Carburization of Low Carbon Steel Using Organic Additives
Carburization of Low Carbon Steel Using Organic Additives
Carburization of Low Carbon Steel Using Organic Additives
A R T I C L E I N F O A B S T R A C T
Keywords: Mild steel is made of iron and other elements, the chief among which is carbon. It is considered one of the most
Mild steel notable alloys in engineering applications because of its high tensile strength advantage and low cost. However,
Carburization mild steel essentially lacks the hard surface quality which is considered key to many structural and industrial
Sustainability
applications. This review explores various aspects of the carburization of mild steel which is targeted at providing
Organic additives
Mechanical properties
the hard surface quality it lacks. This work critically reviews the mechanisms of different carburization methods,
factors affecting carburization quality, and the potential of organic additives for carburizing low-carbon steel.
Furthermore, this review article provides new insights into organic energizers and their benefits to both the
handlers of carburizing operations and the environment in which they are carried out, following the United
Nations’ Sustainable Development Goal number 12 on sustainable production and consumption. Finally, this
review concludes by providing directions for future research on organic additives-based mild steel carburization.
1. Introduction relatively high melting point of between 1450 ◦ C and 1520 ◦ C [2].
However, mild steel lacks the hard surface properties required in some
Iron is ranked only second to aluminum in the hierarchy of the most applications. Hence, the option for surface modification where a com
abundant metallic elements in the earth’s crust [1]. These two elements bination of tough/soft core and hard surface is desirable [3–8]. This
have become the most commonly used structural metals with iron taking results in coating of various types among which is carburization because
the more pre-eminent position. This is partly because of reduced energy the strength, surface treatment, and hardness of low-carbon steel cannot
requirements during extraction from its ores and also owing to the wide be improved only by conventional heat treatment [9].
range of properties its alloys offer. Mild steel, one of such impressive The carburization process, which takes place in two key steps, occurs
alloys, is made of iron and other elements, chiefly carbon, and is when low-carbon steel is brought into close interaction with a solid,
considered the most important material because of its high tensile liquid, or gaseous carburizing medium at an austenitic temperature
strength and low cost. This makes it most suitable for general engi range: releasing free carbon through chemical reactions [10]. These free
neering applications. Like other steels, the high iron content gives mild carbon atoms are rapidly diffused into the surface of steel because of the
steel its ferrous and magnetic nature (hence ferromagnetic) and a large potential difference that exists between atmospheric carbon and
* Corresponding author.
E-mail address: [email protected] (K.O. Yoro).
https://doi.org/10.1016/j.susmat.2023.e00723
Received 30 May 2023; Received in revised form 7 September 2023; Accepted 22 September 2023
Available online 23 September 2023
2214-9937/Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
O. Adedipe et al. Sustainable Materials and Technologies 38 (2023) e00723
steel surface following Fick’s first law of diffusion [11]. The rate of the catalytic effect of shot peening pre-treatment on the plasma nitriding
absorption of additional carbon continues to decline as the surface be process, Unal et al. [25] found that the process could promote nitriding
comes more and more saturated with carbon content until equilibrium is efficiency and increase the thickness of the white layer, thereby
eventually reached; marking the end of the first step. The diffusion of ameliorating the pay-off of nitriding. Similarly, Tang et al. [26] had
carbon takes place in the second step between the surface and the core at earlier posited that pre-laser shot peening treatment is an excellent
a much slower rate as a result of the reduced carbon gradient between promoter of the adsorption of nitrogen atoms under the same plasma
the two regions. It takes a shorter time for the first step to be completed nitriding process, thereby improving the depths of composite layer and
which is then maintained for the succeeding process, the depth of which effective hardening layer. Amanov [27] cited laser shock peening, and
is dependent on the diffusion of carbon from the exterior to the interior ultrasonic peening as other surface engineering technologies that can as
part of the steel material. Carburizing is performed to obtain a surface well improve the adhesion strength between the coating and substrate.
with a carbon content of between 0.6 and 1.10% for steels that usually In a more detailed study on the effect of shot peening coverage on
contain 0.1 to 0.25% carbon. residual stress and surface roughness of 18CrNiMo7–6 steel, Wu et al.
