.
14 GS5 12.3956 22.44122 35.88649
The S/N ratios for quality characteristics are presented
15 GS6 15.4201 29.93195 55.77993
in Table 4.
16 GS7 13.4539 30.84034 41.82337
The mean of quality characteristics (properties) corre-
17 GS8 12.7357 31.33674 42.43867
sponding to parametric level was measured by averaging
18 GS9 11.4106 23.44418 32.62761
S/N ratio and properties from corresponding experimental
conditions. For example, the mean values of properties
were determined by taking nine observations per level for
scrap material source parameter, whereas mean values of determined using standard deviation obtained during
six samples were taken for deciding the effect of the rest of analysis of the results. The effect of parametric levels is
the parameters. High and low values of error were discussed in the following section.

Table 3 Measured properties

Exp. No. Sample details Sintered density (g/cm3) Hardness (HR15T) Max. CS (MPa)
of sintered samples (R1, R2, and
R3: the measurements of R1 R2 R3 R1 R2 R3 R1 R2 R3
different samples for the same
experimental conditions) 1 FS1 4.05 3.99 4.09 6.0 5.7 5.2 29.8 28.5 30.05
2 FS2 4.84 4.90 4.86 13.5 13.5 12.5 134.3 131.3 131.4
3 FS3 4.81 4.53 4.71 9.2 9.7 9.0 426.4 428.4 420.1
4 FS4 4.60 4.68 4.68 13.5 14.0 11.2 110.5 96.4 98.5
5 FS5 4.11 4.25 4.22 18.0 16.2 16.7 59.4 62.3 63.6
6 FS6 4.19 4.20 4.13 6.2 5.7 5.5 45.5 48.6 45.9
7 FS7 3.41 3.50 3.52 6.5 6.7 6.0 77.1 71.2 70.5
8 FS8 4.46 4.53 4.52 7.0 7.0 6.7 132.4 135.7 138.2
9 FS9 3.50 3.53 3.55 4.5 3.7 4.2 18.66 17.8 19.3
10 GS1 5.94 5.86 4.90 41.5 45.7 43.2 441 437.4 445.1
11 GS2 5.69 5.55 5.56 40.2 47.5 40.0 393.4 390.2 395.0
12 GS3 5.89 5.66 5.89 30.7 35.2 34.2 613.2 616.7 614.5
13 GS4 4.12 4.03 4.15 15.7 19.3 17.5 123.4 120.8 121.6
14 GS5 4.16 4.15 4.19 13.0 13.1 13.5 65.1 60.2 62.4
15 GS6 5.81 5.98 5.92 31.5 30.2 32.5 614.4 611.7 616.2
16 GS7 4.73 4.67 4.72 35.2 37.2 32.5 124 123.8 123.3
17 GS8 4.31 4.31 4.38 38.7 37.5 34.7 130.6 132.8 133.2
18 GS9 3.72 3.70 3.74 16.2 13.5 15.25 42.7 45.5 43

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Effect of Material and Process Parameters
on Physical and Mechanical Properties
The effect of the seven parameters (material and process
parameters, Table 2) on the properties was obtained by
performing the above-mentioned calculations followed by
ANOVA. The main effects of the control parameters on the
properties of sintered samples are plotted in Figs. 3, 4, 5,
and 6.
Effect of Scrap Material Source and Graphite
Addition on Properties
The effect of the source of scrap materials on various
mechanical properties is shown in Fig. 3. The source of
material did not have a significant effect on sintering
density. However, the average hardness of the samples
having GS as a source of scrap material was almost three
times higher than that of the FS. The improvement in
sintered density in the samples having GS was observed
because of a dense metallic structure produced from the
higher degree of reduction and densification [29]. Simi-
larly, improvement in compressive strength was observed
in GS by virtue of superior densification.
Graphite addition was found to affect all the properties
measured. The sintered density was found to be the highest
when graphite was added in stoichiometric (10 % by wt.)
proportion. This observation was based on residual carbon
that was left behind after sintering. Decreasing hardness
with increasing graphite addition was because of the
presence of unreacted excess graphite resulting in patches
of carbon-rich spots and porous structures after sintering.
This was also confirmed by SEM analysis and elemental
mapping as shown in Fig. 7. Graphite addition in excess

