recycling

Article
Recycling Potential for Finely Divided Ferrous
Metallic Scrap Using Powder Technology
Kedarnath Rane 1, * and Prashant P. Date 2
1 Dipartimento di Meccanica, Politecnico di Milano, Piazza Leonardo da Vinci, 32, 20133 Milano MI, Italy
2 Department of Mechanical Engineering, Indian Institute of Technology, Bombay, Powai,
Mumbai 400076, India; ppdate@iitb.ac.in
* Correspondence: kedarnath.rane@polimi.it; Tel.: +39-0223998534




Received: 27 September 2018; Accepted: 14 December 2018; Published: 18 December 2018


Abstract: Enormous amount of scrap is generated on the shopfloor during manufacturing.

Energy needed to melt increasing quantities of scrap will be ever increasing, and so will be the
loss of metal during melting. Hence, conversion of scrap directly into marketable products by solid
state processing methods is economical due to a lower energy requirement and a greater yield
compared to the melting route. This makes the process more environmentally friendly. However,
not all materials can be recycled in a solid state, with equal ease. One therefore needs to quantitatively
assess the recyclability of a given kind of scrap. In the present work, a procedure to assess the
recyclability of finely divided ferrous metallic scrap generated on the shopfloor is demonstrated.
Recyclability includes material and the process used for recycling. For instance, a given material
might be more recyclable using one process compared to the other. In the present study, the potential
of powder technology (powder metallurgy (PM) and metal injection molding (MIM) based processes
are compared for solid-state conversion of scrap directly into usable products. Grinding sludge
collected in the shopfloor was pulverized and used as raw material. Properties of sintered parts
were found to be significantly better due to in-situ reduction and densification during sintering.
A quantitative measure of recyclability, namely, the Recyclability Index (RI) was defined to compare
the manufacturability of different products. Recycled ferrous parts manufactured by PM route
are found to have a greater RI (superior recyclability) than those manufactured by the MIM route.
Complex reduction and sintering mechanisms in MIM parts, particularly, the kinetics of diffusion and
volumetric shrinkage, limit suitability of MIM for recycling. In contrast, few industrial parts were
developed and manufactured by conventional PM based approach to demonstrate the suitability of
this novel recycling process especially for manufacture of porous parts.

Keywords: solid state recycling; metallic scrap/sludge; powder metallurgy; in-situ reduction

1. Introduction
Conventional recycling relies on secondary sources (graded metallic scrap and industrial waste)
to reduce the cost of manufacture using metal from the primary sources. Nearly 40 percent of steel
is produced from secondary sources worldwide [1,2]. Secondary Steelmaking using an electric arc
furnace uses metallic scrap as the primary raw material. This process is found to be feasible and
economical when a large quantity of scrap is available [3]. Solid state approaches used for recycling
non-ferrous metallic scrap, and on the other hand, process scrap is available in limited quantities but
requires high capacity presses for deformation and furnaces for heating [4]. The powder technology
based novel solid-state recycling process has the following advantages for the recycling of particulate
ferrous metallic scrap:

Recycling 2018, 3, 59; doi:10.3390/recycling3040059 www.mdpi.com/journal/recycling

Recycling 2018, 3, 59 2 of 15

1. Alloying by adding different metallic powders thereby achieving unique properties and
microstructure.
2. Sintering stage can be used for the thermochemical treatment of materials.
3. Low energy consumption compared to the melting route and shorter overall production time.
4. Significant cost benefits due to a significantly cheaper raw material, i.e., the powder.
5. Net-shape manufacturing. Little or no scrap is further generated during processing.
6. High process yield (high metal recovery).

It is therefore important to quantify the properties and characteristics of products made by

recycling. Usually, recycled manufacturing scrap constitutes metallic particles of greater purity
than the ore from which virgin metal is extracted. However, unless the relationship between the
product properties and manufacturing parameters is standardized and controlled, getting the desired
quality is difficult. For instance, with particulate raw material (powders), large and complex shaped
parts are difficult to make. Moreover, low ductility and low strength of parts, not to mention the
atmospheric contamination due to powder and dust, and the emission from furnaces, are commonly
faced issues [5,6] that need to be overcome to achieve the desired product quality.
Currently, applications of powder metallurgy (PM) may be classified into four major domains,
namely, structural, tribological, cutting tools, and magnetic parts. However, parts produced by PM
based recycling will not be suitable for all these domains and applications within these domains.
Powder Metallurgy based recycling technique yields products of limited strength due to a high level of
porosity, which is inevitable. Thus, this method of recycling suits manufacture of parts for applications
where porosity is desirable and limited structural strength is expected [7,8].
Metal injection molding (MIM) is best suited for high-volume production of small metal parts. As
with injection molding, these parts can be geometrically complex and have thin walls and fine details.
As powdered metal is not melted in the MIM process, high-temperature alloys can be recycled to make
tools without any adverse effect on tool life [9].
A brief overview of PM and MIM process steps in the context of recycling in process ferrous scrap
is given below:
For the PM process, pulverization of identified metallic scrap (a mixture of oxides of iron in
various proportions of oxygen depending on the source of scrap) is performed by crushing and
ball-milling. Brittle iron oxide (e.g., forging scale) is crushed by a jaw crusher followed by ball milling.
In ball-milling, harder ceramic (ZrO2 ) balls impinge on the brittle iron oxide refining the particle size.
After sieving the powder, relatively coarser particles are used for conventional PM. In the MIM process,
fine particles are needed to get adequate mouldability of the feedstock by injection and moulding,
besides getting excellent mechanical properties and dimensional stability of sintered parts.
Phases of iron oxide in scrap were determined quantitatively to calculate the quantity of
(carbonaceous) reducing agents required for carbothermic reduction during sintering. A calculated
amount of reducing agent (here carbonaceous material) is mixed with iron oxide powder for in-situ
carbothermic reduction during sintering. Mixing was performed using a mixer grinder mixing, turbula
mixing, and low-energy ball milling, as well as a combination of these. The powder mixture was
uniaxially compacted using either a hydraulic press or a mechanical press, which enabled compaction
at different strain rates. Compaction of powder mixture to different sample shapes such as a solid
cylinder and cylindrical bushes of various dimensions was also performed using dies designed and
manufactured for the purpose. Compacted samples were then heated to have in-situ reduction and
densification during the PM sintering cycle. A laboratory scale tubular furnace with inert gas flow
arrangement as well as vacuum was utilized [10]. A series of reduction reactions took place during the
initial phase of sintering, as represented schematically in Figure 1.
Recycling 2018, 3, 59 3 of 15
Recycling 2018, 8, 59 3 of 16

Figure 1. Schematic representation of in-situ carbothermic reduction during sintering of PM compacts.

Figure 1. Schematic representation of in-situ carbothermic reduction during sintering of PM compacts.