The engineering of materials’ surfaces to enhance their life and [28] found that the gap between the axial and tangential residual stress
functionality has generated intense interest among researchers and is reduced by shot peening. They concluded that an increase in coverage
other stakeholders in the field. Appropriate thermo-mechanical surface from 100% to 400% favors a corresponding increase in the surface re
treatments result in general rearrangements of atoms in metals and al sidual stress from 628 MPa to 705 MPa while surface roughness pa
loys with a corresponding clear distinction in physical, chemical, and rameters reportedly decrease with full coverage conditions. Ren et al.
mechanical properties [12]. Heat treatment processes such as immersion [29], x-rayed the effect of laser shock peening and carbonitriding on
hardening, induction hardening, and case carburizing form parts of the tribological properties of 20Cr2Mn2Mo steel alloy under dry sliding
very important surface treatment processes deployed to induce the conditions. Parameters like surface roughness and microhardness as
desired improvements to materials’ surfaces. Many metallic materials well as the coefficient of friction improved laser energy and several
can be carburized to raise their effectiveness and functionality. The impacts. However, with growing laser energy, the primary wear mech
choice of which carburizing process to implement for specific applica anism is said to change from abrasive wear to a combination of abrasive
tions follows the benefits accruable from such methods. Many carbu and adhesive wear. Kikuchi et al. [30] agree with earlier submissions
rized parts are processed by gas carburizing which is one of the most that the fatigue limit of carburized steels treated with peening increased
controllable methods in terms of regulation of effective depth of carbon, as the size of surface dents induced by peening decreased, while also
using carbonaceous gases. It is also the fastest method of carburization corroborating the fact that a decrease in size supports the effect of re
[13]. Liquid carburizing was reported to pose a salt disposal challenge sidual stress on the fatigue limit.
and this makes it less desirable compared to gas carburizing [1]. How This review explores the potential of carburizing low-carbon steel
ever, for economic considerations, flexibility, as well as suitability for with organic additives. Studies in this field are fairly abundant but with
small machine parts, the pack carburizing process is preferred to the duo a narrow scope. For instance, Arthur and Azeko [22] conducted a review
of gas and liquid carburizing [14]. Other types of carburizing methods on the surface hardening of ferrous materials via the use of in-situ
include plasma and vacuum carburizing. All of these have varying de diffusion of carbon and nitrogen from cyanide-based bio-processed
grees of temperature requirements and accuracy. cassava wastes and focusing on the effects of bio-cyaniding on the
Romedenne et al. [15] investigated the degree of carburization of microstructure, micro− /nano-hardness, and wear properties of the bio-
three different steel samples exposed to liquid sodium environment at cyanided surfaces in the last decade.Although the studies were insight
600 ◦ C and 650 ◦ C. A larger amount of diffused carbon was observed in ful, it was limited by their area of coverage. In another brief review,
strain-hardened AIM1 steel than in 316 L annealed steel. This was Manne et al. [31] presented different works on the effect of the various
attributed to the higher density of dislocations. These defects, in addi methods of nitriding on mechanical properties, phase changes, and
tion to the presence of grain boundaries, could have triggered a faster corrosion resistance of AISI430 ferritic stainless steel. However, the
conversion of M23C6 into M7C3 carbides. In another study on gas works reviewed appear too few to inform a conclusion on the effects of
carburizing, Oh et al. [16] infiltrated the surface of cold-forged chro nitriding on the properties of the material. Therefore, this study sum
mium alloy steel with carbon from propane (C3H8) gas. Maintaining marized different methods of carburization with examples that reveal
carburizing gas volume flow rate at 350 m3/h and other carburizing specific challenges and resolutions with insightful backing for organic
parameters, the hardness gradient of the carburized layer was found to energizers which are less popular than their inorganic counterparts for
increase as the carbon content of the material decreased. Various carburizing low-carbon steel. This is despite being more beneficial in
research findings regarding the successful use of inorganic carburizers to terms of cost and eco-friendliness. It is believed that this will contribute
achieve good surface hardening of ferrous metallic parts have been re immensely to environmental safety by minimizing carbon emissions and
ported in the literature [17–21]. Romedenne et al. [15], deployed promoting cleaner and responsible production, as well as consumption.