Fig. 3 Effect of scrap material 6 6

source and graphite addition on
Sintered Density (g/cm3)

Sintered Density (g/cm3)

a, b sintered density (g/cm3), c, 5.5 5.5
d hardness (HR 15T), e,
5 5
f maximum compressive
strength (MPa), respectively. D 4.5 4.5
is the difference between the
maximum and minimum value 4 4
of a parameter for given setting.
Larger the difference more is 3.5 3.5
the significance of parameter in Δ 0.52 Δ 1.07
deciding the properties (used as 3 3
Forging Scale Grinding Sludge 10 15 20
a representation for significance
of parameter over the (a) Material Source (b) Graphite added (wt.%)
considered properties, Example:
D for max. compressive strength 35 35
corresponding to variation in (1)
30 30
material source is
Hardness (HR 15T)
Hardness (HR 15T)

(280.92 - 121.56) = 169.68 25 25

and (2) graphite addition is 20
20
(352.59 - 84.87) = 252.18. D
is higher in second case; this 15 15
means graphite addition is more 10
10
important for deciding max.
compressive strength) 5 5
Δ 20.79 Δ 8.30
0 0
Forging Scale Grinding Sludge 10 15 20
(c) Material Source (d) Graphite added (wt.%)

400 400
Max. Comp. Strength (MPa)
Max. Comp. Strength (MPa)

350 350
300 300
250 250
200 200
150 150
100 100
Δ 169.68 Δ 252.18
50 50
Forging Scale Grinding Sludge 10 15 20
(e) Material Source (f) Graphite added (wt.%)

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J. Sustain. Metall. (2017) 3:251–264 257

Fig. 4 Effect of compaction 6 6

pressure and compact weight on

Sintered Density (g/cm3)

Sintered Density (g/cm3)

a, b sintered density (g/cm3), c, 5.5 5.5
d hardness (HR 15T), e,
f maximum compressive 5 5
strength (MPa), respectively
4.5 4.5

4 4

3.5 3.5
Δ 0.30 Δ 0.37
3 3
600 900 1200 2 3 4
(a) Compaction Pressure (MPa) (b) Compact Weight (g)

35 35
30 30

Hardness (HR 15T)

Hardness (HR 15T)

25 25
20 20
15 15
10 10
5 5
Δ 5.12 Δ 5.23
0 0
2 3 4 600 900 1200
(c) Compact Weight (g) (d) Compaction Pressure (MPa)

400 400
Max. Comp. Strength (MPa)

Max. Comp. Strength (MPa)

350 350
300 300
250 250
200 200
150 150
100 100
Δ 145.98 Δ 39.58
50 50
600 900 1200 2 3 4
(e) Compaction Pressure (MPa) (f) Compact Weight (g)

quantities also reduces the compressive strength due to the
formation of voids.
Effect of Compaction Parameters on Properties
The graphite addition in excess obstructed the improve-
ment in green and sintered density with increasing com-
paction pressure. Hence, the addition of graphite lowered
the densities, despite high compaction pressure. This was
in agreement with earlier observations [30]. The changes in
properties with levels of compaction parameters are shown
in Fig. 4.
The compaction pressure of 900 MPa can be considered
to be the optimum for hardness because lower pressure
(i.e., 600 MPa in this study) led to lesser green density.
Hence, it resulted in inadequate surface contact among
particles that hindered the solid-state reaction between iron
oxide and graphite during reduction. Although higher
compaction pressure (i.e., 1200 MPa in the present study)
created dense green samples, gases evolved during the
(reduction) transformation could not be accommodated,
nor could they escape easily. This resulted in incomplete
transformation as well as swelling during reduction. Hence,
the compaction pressure of 900 MPa was found to give the
best outcome among the three levels of compaction pres-
sures studied.
In the present study, the green cylindrical sample had a
diameter of around 10 mm, and heights varying from 07 to

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Fig. 5 Effect of sintering 6 6

temperature and sintering time

Sintered Density (g/cm3)