The first step of MIM process is to create a feedstock (a mixture) of metal powder, a reducing agent
The first step of MIM process is to create a feedstock (a mixture) of metal powder, a reducing
as before, and a polymer. The metal powder was mixed with a thermoplastic binder, cooled, and then
agent as before, and a polymer. The metal powder was mixed with a thermoplastic binder, cooled,
granulated into a homogeneous
and then granulated feedstock in feedstock
into a homogeneous the form of in pellets.
the form Usually, sigma
of pellets. blade mixer
Usually, sigmawas used
blade
tomixer
preparewastheused
feedstock, which
to prepare thetypically
feedstock,hadwhich
60% metal and had
typically 40% 60%polymermetal byand
volume. The feedstock
40% polymer by
was shaped using the equipment and tooling similar to what is used
volume. The feedstock was shaped using the equipment and tooling similar to what is used in plastic injection molding.
in
However, the mold
plastic injection cavitiesHowever,
molding. have to bethedesigned approximately
mold cavities have to be20% larger approximately
designed to account for the 20%shrinkage
larger
oftothe moulded
account product
for the during
shrinkage sintering.
of the moulded During
product the molding
during cycle,
sintering. the feedstock
During the molding is melted
cycle, theand
injected into the mold cavity, where it cools and solidifies into the shape of
feedstock is melted and injected into the mold cavity, where it cools and solidifies into the shape of the part. The molded
“green”
the part.part
Theismolded
ejected.“green”
In the part
subsequent
is ejected. step, polymer
In the subsequentbinders
step,are removed
polymer fromare
binders theremoved
solidified
moulded
from the shape.
solidified In moulded
some cases, solvent
shape. In somedebinding is firstdebinding
cases, solvent performed in which
is first performedthe “green”
in whichpart
the is
placed
“green”in water
part isorplaced
chemical bath (depending
in water or chemicalon the (depending
bath solubility ofon thethe
binder) to dissolve
solubility of the the sacrificial
binder) to
dissolve
binder the sacrificial
component. The binder
solventcomponent.
debinded part Theissolvent
heateddebinded
at a gentlepart is heated
heating rate inat aa low-temperature
gentle heating
rate to
oven in remove
a low-temperature
the residualoven to remove
solvent the residual
left behind solventAfter
in the pores. left behind
this step,in the pores.debinding
thermal After this or
step, thermal debinding or pre-sintering is performed in vacuum to remove
pre-sintering is performed in vacuum to remove the polymer binder by evaporation. As a result, the polymer binder by
evaporation. As a result, the remaining “brown” metal part contains
the remaining “brown” metal part contains approximately 40% voids by volume. The final step ofapproximately 40% voids by
volume. isThe
sintering final step
required of sinteringthe
to consolidate is required to consolidate
loosely bound powder the loosely
in the “brown”bound powder
part, in the
resulting in a
“brown” part, resulting in a high-density (95–99%) metal part. Sintering is usually
high-density (95–99%) metal part. Sintering is usually carried out in an inert gas atmosphere or in the carried out in an
inert gasSintering
vacuum. atmosphere or in the are
temperatures vacuum.
usuallySintering temperatures
close to 85% are usually
of the metal’s meltingclosepointto[11,12].
85% of the
metal’s melting point [11,12].
Literature available so far does not contribute to the knowledge of the effect of process variables
Literature available so far does not contribute to the knowledge of the effect of process variables
on the process of solid state recycling, and the resulting product properties.
on the process of solid state recycling, and the resulting product properties.
The primary objective of the present work is to establish a correlation between the properties of
The primary objective of the present work is to establish a correlation between the properties of
the product (at the end of in-situ reduction during sintering wherein metallic iron is obtained from iron
the product (at the end of in-situ reduction during sintering wherein metallic iron is obtained from
oxide), and process variables (thermal debinding temperature, sintering temperature, sintering time,
iron oxide), and process variables (thermal debinding temperature, sintering temperature, sintering
thermal debinding atmosphere, and sintering atmosphere). Finally, an attempt is made to analyze the
time, thermal debinding atmosphere, and sintering atmosphere). Finally, an attempt is made to
recyclability of metallic scrap by the PM and MIM process.
analyze the recyclability of metallic scrap by the PM and MIM process.
2. Materials and Methods
2. Materials and Methods
Metallic waste generation in a forging plant at every intermediate process starting from hot
Metallic waste generation in a forging plant at every intermediate process starting from hot
forging, cutting to final finishing operation, was analyzed. Oxide scales, chips, and trimmed flash
forging, cutting to final finishing operation, was analyzed. Oxide scales, chips, and trimmed flash
are
areusually recycled
usually recycledin a in
conventional steel making
a conventional processprocess
steel making by melting,
by whereas
melting, metallic
whereasconstituents
metallic
inconstituents
grinding sludge are used for landfilling. Grinding sludge/swarf is a crude mixture
in grinding sludge are used for landfilling. Grinding sludge/swarf is a crude mixture of metallic
of
(about
metallic (about 50 wt. % of iron oxides and pure metal particles) and nonmetallic constituentsas
50 wt. % of iron oxides and pure metal particles) and nonmetallic constituents such dust,
such
cutting fluids,
as dust, and
cutting lubricants.
fluids, Many new
and lubricants. Manytechniques have been
new techniques adopted
have for recycling
been adopted such scrap
for recycling suchby
hot consolidation
scrap for manufacturing,
by hot consolidation pigments for
for manufacturing, paint industry,
pigments for paint etc. These etc.
industry, processes do not provide
These processes do
 Recycling 2018, 3, 59 4 of 15
Recycling 2018, 8, x FOR PEER REVIEW 4 of 16