inorganic carburizing sources for the precipitation of carbides on the The review focuses on the most recent studies with >70% of the studies
surfaces of alloys, while Arthur and Azeko [22], on the other hand, opted carried out within the last 5 years.
for organic carbon additives. In a bio-cyaniding work on ferrous mate
rials, they used cassava leaves as a source of cyanide because of their 2. Carburization methods
rich cyanide content. Similarly, Umunakwe et al. [23] used carburizing
powders from palm kernel and coconut shells in a pack carburizing Different methods of carburizing mild steel are reviewed in this
procedure to carburize steel with significant success. The reports were section to provide an understanding of how they relate to each other and
akin to an earlier one by Syahid et al. [14] who successfully improved affect the ultimate results of depth and quality of carburizing. Carbu
the fatigue strength of low-carbon steel through the use of a carburizing rizing affects fatigue life by changing the chemical composition,
process in the media of coconut shell charcoal and shell powder as a microstructure, hardness, or residual stresses of the carburized mild
catalyst. steel. Carburization could also be supported by material modification
Certain post-carburizing processes are also often carried out to processes such as shot peening, and surface rolling which are often used
improve the properties of the carburized surfaces, chief among which is to introduce compressive residual stresses on steel surfaces to delay
shot peening. Wu et al. [24] described shot peening as a mechanical crack initiation and propagation consequently [32–34].
strengthening method of carburized surfaces which is widely used to
improve fatigue strength of gear, bearing, crankshaft, and other me
chanical components due to its high efficiency and low cost. In a study of
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Fig. 1. Schematics of an experimental setup of the pack (bottom), liquid (middle), and gas (top) carburizing processes [35].
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where Fe(C) represents carbon dissolved in austenite. The reactions in transformation and carbon diffusion. This method, like the ones dis
Eqs. (22) and (23) yield two decarburizing gaseous products of CO2 and cussed in the preceding sections, is capable of providing parts that are
H2O. These products decrease the carbon potential of the atmosphere, more resistant to fracture (because of the soft core that can absorb
thereby making room for the addition of more carburizing agents like stresses without cracking) and also provides adequate wear resistance
CH4 to yield H2 and CO, which react with the steel surface according to on the surface. While the process enjoys easy integration into
Eqs. (24) and (25) to further enrich the surface with carbon content. manufacturing (clean, safe, simple to operate, and easy to maintain),
excellent and environmentally sustainable working conditions with full
CH4 + CO2 →2CO + 2H2 (24) automation capability using technology, as well as precise process
control, it, however, suffers some drawbacks. The initial set-up cost of
CH 4 + H2 O→CO + 3H2 (25) the equipment is high and the formation of soot and tar, which occur due
All these reactions take place in the carburizing furnace as illustrated to the type, pressure, and quantity of hydrocarbon gas introduced con
in Fig. 1. After a time (t > 0) of carburization, the variation of the carbon stitutes major disadvantages.
concentration may be taken to vary linearly from the gas/steel interface There also exist other carburization methods which are not detailed
(x = 0) to Co at a distance x towards the core, and the carbon content in this work. The underlying principle is the same for all the processes
equals the original carbon content of the steel, where x is the case depth. and the overarching goal is to achieve hardened surfaces and soft/tough
As carburization continues, the number of carbon atoms added per cores. While the methods discussed in the preceding sections involve the
second to the steel is given by Fick’s first law expressed in Eq. (26): introduction of carbon to the surface of low and medium-carbon steel,
the hardening agent in others is nitrogen (nitriding for instance) [62]. In
J = − Dyc
dC
= Dyc
Cs − Co
(26) the case of cyaniding, carbon and nitrogen are introduced into the sur
dx x face of steel by heating it to a suitable temperature and holding it in
y contact with molten cyanide to form a thin coating which, after
where J is the net carbon flux per unit area per second and Dc is the
quenching, becomes hardened. More advanced techniques are carbon
diffusion coefficient of carbon in austenite (Fig. 2). As the component
itriding, flame hardening, and induction hardening [63]. They all are
attains maximum carbon content from the atmosphere at the end of the
focused on improving the surface hardness of the substrate while
first phase of carburizing, the second phase of carbon diffusion begins
maintaining a soft interior for tailored applications.
where the carbon content reaches a maximum value [28]. Diffusion, at
this second stage, follows Fick’s second law of diffusion given in Eq.