Sintered Density (g/cm3)

on a, b sintered density (g/cm3), 5.5 5.5
c, d hardness (HR 15T), e,
f maximum compressive 5 5
strength (MPa), respectively
4.5 4.5

4 4

3.5 3.5
Δ 0.91 Δ 0.53
3 3
1050 1150 1250 30 60 90
(a) Sintering Temprature (oC) (b) Sintering Time (min)
35 35
30 30

Hardness (HR 15T)

Hardness (HR 15T)

25 25
20 20
15 15
10 10
5 5
Δ 7.35 Δ 6.62
0 0
1050 1150 1250 30 60 90
(c) Sintering Temprature (oC) (d) Sintering Time (min)

300 300
Max. Comp. Strength (MPa)

Max. Comp. Strength (MPa)

250 250

200 200

150 150

100 100
Δ 179.69 Δ 148.35
50 50
1050 1150 1250 30 60 90
(e) Sintering Temprature (oC) (f) Sintering Time (min)

14 mm, giving different green densities due to varying
additions of graphite and compaction parameters. The
variation in the properties of the sintered samples was
marginal with varying H/D ratios (for the narrow range of
compact weights studied). This was because the decrease in
weight during reduction of iron oxides was compensated by
volumetric shrinkage during reduction and sintering,
resulting in negligible variation in the sintered density.
Effect of Sintering Parameters on Properties
The effect of sintering temperature is shown in Fig. 5a, c,
and e as it was one of the most significant parameters.
Although carbothermic reduction starts from 1050 °C, the
sintering temperature below 1150 °C resulted in an inad-
equate reduction of iron oxide and hence no sintering
occurred. Thus, samples sintered at 1050 °C have lower
sintered density.
The effect of sintering temperature on hardness is the
highest at 1150 °C as shown in the plot. Although a higher
sintering temperature, i.e., 1250 °C, would cause faster
reduction at the surface, bulk densification and mechanical
properties are adversely affected. This is because of the
impervious shell of reduced iron getting formed in the
initial phases of sintering, thereby hindering the passage of
gases needed for further reduction and densification. The

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J. Sustain. Metall. (2017) 3:251–264 259

Fig. 6 Effect of heating-to- 6 35

cooling rate ratio during
sintering on a sintered density 30

Sintered Density (g/cm3)

5.5
(g/cm3), b hardness (HR 15T),

Hardness (HR 15T)

25
and c maximum compressive 5
strength (MPa) 20
4.5
15
4
10
3.5 5
Δ 0.18 Δ 5.53
3 0
3/7 5/7 7/7 3/7 5/7 7/7
(a) Ratio of Heating to cooling rate (b) Ratio of Heating to Cooling rate

400

Max. Comp. Strength (MPa)

350
300
250
200
150
100
Δ 87.42
50
3/7 5/7 7/7
(c) Ratio of Heating to Cooling rate

Reduced Iron

(a) (b)

Porous structures Carbon rich spots

Elemental analysis (in %) at Point 1: 1.29 C, 0.48 Si, 0.80 Mn, 97.42 Fe, Point 2: 9.72 C, 17.0 O, 73.21 Fe

Fig. 7 Metallography of sintered samples for G2 experimental condition a SEM image at 2000X b SEM image at 93000 magnification
(elemental analysis from EDAX)

rate of formation of reduced iron shell formation increases hardness of the scrap powder samples with sintering tem-
with sintering temperature. Thus, the intermediate level of perature can be correlated with the reduction of the oxides.
sintering temperature of 1150 °C, therefore, seems to be The effect of sintering time on mechanical properties is
optimum compared to the other two temperatures from the presented in Fig. 5b, d, and f. With increasing sintering
standpoint of properties considered. The increase in time, all the mechanical properties were improved. The