direct application of these essential metallic resources. Powder technology (particularly PM and MIM),
not provide direct application of these essential metallic resources. Powder technology (particularly
as discussed in the previous section, is used to get usable products directly after recycling. Grinding
PM and MIM), as discussed in the previous section, is used to get usable products directly after
sludge was dried to remove moisture, roasted under controlled conditions to obtain pyrolytic carbon
recycling. Grinding sludge was dried to remove moisture, roasted under controlled conditions to
from nonmetallic constituents, and ball milled for pulverization.
obtain pyrolytic carbon from nonmetallic constituents, and ball milled for pulverization.
SEM-EDS study of powder samples was performed in order to find the semi quantitative elemental
SEM-EDS study of powder samples was performed in order to find the semi quantitative
composition and the grade of steel. The powder was first coated with an ultra-thin film of gold in an
elemental composition and the grade of steel. The powder was first coated with an ultra-thin film of
ion sputter (Anatech, Model: Hummer VI-A) and was observed under a Scanning electron microscope
gold in an ion sputter (Anatech, Model: Hummer VI-A) and was observed under a Scanning electron
(Hitachi,
microscope Model:
(Hitachi, S-3400N).
Model: The XRD
S-3400N). Theanalysis
XRD was carried
analysis out carried
was using Analytical Diffractometer
out using Analytical (X’Pert)
for determining the iron oxide phases of the sludge. A diffraction pattern was
Diffractometer (X’Pert) for determining the iron oxide phases of the sludge. A diffraction pattern obtained over a range
5 ◦ to 90◦ at an average increment size of 0.015◦ . As each of the oxide phases exhibits characteristic
was obtained over a range 5° to 90° at an average increment size of 0.015°. As each of the oxide
reflection
phases exhibits peaks corresponding
characteristic reflection to its d-values,
peaks these sets
corresponding to of
itsd-values
d-values,were matched
these sets ofwith standards for
d-values
were matched with standards for iron oxide phases and various species of oxides were identifiedthe
iron oxide phases and various species of oxides were identified in the sludge. Table 1 gives in chemical
composition of the powdered grinding sludge, which served as the raw material
the sludge. Table 1 gives the chemical composition of the powdered grinding sludge, which served for this study.
as the raw material for this study.
Table 1. Semi-quantitative abundance of major and minor elements in powdered grinding
sludge sample.
Table 1. Semi-quantitative abundance of major and minor elements in powdered grinding sludge
sample. Elements C O Al Si Mn Fe
wt. %
Elements C6.21 O 29.03Al 0.39
Si Mn0.57 Fe 0.42 63.38
wt. % 6.21 29.03 0.39 0.57 0.42 63.38
Iron (Fe) and oxygen (O) are the major constituents in powder sample, whereas carbon (C) is a
Ironminor
(Fe) and oxygen
element. The(O)presence
are the major constituents
of alloying elements insuch
powder sample,
as Mn, Si, andwhereas carbonform
Al in powder (C) isina grinding
minor element. The presence of alloying elements such as Mn, Si, and Al in powder
sludge confirms that scrap is derived from finishing operations of micro-alloyed steel. The XRD form in grinding
sludge confirms
analysis that scrap is derived
also confirmed from finishing
the presence of Fe3 O4 operations
(92.8 wt. %),ofFeOmicro-alloyed
(1.9 wt. %), steel.
Fe(CO) The XRD
5 (1.5 wt. %) and
analysis also confirmed
negligible portiontheorpresence
absenceofofFe Fe3O O4 (92.8
2 3 in wt.
the %), FeO
Grinding (1.9
Sludgewt. %),
(GS). Fe(CO) 5 (1.5
Similar wt. %)
observations andhave been
negligible portion or absence of Fe O in the Grinding Sludge (GS). Similar observations
reported by F. Demirci et al. [13] using a microstructural examination of a section of the mill scale.
2 3 have been
reportedTheby F. Demirci
absence ofettheal.Fe
[13] using a microstructural examination of a section of the mill scale.
2 O3 phase in grinding sludge is due to a very short exposure of iron to high
The absence of the Fe O phase
temperature and rapid cooling
2 3 in grindingof thesludge
grinding is chip.
due to a verythe
Neither short exposureattained
temperature of iron to norhigh
the duration
temperature and rapid cooling of the grinding chip. Neither the temperature
of exposure is adequate to form Fe2 O3 during the grinding process [13]. Determined values attained nor the of iron
durationoxide
of exposure
phasesiswereadequate
used to tocalculate
form Fe2O the3 during
amount theofgrinding processfor
carbon needed [13]. Determined
carbothermic values
reduction.
of iron oxide phases were used to calculate the amount of carbon needed for carbothermic
The theoretical requirement of carbon for reduction of 1 g of Grinding Sludge powder (92.78% reduction.
The Fe
theoretical requirement of carbon for reduction of 1 g of Grinding Sludge powder (92.78%
3 4 , 1.92% FeO, 1.44% Fe, and 3.84% C by wt.) may be calculated as:
O
Fe3O4, 1.92% FeO, 1.44% Fe, and 3.84% C by wt.) may be calculated as:
2Fe3 O4 + C = 6FeO CO2
2 Fe3O4 + C = 6 FeO CO2 (1) (1)
(0.9278) ∗ 0.0247 [0.864] 0.088
(0.9278) * 0.0247 [0.864] 0.088
FeO + C =
FeO Fe +CO2 C = Fe CO2 (2)
(2)
(0.0192) + [0.864] (0.0192) + [[0.692]
0.0738 0.864] 0.272
0.0738 [0.692] 0.272
∴ Total
Total theoretical
theoretical CCneeded
neededper gram
per of grinding
gram sludge
of grinding (by wt.)
sludge (by= wt.)
0.0247
= +0.0247
0.0738+= 0.0738
0.0985 g= 0.0985
(3) g (3)

* ( ) represents mass obtained

* ( ) represents from source,
mass obtained fromand [ ] represents
source, mass obtained
and [ ] represents from reaction.
mass obtained from reaction.
As carbon is the limiting reactant (controls carbothermic reduction reaction)
As carbon is the limiting reactant (controls carbothermic reduction reaction) and stoichiometric
and stoichiometric
proportion of carbonofmay
proportion not may
carbon produce the desired
not produce the degree
desiredofdegree
reduction [14]. Carbon
of reduction [14]. isCarbon
mixed iswith
mixed with
powdered scrap inscrap
powdered 25%inexcess than than
25% excess the stoichiometric
the stoichiometricquantity [13,15].
quantity Commercial
[13,15]. Commercialpure pureiron
iron powder
powder and carbonyliron
and carbonyl ironpowder
powder (as(as detailed
detailed in Table
in Table 2) used
2) were wereasused as benchmarks
benchmarks in PM and in MIM,
PM andrespectively,
MIM, respectively,
to facilitatetonormalization.
facilitate normalization.
CP, GS, and GSGR powder mixtures were compacted to cylindrical shaped samples having
10 mm height as well as diameter. Sintered cylindrical samples (CP iron, GS, and GSGR) obtained after
conducting 33 full factorial experiments were used for characterization of properties. Important process
parameters, namely, compaction pressure (levels: 900, 1050, and 1200 MPa), sintering temperature
(levels: 1100, 1200, and 1300 ◦ C), sintering atmosphere (levels: Vacuum, argon gas, nitrogen gas) were
Recycling 2018, 3, 59 5 of 15

varied according to experimental settings (listed in Appendix A). Other parameters such as graphite
addition (25% excess than a stoichiometric requirement), reduction temperature (100 ◦ C below sintering
temperature), reduction time 30 min, and sintering time 60 min were kept constant. Three samples
per experimental condition were used for measurement of Degree of Reduction, i.e., DOR (for GS and
GSGR), sintered density, hardness, and yield strength (in compression).

Table 2. Physical properties of source material used in the present study.