2.6. Grain boundary condition of carburized steel
(27).
dCM d2 CM The phenomena of internal and grain boundary oxidations and their
= DM eff (27)
dt dx2 associated twists and turns in conventional carburization procedures are
a subject of debate among researchers, especially as they relate to gas
where CM is the mobile solute carbon concentration and DM eff is the and pack carburization methods [64]. The control of carbon dioxide
effective diffusion coefficient of mobile solute carbon (cm2/s) assumed (CO2) is critical to gas carburization as high CO2 signals the risk of grain-
to be constant throughout the entire diffusion zone as seen in Fig. 2. boundary oxidation, which weakens the carburized surface [65]. In
ternal oxidation occurs as a result of the diffusion of oxygen (O2) into the
2.4. Plasma carburization grain boundary of the steel being carburized. In addressing this chal
lenge, vacuum carburization, a process that exceeds the accelerating
To improve the tribological, fatigue behavior, and surface hardness rate of other carburizing methods is adopted to avoid oxidation [65]. In
of carburized steels, several surface modification methods, including the vacuum carburization, the temperature of the alloy is raised to 1000 ◦ C
plasma carburization method have been widely researched [55,56]. in a vacuum and maintained at very low pressure. Upon attaining the
Plasma carburization involves spreading carbon-containing paste over desired temperature, a carbonaceous gas (for example propane) is
the surface of the component which is melted when exposed to introduced into the compartment as shown in Fig. 1. The carbon pro
concentrated energy flow from a laser, electronic beam, plasma arc, or duced by the decomposition of the carbon-rich gas is then diffused
jet source [57]. It offers outstanding control and reproducibility, low uniformly into the surface of the workpiece (Fig. 1), thereby minimizing
energy consumption, and fast carburization time over conventional the risk of oxidation on the surface of the workpiece and extending the
approaches [48]. A gas mixture which is the critical parameter of the lifespan of the steel [66].
plasma carburization process has been widely investigated over the According to Dong et al. [67], the oxidation phenomenon is also
years. According to Biserova-Tahchieva et al. [57], plasma-based alien to the plasma carburization process. It enjoys a uniform carbon
treatments during case-hardening are considered advantageous over layer without internal oxidation. The process is considered effective for
gaseous processes as removing the natural inert layer of parts to be the high rate of carburization because it prevents many dissociation
carburized facilitates the inward diffusion of carbon. Plasma-carburized steps associated with most carbon-containing gases that produce active
alloys show improved surface finish, but increased production costs carbon, while also increasing the amount of carbon that reaches the
[58,59]. surface of the material by inducing directional movement in the electric
field. In a study of the effect of grain boundary oxidation on certain
2.5. Vacuum carburization mechanical properties during active applications, Krobath et al. [68]
observed that at a holding temperature of 1200 ◦ C, selective grain
Vacuum carburization (also known as Low-Pressure Carburizing) is boundary oxidation occurs and results in the formation of a network of
an alternative technology to traditional gas carburiziation. It has been notches at the coarsened austenite grain boundaries. This ultimately
proven to be very effective in improving the surface hardness and amounts to stress concentration and undeterred formation of cracks
tribological properties of heavy-duty gear steel, which is attributed to during a succeeding tensile deformation at critical temperatures. A more
the advantages of non-intergranular oxidation on the surface and less recent study by Shi et al. [69] revealed that finer austenite grains favor
quenching distortion [60,61]. The quality of this carburizing technique subsequent acicular martensite which is driven by grain boundary
has been reported to be much better when compared to other surface migration, a semblance of atomic diffusion. They posited also that
treatment techniques like quench-tempering treatment of 20Cr2Ni4 austenite grains obtained as a result of multiple cycles of carburizing are
steel. The carbon concentration profile from the surface to the core largely refined, causing a significant increase in the volume fraction of
during vacuum carburizing offers the kinetic driving force for austenite the prior austenite grain boundaries. This creates sites for the formation
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of γ-Fe to α-Fe in a subsequent carburization process. Therefore, it can be in Fig. 4. Carbon content of low-carbon steel is justifiably enriched from
concluded that grain boundary conditions play a significant role in the carbonaceous atmosphere around it. Liew et al. [21] examined the
determining the quality of any carburized components. microstructure of the surface of carburized steel to about 100 μm depth.