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completion of densification and grain growth took place
with the increasing sintering time as both reduction and
densification were diffusion-controlled characteristics.
The effects of heating and cooling rates during the
sintering cycle on the mechanical properties are given in
Fig. 6. There was a marginal variation in properties when
the heating rate varied. The hardness and compressive
strength were both seen to be the highest when a heating
rate of 5 °C/min was used.
Multiobjective Optimization of Physical
and Mechanical Properties
The previous section deliberated the optimal values of the
control parameters on individual properties like sintered
density, hardness, and maximum compressive strength.
However, one needs a single optimal level of control
parameters to satisfy the overall objective of achieving the
highest possible sintered density for solid-state recycling of
scrap via powder metallurgy. Thus, a multiobjective opti-
mization technique like the gray relational analysis (GRA)
[31–33] would be appropriate for the purpose.
In the first step of the GRA, all the responses were
normalized in the range of 0–1 with the highest response
value in the given set of experiments. Normalized values
were determined using the following relation (5):
xoi ðkÞ  minx0i ðkÞ
xi ðkÞ ¼ ; ð5Þ
maxx0i ðkÞ  minx0i ðkÞ
where i is the trial number, i = 1 to 18, k = 1 to n, and n is
the performance characteristic (n = 3 in the present study)
The normalized values of sintered density, hardness, and
maximum compressive strength are shown in Table 5. The
gray relation coefficient, fi(k) was also computed for each
performance characteristic (k) using the following relation
(6):
Dmin ðkÞ þ WDmax ðkÞ
fiðkÞ ¼ ð6Þ
D0i ðkÞ þ WDmax ðkÞ
D0i ¼ jj x0 ðkÞ  xi ðkÞ jj ¼ difference between absolute
values of x0 ðkÞ and xi ðkÞ
W = distinguishing coefficient 0 B W B 1 (here
W = 0.333 in order to assign equal weightage to all three
responses, i.e., quality characteristics)
Dmin ¼ min min x0 ðkÞ  xi ðkÞ the smallest value of D0i
rj2i rj2k
Dmax ¼ max max x0 ðkÞ  xi ðkÞthe largest value of D0i
rj2i rj2k
Gray relational grade  i was calculated by averaging
gray relational coefficients of all responses using the fol-
lowing relation (7):

Table 5 Gray relational coefficients for considered properties and gray relational grade
Exp. Sample Sintered density Hardness Max. compressive strength Overall
No. description
Normalized Gray relation Normalized Gray relation Normalized Gray relation Gray relation Rank
coeff. coeff. coeff. grade

1 FS1 0.23 0.30 0.04 0.26 0.02 0.25 0.27 16

2 FS2 0.55 0.43 0.23 0.30 0.19 0.29 0.34 9
3 FS3 0.79 0.61 0.13 0.28 0.68 0.51 0.46 5
4 FS4 0.47 0.38 0.22 0.30 0.14 0.28 0.32 10
5 FS5 0.68 0.51 0.33 0.33 0.07 0.26 0.37 8
6 FS6 0.28 0.31 0.04 0.26 0.05 0.26 0.28 15
7 FS7 0.00 0.25 0.06 0.26 0.09 0.27 0.26 17
8 FS8 0.41 0.36 0.07 0.26 0.19 0.29 0.30 12
9 FS9 0.02 0.25 0.00 0.25 0.00 0.25 0.25 18
10 GS1 0.99 0.96 1.00 1.00 0.70 0.53 0.83 2
11 GS2 0.85 0.69 0.98 0.93 0.62 0.47 0.70 4
12 GS3 1.00 1.00 0.74 0.56 1.00 1.00 0.85 1
13 GS4 0.25 0.31 0.34 0.33 0.17 0.29 0.31 11
14 GS5 0.27 0.31 0.23 0.30 0.07 0.26 0.29 13
15 GS6 0.97 0.92 0.69 0.52 0.99 0.98 0.80 3
16 GS7 0.49 0.39 0.78 0.60 0.18 0.29 0.43 7
17 GS8 0.34 0.33 0.83 0.67 0.19 0.29 0.43 6
18 GS9 0.09 0.27 0.28 0.31 0.04 0.26 0.28 14

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J. Sustain. Metall. (2017) 3:251–264 261