Mean/Avg. Powder Loading

Process Material Particle Shape Density (g/cc) Identifier
Particle Size (µm) by wt. %
PM Commercial Pure (CP) Iron Spherical 48.03 7.73 CPI —-
PM Grinding Sludge (GS) Irregular 45.84 5.61 GS —-
PM GS - Graphite (GR) Irregular -Flakes 45.84 - < 5 5.61 - 2.26 GSGR —-
MIM Carbonyl Iron (CI) Spherical 3.29 7.60 CI90 90
MIM Grinding Sludge (GS) Irregular 2.64 5.71 GS75 75
MIM GS - Graphite (GR) Irregular -Flakes 2.64 - < 5 5.71 - 2.26 GSGR75 75

Previous studies have established that an organic binder system (Paraffin wax-HDPE-S.A)
improves the ease and homogeneity of melt flow by reducing interparticle friction during powder
injection molding by covering the entire surface area of the hard metallic powder particles.
The rheology of the feedstock depends on the nature, size, and shape of the metal or ceramic
particles [16,17]. Thus, in the present study, a binder system having 70 wt. % paraffin wax, 25 wt. %
HDPE and 5 wt. % stearic acid (S.A) was mixed with metallic powder using a Sigma Blade Mixer
running at 50 rpm [18] to prepare two separate MIM feedstocks, one designated as CI 90 (90% solid
loading of Carbonyl Iron powder), and the other GSGR75 (75% solid loading of a mixture of 65.77 wt. %
Grinding Sludge and 9.22 wt. % GRaphite).
Dogbone and cylindrical shaped samples were injection molded for tensile and compression
testing, respectively. Solvent debinding was performed on parts of different shapes made from different
feedstock materials. Parts were debinded in n-Heptane at 56 ◦ C. To analyze the sintered properties of
MIM test samples made at different sintering temperatures and sintering atmospheres, a full factorial
(32 ) design was used. Nine experiments with three repetitions per experiment were performed to
study the effect of sintering atmosphere and temperature, each at three levels. Nine experimental
settings (sintering cycles) used to perform debinding and sintering of samples are given in Appendix B.
Three samples per experimental condition were used for measurement of DOR (for GSGR75), sintered
density, yield strength, UTS, elongation, and elastic modulus. The average values and standard
deviation of properties were determined to represent the corresponding experimental characteristics.

3. Results and Discussion

Process quality characteristics like Degree of Reduction (DOR) and Degree of Densification (DOD)
were determined by Equations (4) and (5).
 
Actual weight change
Degree of Reduction (DOR) = Theoretical weight × 100%
  change (4)
Initial weight−Final weight of the sample
= Initial weight− Theoretical reduced weight × 100%

ρSintered − ρGreen
 
Degree of Densification (DOD) = × 100% (5)
ρIron − ρGreen
During carbothermic reduction, the weight of the sample progressively decreased as oxygen from
the oxide was lost. The initial and final weight of the sample was measured. Weight change is the
sum total of the change in the weight of the constituents (oxide powder plus graphite). The ideal
(theoretical) weight of the reduced sample was calculated.
For example, if the compacted sample having 86.9565 wt. % iron oxide powder and 13.0435 wt. %
graphite (if 25% excess graphite added) weighed 3 g, then the theoretical reduced weight of iron can
be determined from relation (6) as,
Recycling 2018, 3, 59 6 of 15

Theoretical reduced weight of iron in sin tered part = 3 × 0.8695 × 0.704∗∗ = 1.8363 g (6)

(** Amount of iron obtained after reduction of 1 g of scrap powder, considering iron oxide phases in
scrap and stoichiometric calculations illustrated in relation (1) and (2) 0.692 + 0.012 of iron in scrap).
The density of the cylindrical compact was calculated by measuring its weight using a weighing
balance of 0.01 g accuracy and volume using dimensions measured by the calipers to 0.01 mm precision.
“Degree of Densification” of the sintered iron samples was calculated using relation (5) by
substituting the densities of the part into it before sintering (green density), after sintering (sintered
density), and assuming ρIron = 7.86 g/cm3 .
DOR, DOD, and mechanical properties of sintered parts are influenced by material and process
parameters (such as the composition of the scrap, reducing agent and reducing gas, sintering time,
compaction, injection, sintering and debinding temperatures, the particle size of iron oxide, compaction
pressure, etc.) of the recycling process. Effect of these parameters on process characteristics and
mechanical properties of recycled and sintered parts are discussed elsewhere [19,20]. However,
the correlation between process characteristics, particularly Degree of Reduction (DOR) and properties
of sintered parts is essential to understand the improvement in properties of GSGR and GSGR75 via
in-situ carbothermic reduction by powder technology (PM and MIM) based recycling approach in the
present work. The recycled material and part made from the recycled material should have comparable
properties as that of virgin wrought material besides similar or lesser energy consumption. Following
sections discuss the correlation between Degree of Reduction (DOR) and sintered properties along
with a novel quantitative evaluation of recyclability using the Powder Technology based recycling
approach. Optimized material and process parameter settings for Powder Metallurgy based recycling
were selected based on process characteristics (DOR and DOD), and properties of compacted and
sintered PM parts, as illustrated in References [10,15]. The latter part of this section demonstrates the
suitability and prospective applications of the proposed recycling technique.

3.1. Correlation between DOR and Sintered Properties of PM and MIM Parts
In PM sintering, in the absence of separately added graphite powder, in-situ reduction in a
grinding sludge (GS) sample occurs by carbothermic reduction of iron oxide through pyrolytically
generated carbon. Carbon (~4.32% by wt.) in grinding sludge is generated by pyrolytic transformation
of nonmetallic constituents during roasting of the GS. In the GSGR samples, carbothermic reduction
of iron oxide occurred due to both pyrolytically generated carbon and 25% excess graphitic carbon
added for carbothermic reduction.
Sintered density, hardness, and yield strength show an increasing trend with DOR. The reason
is the characteristics (properties and DOR) are simultaneously influenced by in-situ reduction and
setting of control parameters. Sintered densities of GS and GSGR samples were similar for 65% to 80%
DOR (Figure 2a). However, sintered density of GSGR samples further improved from 5.5 to 6.5 g/cm3
with an increase in DOR facilitated by 25% excess (compared to stoichiometry) carbon, compaction
pressure (1050 MPa), sintering temperature (1200–1300 ◦ C), and argon gas atmosphere in sintering.
Hardness measured on the surface of cylindrical sintered samples does not correlate well with DOR
(which is a bulk characteristic) [21]. The yield strength of sintered samples also correlated well with
DOR because the increase in the metallic transformation resulting from reduction and densification
enable a proportional increase in yield strength of the GSGR samples.
The effect of sintering parameters (sintering temperature and sintering atmosphere) on CI90 and
GSGR75 feedstocks was studied for suitability of MIM for recycling. These parts were characterized
to recognize the physical and mechanical property changes with sintering parameters and feedstock
materials. Properties of sintered samples of CI90 were used as a reference to normalize the
improvement in properties of sintered GSGR75 samples obtained from the MIM process.
Recycling 2018, 3, 59 7 of 15
Recycling 2018, 8, 59 7 of 16

7 7

Sintered Density (g/cm3)

Sintered Density (g/cm3)

6 6

5 5

4 4

3 3
GS GSGR
2 2
60 70 80 90 100 60 70 80 90 100
DOR (%) DOR (%)

(a) Improvement in sintered density with Degree of Reduction (DOR).

70 70

60 60
Hardness (HR15T)

Hardness (HR15T)

50 50

40 40

30 30

20 20

10 10
GS GSGR
0 0
60 70 80 90 100 60 70 80 90 100
DOR (%) DOR (%)

(b) Variation in hardness of sintered samples with Degree of Reduction (DOR).

300 300

250 250
Yield Strength (MPa)
Yield Strength (MPa)

200 200

150 150

100 100

50 50
GS GSGR
0 0
60 70 80 90 100 60 70 80 90 100
DOR (%) DOR (%)

(c) Variation in yield strength of sintered samples with Degree of Reduction (DOR).

Figure
Figure 2. Influence
2. Influence of Degree
of Degree of Reduction
of Reduction on properties
on sintered sintered properties of GSparts
of GS and GSGR and manufactured
GSGR parts
viamanufactured via Powder
Powder Metallurgy Metallurgy route.
route.

In-situ reduction
The effect of grinding
of sintering sludge took
parameters place in
(sintering GSGR75 samples
temperature by carbothermic
and sintering reduction
atmosphere) of
on CI90
andoxide
iron GSGR75
duringfeedstocks was
sintering of MIMstudied for suitability
parts. The of MIM
carbon is sourced forpyrolytically
from recycling. These partscarbon
generated were
characterized to recognize the physical and mechanical property changes with sintering parameters
and feedstock materials. Properties of sintered samples of CI90 were used as a reference to
normalize the improvement in properties of sintered GSGR75 samples obtained from the MIM
process.
In-situ2018,
Recycling reduction
3, 59 of grinding sludge took place in GSGR75 samples by carbothermic reduction 8 of 15
of iron oxide during sintering of MIM parts. The carbon is sourced from pyrolytically generated
carbon and externally added graphite in 25% excess for carbothermic reduction. The trend of
and externally
increasing sintered added graphite
properties in 25% parts
of GSGR75 excesswith
for DOR
carbothermic
is similarreduction.
to that of The
GSGR,trend of increasing
as shown in
Figure 2. However, the correlation between sintered properties and DOR is weak in MIM-based 2.
sintered properties of GSGR75 parts with DOR is similar to that of GSGR, as shown in Figure
GSGR75However, theas
parts, correlation
compared between
to PMsintered
basedproperties
GSGR. The and DOR
weak iscorrelation
weak in MIM-based GSGR75
is because of the parts,
as compared to PM based GSGR. The weak correlation is because of the heterogeneous
heterogeneous distribution of graphite in grinding sludge (arises from low solid loading in GGS75 distribution
i.e., of
75graphite in grinding
wt. %) limits sludge (arises
the carbothermic from low
reduction, solid loading
densification, in properties
and GGS75 i.e.,of75sintered
wt. %) limits
parts. the
Figurecarbothermic
3 shows reduction,
micrographs densification,
of sinteredand properties
GSGR of sintered
at 1200 °C andparts.
argon Figure
gas 3atmosphere.
shows micrographs
Grain of
sintered GSGR at 1200 ◦ C and argon gas atmosphere. Grain boundaries of free ferrite, pearlite colonies
boundaries of free ferrite, pearlite colonies (laminar structure of ferrite-cementite phases), and pores
(laminar
are clearly structure of ferrite-cementite phases), and pores are clearly visible.
visible.

Pearlite colonies

Ferrite

Porosity

Figure 3. Micrograph of cross section of cylindrical shaped GSGR (PM) sample sintered at 1200 oC ◦
Figure 3. Micrograph of cross section of cylindrical shaped GSGR (PM) sample sintered at 1200 C
withwith
argon gas purge.
argon gas purge.

The The quantification

quantification (DOR(DOR
and and
DOD)DOD) during
during the the recycling
recycling process
process via PM
via PM andand
MIM MIM suggest
suggest a a
lowerlower degree
degree of completion
of completion of reduction
of reduction andand densification.
densification. During
During recycling,
recycling, the optimal
the optimal parametric
parametric
setting
setting provides
provides ~92%~92%
DORDOR
andand
~70%~70%
DOD DOD by PM
by PM technique;
technique; andand ~69%
~69% DORDORandand
~74%~74%
DOD DOD by the
by the
MIM MIM technique.
technique. Additional
Additional improvement
improvement in these
in these characteristics
characteristics is not
is not possible
possible because:
because:
1. 1.The The
residual carbon
residual afterafter
carbon carbothermic
carbothermic reduction
reduction during sintering
during hinders
sintering the physical
hinders contact
the physical contact
between
betweeniron iron
particles, which
particles, limits
which the extent
limits of reduction
the extent of reductionand and
prolongs the process
prolongs of necking
the process of necking
for densification
for densification in PM. Particle
in PM. contact
Particle developed
contact developed during sintering
during of injection
sintering molded
of injection moldedpartpart
of of
GSGR75GSGR75 feedstock is even
feedstock weaker
is even due due
weaker to substantial
to substantial porepore
volume created
volume during
created debinding,
during debinding,
i.e., before the start
i.e., before of the
the start of sintering
the sinteringstage.
stage.
2. 2.The The
existence of pores
existence during
of pores sintering
during is prolonged
sintering (densification
is prolonged gets delayed)
(densification becausebecause
gets delayed) of the of
presence of irregularly sized and shaped pores, which hinder even volumetric
the presence of irregularly sized and shaped pores, which hinder even volumetric diffusion diffusion during
densification.
during densification.
3. 3.The The
energy
energychange during
change carbothermic
during carbothermic reduction
reductionis considerably higher
is considerably thanthan
higher the the
interfacial
interfacial
energy of particles. This does not support the pore removal mechanism
energy of particles. This does not support the pore removal mechanism (which requires (which requires highhigh
interfacial energy) and hence leads to decrease in densification. A more
interfacial energy) and hence leads to decrease in densification. A more substantial volume substantial volume
difference between
difference betweenreactant (iron(iron
reactant oxide and and
oxide carbon) and and
carbon) the product (iron)
the product opposes
(iron) reduction
opposes reduction
and and
densification due to the high energy required to enhance the volumetric
densification due to the high energy required to enhance the volumetric diffusion. diffusion.
4. 4.In the
In case of MIM,
the case of MIM,finerfiner
powder
powder particles accelerate
particles acceleratedensification because
densification of higher
because activation
of higher activation
energy for surface diffusion compared to reduction
energy for surface diffusion compared to reduction reaction rate.reaction rate.
5. If densification started earlier complete reduction would be expected (especially in the case of
5. If densification started earlier complete reduction would be expected (especially in the case of
very high sintering temperatures). However, bulk diffusion and grain coarsening would
very high sintering temperatures). However, bulk diffusion and grain coarsening would enhance
the densification rate of reduced iron, which would entrap the unreduced portion and decrease
the extent of reduction and sintered density.
Recycling 2018, 8, 59 9 of 16