Gray relational grade for i the experiment ð i Þ
1X n
¼ f ðkÞ;
n k¼1 i
where n = number of performance characteristics (here
n = 3).
For example, in case of the FS8 experimental condition,
4:50  3:48
x08 ðkÞ ¼ x08 ð1Þ ¼ ¼ 0:41
5:98  3:48
D0i ¼ D08 ¼ 1  0:41 ¼ 0:59
0 þ 0:33
fiðkÞ ¼ f8ð1Þ ¼ ¼ 0:36
0:59 þ 0:33
1 marginal effect on the responses. However, its second level
 i ¼  8 ¼ ðf8ð1Þ þ f8ð2Þ þ f8ð3ÞÞ
3
0:36 þ 0:26 þ 0:29
¼ ¼ 0:30
3 tering time) did not show a single optimal condition satis-
where i = 8 (8th experimental condition), k = 1 for sin-
tered density, k = 2 for hardness, and k = 3 for uniaxial
compressive strength.
The gray relational coefficients and grades for the 18
experiments in the L18 experimental array were calculated,
and are listed in Table 5. Gray relational coefficient with
W = 0.333 provided equal weightage for each considered
mechanical property response. Gray relational grade aggre-
gated the gray relational coefficients (corresponding to the
considered mechanical properties) to form an overall quality
characteristic function. A higher value (near to 1) of Gray
Relational Grade (GRG) implied near-optimal parametric
setting. The experimental conditions were ranked on the basis
of gray relational grade. The main effects of control param-
eters were determined after applying ‘‘Larger the better’’
criteria to the GRG and their values are shown in Table 6.
Based on gray relational analysis, the optimum setting
for overall process characteristics was determined as A2,
B1, C2, D1, E2, F3, and G2. This setting corresponded to
the highest GRG among the three levels of each of the
parameters A to G. Material parameters with sintering
temperature and time influenced the individual properties
the most (shown by the main effect plots in Figs. 3, 4, 5,
and 6). Optimal levels of comparatively insignificant
ð7Þ parameters (compaction pressure and compact weight)
were found to be dissimilar to studied properties’ charac-
teristics and optimal level from GRA.
From the foregoing, it is clear that the source material has
the same optimal level (A2) for each of the three response
variables, i.e., GS was found to be superior when recycled
using powder technology. Hence GS was chosen as the
source of material for all subsequent experimentation.
Samples sintered at 1150 °C with 90 min of sintering time
resulted in improvement in the properties of interest, as
discussed earlier. The ratio of heating-to-cooling rate has a
was found to give the best properties. The rest of the
insignificant control parameters (compact weight and sin-
fying all the objectives. Hence optimal condition for a
control parameter was chosen on the basis of overall opti-
mum parameter settings. A single optimum setting corre-
sponding to c using GRA optimization approach was A2, B1,
C3, D1, E2, F3 and G2. This, however, did not agree with any
of the experimental conditions in the L18 array. The exper-
imental condition ‘‘GS3’’ in the L18 array (which was used
as the initial setting to arrive at the optimal condition) pro-
vided the best of quality characteristics among the L18 sets of
experimental conditions. Thus, the process characteristics
corresponding to an overall optimal experimental condition
as predicted was verified with a confirmatory experimental
run using three samples.
The predicted gray relational grade at optimal setting ðc^Þ
is calculated using the following relation (8):
X
p
 
c^ ¼ cm þ cj  cm ; ð8Þ
j¼1
where cm is the total mean gray relational grade
 j is the mean gray relational grade at optimal level (see
Table 5), and p is the number of parameters which affect
the quality characteristics.

Table 6 Average gray

Parameters Levels Range (max–min)
relational grade at each level of
control parameters 1 2 3

A: Material source 0.316 0.546* – 0.230

B: Graphite addition (% excess) 0.574* 0.394 0.324 0.250
C: Compaction pressure (MPa) 0.401 0.404 0.487* 0.085
D: Compact weight (g) 0.461* 0.400 0.431 0.060
E: Sintering temperature (oC) 0.344 0.507* 0.440 0.162
F: Sintering time (min) 0.406 0.384 0.502* 0.118
G: Ratio of heating-to-cooling rate 0.409 0.488* 0.394 0.094
* Indicates the optimal parametric setting/level

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Table 7 Comparison between predicted values and experimental outcomes