enhance
Recycling the
2018, 3, 59densification rate of reduced iron, which would entrap the unreduced portion9 of and15
decrease the extent of reduction and sintered density.
6. The growing preliminary iron grains surround the secondary (small) pores formed in a
6. close-packed
The growing arrangement
preliminary leading
iron grainsto lowsurround the secondary
shrinkage. A considerable(small) pores formed
shrinkage in a
is observed
close-packed arrangement
when large pores get eliminated. leading to low shrinkage. A considerable shrinkage is observed
when large pores get eliminated.
3.2. Evaluation of Recyclability Index of GS, GSGR (PM) and GSGR75 (MIM)
3.2. Evaluation of Recyclability Index of GS, GSGR (PM) and GSGR75 (MIM)
As a general observation from Figure 2, measured properties showed more improvement in
GSGR Asthan
a general observation
in GS with increasing from
DOR,Figure 2, measured
though samples ofproperties showed more
the two feedstocks were improvement
processed under in
GSGR thanconditions.
identical in GS with To increasing
evaluate DOR, though
relative samples of the
improvement of two feedstocks
properties by were processed
in-situ under
carbothermic
identical conditions. To evaluate relative improvement of properties by in-situ carbothermic
reduction of grinding sludge being recycled, samples of CP iron processed under similar conditions reduction
of grinding
were sludge and
characterized being recycled,
used samples(for
as a reference of normalizing).
CP iron processed under
Sintered similarof
properties conditions
GSGR sampleswere
characterized
were normalized with CP iron properties for the same experimental setting (Exp. No. 1–27)were
and used as a reference (for normalizing). Sintered properties of GSGR samples and
normalized with CPiniron
plotted, as shown properties
Figure for the same
4. Normalized experimental
properties of GSGRsetting
show(Exp.
an No. 1–27) and
increasing trendplotted,
with
as shown temperature
sintering in Figure 4. fromNormalized
1100°C to properties
1300 °C of forGSGR
any ofshow an increasing
the selected trend pressures.
compaction with sintering
The
temperature from 1100 ◦ C to 1300 ◦ C for any of the selected compaction pressures. The variation in
variation in compaction pressure does not show significant improvements in the normalized
compaction
properties ofpressure does not show
GSGR samples. significant
Furthermore, improvements
these in the normalized
individual normalized properties
properties of GSGR
were averaged
samples. Furthermore,
and represented these individual
as a Recyclability Indexnormalized
(relation 7)properties were averaged
corresponding and represented
to the experimental settingasfor
a
Recyclability Index (relation 7) corresponding to the experimental setting for
GS and GSGR samples. For example, Recyclability Index for corresponding to Exp. No.14 for GSGR GS and GSGR samples.
For example, as:
is calculated Recyclability Index for corresponding to Exp. No.14 for GSGR is calculated as:

Normalized Density
Normalized ++Normalised
Density Hardness
Normalised Hardness + Normalised
+Normalised YS YS
Recyclability
Recyclability = =
IndexIndex 3
3 (7)
(7)
Recyclability Index (for GSGR at Exp. No. 14) 0.61
(forGSGR ++0.69
= 0.61 0.69++ 0.45
0.45
= 0.58
Recyclability Index at Exp. No. 14) = 3 = 0.58
3

1.00 Compaction Pressure Compaction Pressure

Compaction Pressure
1050 MPa 1200 MPa
0.90 900 MPa

0.80

0.70
Normalised Properties

0.60

0.50

0.40

0.30

0.20 Normalised Density

0.10 Normalised YS
Normalised Hardness
0.00
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27

Experiment No. for GSGR (PM)

Figure 4. Variation in normalized properties of GSGR
Figure 4. GSGR (PM)
(PM) sintered
sintered samples
samples with
with experimental
experimental
condition (parametric setting corresponding to the Exp. No. is given in Table A1).
condition (parametric setting corresponding to the Exp. No. is given in Table A1).

Recyclability
Recyclability Index
Index (averaged
(averaged sintered
sintered properties)
properties) quantifies
quantifies the
the overall
overall normalized
normalized property
property ofof
sintered samples for a given experimental setting. This effectively quantifies improvement
sintered samples for a given experimental setting. This effectively quantifies improvement in sintered
in
properties by carbothermic
sintered properties reduction.reduction.
by carbothermic This improvement was greater
This improvement in GSGR
was greaterthan GS as than
in GSGR the energy
GS as
input
the energy input for processing CP iron, GS, and GSGR are identical. This Recyclability Indexused
for processing CP iron, GS, and GSGR are identical. This Recyclability Index is only to
is only
characterize the relative improvement in properties (for structural strength) of GS and GSGR
used to characterize the relative improvement in properties (for structural strength) of GS and GSGR with
corresponding properties of CP iron under identical processing conditions. Recyclability Index is
Recycling 2018, 8, 59 10 of 16
Recycling 2018, 3, 59 10 of 15

with corresponding properties of CP iron under identical processing conditions. Recyclability Index
is arranged
arranged ininascending
ascendingorder
orderwith
withcorresponding
correspondingexperiment
experiment number
number for
for GS
GS and
and GSGR
GSGR samples,
samples,
as
as given in Figure 5. Except for four experimental conditions (Exp. 1, 2, 3, and 10), Recyclability
given in Figure 5. Except for four experimental conditions (Exp. 1, 2, 3, and 10), Recyclability
Index
Index ofofGSGR
GSGRis higher
is higher
thanthan that
that of GS. of GS.experimental
These These experimental
conditionsconditions have temperature
have a sintering a sintering
temperature
◦ of 1100 °C and lower compaction pressure, which resulted in a limited
of 1100 C and lower compaction pressure, which resulted in a limited carbothermic reduction, carbothermic
reduction,
residues of residues
graphite,of graphite,
and and partial
partial metallic metallic transformation
transformation of grinding
of grinding sludge. sludge.magnitude
The highest The highestof
magnitude of Recyclability Index is observed in GSGR samples from Experiments 25
Recyclability Index is observed in GSGR samples from Experiments 25 and 27, which is almost 17% and 27, which
is almost
more than17%
the more than the corresponding
corresponding highest value forhighest value
the GS for the GS samples.
samples.

Experiment No. for GSGR (PM)

10
12
11
19
21
20

15

13
14
16

17
24

18
22
26

23
27
25
1
2
3

6
4

9
1.00
0.90

0.72
0.80

0.71
0.68
0.68
0.67
0.67
0.67
0.65
0.65
0.65
0.65
0.70

0.60
0.58
0.56
0.56
0.53
0.53
0.52
Recyclability Index

0.60
0.51
0.50
0.49
0.43

0.50
0.41

0.55
0.54
0.38

0.53
0.53
0.53
0.51
0.51
0.51
0.35
0.35

0.50
0.50
0.50
0.49
0.33

0.47
0.40
0.46
0.46
0.45
0.45
0.45
0.44
0.43
0.40
0.40
0.40
0.39
0.37

0.30
0.35
0.35

0.20
GS (PM)
0.10
GSGR (PM)
0.00
10
1
2
3
12
19
11
21
13
16
4
20
15
26
6
5
14
18
22
17
7
27
8
25
24
23
9
Experiment No. for GS (PM)
Figure 5.
Figure Improvement in
5. Improvement in Recyclability
Recyclability Index
Index of
of grinding
grinding sludge
sludge by
by carbothermic
carbothermic reduction
reduction for
for
different experimental settings using Powder Metallurgy route.
different experimental settings using Powder Metallurgy route.

In order to evaluate the suitability of MIM-based recycling approach, sintered properties of

In order to evaluate the suitability of MIM-based recycling approach, sintered properties of
GSGR75 samples were normalized with C90 properties for the corresponding experimental setting
GSGR75 samples were normalized with C90 properties for the corresponding experimental setting
(Exp. No. 1–9 from Appendix B) and plotted in Figure 6. Normalized properties of GSGR75 show an
(Exp. No. 1–9 from Appendix B) and plotted in Figure◦ 6. Normalized properties of GSGR75 show an
increasing trend with sintering temperature from 1100 C to 1300 ◦ C especially in experiments wherein
increasing trend with sintering temperature from 1100°C to 1300 °C especially in experiments
samples were thermally debinded in vacuum followed by immediate sintering in argon.
wherein samples were thermally debinded in vacuum followed by immediate sintering in argon.
Furthermore, these individual normalized properties were averaged and represented as a
Furthermore, these individual normalized properties were averaged and represented as a
Recyclability Index (see relation 6) corresponding to the experimental setting for GGSR75 samples.
Recyclability Index (see relation 6) corresponding to the experimental setting for GGSR75 samples.
These averaged numbers (Recyclability Index) quantify the overall normalized property of sintered
These averaged numbers (Recyclability Index) quantify the overall normalized property of sintered
samples for a given experimental setting (Exp. No. 1–9 from Appendix B). This Recyclability
samples for a given experimental setting (Exp. No. 1–9 from Appendix B). This Recyclability Index is
Index is useful for comparison between the overall structural strength of GSGR75 and CI90 with
useful for comparison between the overall structural strength of GSGR75 and CI90 with equivalent
equivalent energy input for MIM processing. Recyclability Index is arranged in ascending order with
energy input for MIM processing. Recyclability Index is arranged in ascending order with
corresponding experiment number for GSGR75 and given in Figure 6.
corresponding experiment number for GSGR75 and given in Figure 6.
Maximum Recyclability Index (0.59) of GSGR75 is observed from Figure 7 with Exp. No. 8 (sintering
temperature: 1300 ◦ C and sintering atmosphere: V-Ar wherein samples were thermally debinded in
vacuum followed by immediate sintering in argon). Experiments (Exp. No. 1, 4, 7) with a sintering
temperature of 1100 ◦ C and vacuum sintering result in limited carbothermic reduction and formation of
highly porous structure.
 1.00 Normalised Densiy Normalised YS
Normalised UTS Normalised Elongation
0.90
Normalised Elastic Modulus Sintering with Sintering with
Vacuum or Ar V -> Ar
0.80 3, 59
Recycling 2018, Transition 11 of 15
Recycling 2018, 8, 59 11 of 16
0.70

Normalised Properties 1.00

0.60
Normalised Densiy Normalised YS
Normalised UTS Normalised Elongation
0.90
0.50 Normalised Elastic Modulus Sintering with Sintering with
Vacuum or Ar V -> Ar
0.80 Transition
0.40
0.70
0.30
Normalised Properties

0.60
0.20
0.50
0.10
0.40
0.00
1

9
0.30 Experiment No. for GSGR75 (MIM)
0.20
Figure 6. Variation in normalized properties of GSGR75 (MIM) sintered samples with experimental
condition.
0.10

0.00
Maximum Recyclability Index (0.59) of GSGR75 is observed from Figure 7 with Exp. No. 8
1

9
(sintering temperature: 1300 °C and sintering atmosphere: V-Ar wherein samples were thermally
Experiment No. for GSGR75 (MIM)
debinded in vacuum followed by immediate sintering in argon). Experiments (Exp. No. 1, 4, 7) with
a sintering
Figure temperature
6. Variationof in
1100 °C and vacuum
normalized sintering
properties result (MIM)
of GSGR75 in limited carbothermic
sintered samples reduction
with
Figure 6. Variation in normalized properties of GSGR75 (MIM) sintered samples with experimental
and formation ofcondition.
experimental highly porous structure.
condition.

1.00
Maximum Recyclability Index (0.59) of GSGR75 is observed from Figure 7 with Exp. No. 8
(sintering temperature: 1300 °C and sintering atmosphere: V-Ar wherein samples were thermally
debinded0.90in vacuum followed by immediate sintering in argon). Experiments (Exp. No. 1, 4, 7) with
a sintering
0.80 temperature of 1100 °C and vacuum sintering result in limited carbothermic reduction
and formation of highly porous structure.
0.70
1.00 0.59
0.60
Recyclability Index Recyclability Index

0.50
0.90
0.50
0.80 0.36 0.36
0.40 0.35 0.35
0.70 0.27 0.28
0.30
0.22 0.59
0.60
0.20 0.50
0.50
0.10
GSGR75 (MIM)
0.40 0.35 0.35 0.36 0.36
0.00
0.28
4

0.27
0.30
0.22 Experiment No. for GSGR75 (MIM)
0.207. Recyclability of grinding sludge by carbothermic reduction for different experimental settings
Figure
Figure 7. Recyclability
using Metal of grinding
Injection Molding (MIM) sludge
route. by carbothermic reduction for different experimental
0.10 using Metal Injection Molding (MIM) route.
settings
GSGR75 (MIM)
Based on the experimental observations, the following mechanism of solid state sintering for
0.00
recycling based on powder technology is proposed. Evolution of properties is also consistent with
4

the degree of physical changes after sintering.

ExperimentTheNo.carbothermic
for GSGR75 reduction
(MIM) involves about 17 to 23
(depending upon the presence of iron oxide phase and corresponding reaction rate favoring conditions)
volume percent
Figure change dueoftogrinding
7. Recyclability rearrangement ironcarbothermic
sludge by lattice and atomic oxygen
reduction transport
for different [22,23].
experimental
settings using Metal Injection Molding (MIM) route.
Recycling 2018, 3, 59 12 of 15

In the present study, densification proceeds through the following stages during sintering:
1. Particle contact develops during compaction or injection, and the contacting particles start necking
by surface and grain boundary diffusion. This leads to the formation of pores of various sizes.
2. Pores tend to become rounded to lower the surface energy. The rate of reduction of porosity
diminishes with decreasing pore size and hence resulting in lowered densification rate as
sintering progresses.
3. Combination of volumetric (bulk) diffusion and grain coarsening further enhances the
densification rate and tends to eliminate the remaining porosity [24].