Level setting Initial (GS3 experiment) condition Optimum condition derived from GRA
A2, B1, C3, D2, E2, F1, and G1 A2, B1, C3, D1, E2, F3, and G2

Measured properties from experiments

Sintered density (g/cm3) 5.68 6.06
Hardness (HR 15T) 35.41 38.24
Max. compressive strength (MPa) 614.15 618.47
GRG
Overall 0.85 (from Table 5) 0.98 (predicted)

A set of three samples (made under A2, B1, C3, D1, E2,
F3, and G2 conditions) were tested for properties like
sintered density, hardness, and maximum compressive
strength, and the average value across the three quality
characteristics was calculated. The improvement in indi-
vidual as well as overall characteristics using optimal
parametric setting is presented in Table 7.
The improvement in the measured properties, individual
as well as overall, may be inferred from Table 4, wherein the
properties from the GRA-optimized conditions are about
14 % superior to those from the L18 experiments. The
improvement in the properties of recycled parts (produced
with the parametric combination based on the GRA tech-
nique) from other parts produced with L18 experimental
setting is caused by comparative chemical composition and
level of porosity after sintering. The chemical composition
of recycled iron (PM) parts (1.12 wt% C, 0.42 wt% Si, 0.76
wt% Mn, and balance Fe) is similar to high-carbon steel
which contains approximately 0.7–2.5 wt% carbon.
(1) Grinding sludge as a source of scrap enables
achieving superior mechanical properties due to
complete reduction of iron oxide along with densi-
fication during sintering.
(2) The graphite addition in stoichiometric proportions
for reduction results in higher degree of densification
regardless of inferior reduction.
(3) Compact weight and ratio of heating-to-cooling rate
in sintering have been proven to be insignificant in
improving the mechanical properties due to their
narrow range of variation.
(4) Process parameters, particularly sintering tempera-
ture of 1150 °C and 90-min sintering time, signif-
icantly improve mechanical properties of the
samples obtained using powder metallurgy-based
recycling process.
(5) Mechanical properties of samples obtained from
optimized GRA experimental setting are superior to
those obtained from the best experimental condition
(GS3) in Taguchi L18 array by 14 %.

Conclusions
Appendix
Experimental studies on in situ carbothermic reduction and
PM process with the considered process variables for
See Table 8
recycling of ferrous metallic scrap were conducted. The
outcomes are summarized as follows:

Table 8 L18 array of Taguchi’s experimental design

Exp. Sample A: Material B: Graphite C: Compaction D: Compact E: Sintering F: Sintering G: Ratio of
No. details source addition (% pressure (MPa) weight (g) temperature (°C) time (min) H/C rate
excess)

1 FS1 Forging scale 0 600 2 1050 30 3/7

2 FS2 Forging scale 0 900 3 1150 60 5/7
3 FS3 Forging scale 0 1200 4 1250 90 7/7
4 FS4 Forging scale 50 600 2 1150 60 7/7
5 FS5 Forging scale 50 900 3 1250 90 3/7
6 FS6 Forging scale 50 1200 4 1050 30 5/7
7 FS7 Forging scale 100 600 3 1050 90 5/7

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Table 8 continued
Exp. Sample A: Material B: Graphite C: Compaction D: Compact E: Sintering F: Sintering G: Ratio of
No. details source addition (% pressure (MPa) weight (g) temperature (°C) time (min) H/C rate
excess)

8 FS8 Forging scale 100 900 4 1150 30 7/7

9 FS9 Forging scale 100 1200 2 1250 60 3/7
10 GS1 Grinding sludge 0 600 4 1250 60 5/7
11 GS2 Grinding sludge 0 900 2 1050 90 7/7
12 GS3 Grinding sludge 0 1200 3 1150 30 3/7
13 GS4 Grinding sludge 50 600 3 1250 30 7/7
14 GS5 Grinding sludge 50 900 4 1050 60 3/7
15 GS6 Grinding sludge 50 1200 2 1150 90 5/7
16 GS7 Grinding sludge 100 600 4 1150 90 3/7
17 GS8 Grinding sludge 100 900 2 1250 30 5/7
18 GS9 Grinding sludge 100 1200 3 1050 60 7/7

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