3.3. Applicability of Recycling and Manufacture of Porous PM Parts

Solid state recycling attempted in the present study involves in-situ carbothermic reduction
of iron oxide from a source of scrap and densification during sintering of PM and MIM compacts.
Full reduction and densification is not possible at the same time in such a complex carbothermic
reduction involving multiple stages and modes of reduction. However, based on the experimental
observations and characterization of sintered properties, some optimal parametric settings have been
arrived at.
In recycled parts, a maximum of 70% of the properties of sintered Carbonyl iron can be achieved
in PM, while about 59% properties of the sintered carbonyl iron can be achieved in MIM after recycling.
The deviation in the properties of recycled parts from those of sintered carbonyl iron properties is
caused by the difference in the 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 that of a high carbon steel, which contains approximately 0.7–2.5 wt. % carbon. Recycled
iron parts obtained by the MIM process may have an even higher carbon content (1.37 wt. %).
The quality characteristics of the usable products made from downgraded metallic scrap (grinding
sludge) using the powder technology based recycling process may be identified as the degree of
reduction, the degree of densification, sintered density, and mechanical properties. Material and
processing conditions of sintered samples of ~0.7 Recyclability Index are further utilized for
simultaneous powder metallurgy based recycling in which in-situ reduction of grinding sludge shaped
into a product shape is used to manufacture porous products. The proposed recycling technique is used
in manufacturing simple geometric shapes like a solid cylinder, bush, circular ring, and plain bearing.
A mixture of grinding sludge and graphite (25% excess than the stoichiometric requirement for
carbothermic reduction) GSGR was prepared. The mixed powder was then compacted at 1050 MPa
compaction pressure. Compacted (green) samples were then sintered in a tubular furnace with a
constant flow of argon gas at 150 mL/min. Parts sintered at 1200 ◦ C are porous and shows considerable
shrinkage, as shown in Figure 8.
Recycling 2018, 8, 59 13 of 16

Figure
Figure 8. 8.Green
Greenand
andsintered
sintered PM
PMparts
partsofofGSGR
GSGRmaterial.
material.

Compaction die design considerations need to be developed for implementation of PM based

recycling-for porous product manufacturing. This is because GSGR parts show significant
volumetric shrinkage after sintering than CI parts because of simultaneous effect of carbothermic
reduction and densification during sintering. These porous parts may work well for air film
rolls/bearings, instrument filters, flow restrictors, flame arrestors, etc., in view of the performance
Recycling 2018, 3, 59 13 of 15

Compaction die design considerations need to be developed for implementation of PM based

recycling-for porous product manufacturing. This is because GSGR parts show significant volumetric
shrinkage after sintering than CI parts because of simultaneous effect of carbothermic reduction
and densification during sintering. These porous parts may work well for air film rolls/bearings,
instrument filters, flow restrictors, flame arrestors, etc., in view of the performance requirements
like filtration, flow control, porosity, and distribution. However, structural properties like sintered
density and mechanical properties will have some limitations on account of porosity that is needed for
functional needs of a porous part.

4. Conclusions
Extensive experimental studies were conducted to confirm possible implementation of powder
technology (powder metallurgy and metal injection molding) for the development of a manufacturing
process involving recycling of downgraded shop floor grinding sludge. Distinct experiments were
performed to optimize PM and MIM based processing, on the sintered properties. It may be concluded
that the interaction of sintering temperature (1200 ◦ C) and sintering atmosphere (a constant flow of
argon gas at 150 mL/min) significantly improves the characteristics of sintered parts after in-situ
reduction and densification.
The mechanical properties of GSGR (PM) parts are better correlated with the degree of reduction
(DOR) than GSGR75 (MIM) parts because of controlled carbothermic reduction and volumetric
shrinkage in the sintering step of the PM process. A quantitative measure, namely, “Recyclability
Index” was established to relate the effect of process parameters and process characteristics (DOR and
DOD) with the sintered properties.
Recyclability Index of GSGR (PM) samples is significantly higher (~17%) than GS (PM)
samples thanks to additional stoichiometric carbon (for completing in-situ carbothermic reduction).
Recyclability Index of GSGR75 at the optimal parametric setting is 59% (meaning parts produced
from this recycling technique have 59% physical and mechanical properties compared to those of the
pure iron dense parts). Hence, the proposed MIM-based recycling approach would not be practically
suitable for manufacturing of usable porous products. However, RI of GSGR parts is enough to
implement powder metallurgy route for recycling to manufacture porous parts. Thus, PM based
recycling of grinding sludge is possible for manufacturing of net-shaped porous products. Significantly
high volumetric shrinkage during sintering also demands further optimization of compaction die
design for dimensional control of sintered products.

Author Contributions: K.R. designed and performed the experiments. K.R. and P.D. analyzed the data with
equal contribution. K.R. wrote the paper, and he is the corresponding author.
Funding: This research received no external funding.
Acknowledgments: The authors of this research paper acknowledge the support extended by the Department of
Mechanical Engineering, IIT Bombay, that provided all necessary experimental and analytical resources.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature
Acronyms
PIM/MIM : Powder/Metal Injection Moulding
PM : Powder Metallurgy
RI : Recyclability Index
ZrO2 : Zirconia
GS : Grinding Sludge
GSGR : Grinding Sludge–Graphite mixture
CI : Carbonyl Iron
CI90 : 90% solid loading of Carbonyl Iron powder
Recycling 2018, 3, 59 14 of 15

GSGR75 : 75% solid loading of GSGR powder

DOR : Degree of Reduction
DOD : Degree of Densification

Appendix A

Table A1. Experimental condition for Full Factorial 33 experiments conducted for PM study.

Experimental Settings for CP Fe, GS and GSGR

Experiment No.
Compaction Pressure (MPa) Sintering Temperature (◦ C) Sintering Atmosphere
1 900 1100 Vacuum
2 900 1100 Argon
3 900 1100 Nitrogen
4 900 1200 Vacuum
5 900 1200 Argon
6 900 1200 Nitrogen
7 900 1300 Vacuum
8 900 1300 Argon
9 900 1300 Nitrogen
10 1050 1100 Vacuum
11 1050 1100 Argon
12 1050 1100 Nitrogen
13 1050 1200 Vacuum
14 1050 1200 Argon
15 1050 1200 Nitrogen
16 1050 1300 Vacuum
17 1050 1300 Argon
18 1050 1300 Nitrogen
19 1200 1100 Vacuum
20 1200 1100 Argon
21 1200 1100 Nitrogen
22 1200 1200 Vacuum
23 1200 1200 Argon
24 1200 1200 Nitrogen
25 1200 1300 Vacuum
26 1200 1300 Argon
27 1200 1300 Nitrogen

Appendix B

Table A2. Experimental 32 design matrix and sintering condition for MIM sintering cycle.

B: Furnace Atmosphere during

Cycle A: Sintering Temperature (◦ C) Coded Representation
Thermal Debinding and Sintering
1 1100 TD: Vacuum followed by S: Vacuum 1100V
2 1200 TD: Vacuum followed by S: Vacuum 1200V
3 1300 TD: Vacuum followed by S: Vacuum 1300V
4 1100 TD: Vacuum, S: Ar gas separate 1100Ar
5 1200 TD: Vacuum, S: Ar gas separate 1200Ar
6 1300 TD: Vacuum, S: Ar gas separate 1300Ar
7 1100 TD: Vacuum, S: Ar gas immediate transition 1100V-Ar
8 1200 TD: Vacuum, S: Ar gas immediate transition 1200V-Ar
9 1300 TD: Vacuum, S: Ar gas immediate transition 1300V-Ar
where TD: Thermal debinding and S: Sintering.

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