Grains with retained austenite and martensite microstructure are shown
3. Factors affecting the quality of case-hardening of carburized in Fig. 4(b). Martensitic structure, however, dominated the subsurface at
components 10–20 μm beneath the surface as illustrated in Fig. 4(c and d) with fewer
grain boundaries. Extra polishing of the surface of 20 μm to 100 μm
The depth of carburization is usually associated with the total depth depth revealed a region that is rich in martensite but deficient in grain
of carbon penetration during carburization. It is a major determinant of boundary (Fig. 4(e)). Elmi Hosseini and Li. [30], in an earlier study,
carburization quality, and it depends on several factors among which are similarly observed the formation of martensite microstructure at the
time and temperature of carburization, carbon potential of the carbu surface of carburized steel upon quenching, and ferrite-pearlite micro
rizing media, and composition of the parts to be carburized. This section structure in the core. Chen et al. [56] gave an idea of the trajectory of the
reviews various factors that influence the quality of case-hardening of hardness profile from the surface of the carburized part to the core
carburized components. where the hardness number is minimum. It was reported that hardness
decreases significantly from the surface where the hardness number is
maximum and continues slowly after about 1.5 mm into the core until it
3.1. Carburization time and temperature finally stabilizes. Consequently, it can be concluded that carburizing
time and temperature are vital to the overall mechanical properties and
Holding time plays an important role in the resulting properties of microstructure of carburized parts. Therefore, the control of tempera
most carburized components. It is described as the length of time parts to ture and time during the process is one key requirement to achieving
be carburized are allowed to stay in the carburizing environment excellent carburized parts.
[69–71]. Holding time has been reported to influence the mechanical
properties of carburized materials [33]. According to scientific reports 3.2. Carbon potential of the carburizing atmosphere
describing the relationship between carburization time and tempera
ture, higher carburization temperature forces the time of carbon diffu The carbon potential of a carburizing environment is said to influ
sion to reduce. Hence, the rate of carbon diffusion is directly influenced ence both the rate at which carbon is diffused into steel surfaces during
by carburization temperature. Supriyono & Jamasri [33] corroborated carburization and the depth of penetration. To enhance the carburiza
the submission of earlier researchers by concluding that longer holding tion process and enrich the carbon content of case-hardened zones,
time favors a deeper carburized surface, which in turn enhances the energizers are often deployed to help materials with low carbon po
increase in fatigue strength due to higher carbon content on the surface tentials. Industrial chemicals are traditionally used to energize the
of the material. The outcome of the effect of longer holding time on case process. However, viable alternatives have been discovered in plants
depth is illustrated in Table 3. Similarly, Abdenour et al. [72] also and other organic matter [75]. A list of some of these organic energizers
confirmed that case depth and richness in carbon increase is directly is summarized in Table 4 and discussed in one of the previous sections.
proportional to carburization time. This section focuses on the potential of waste organic materials as sus
In a similar study, Betan et al. [73] investigated the influence of tainable replacements for the enhancement of case-hardened surfaces of
temperature and holding time on the shear strength of Schleicheraoleosa low-carbon steel, given environmental concerns raised about industrial
charcoal-powder carburized mild steel. A similar trend was reported on chemical energizers [62].
the improvement of the mechanical performance of the carburized Kolawole et al. [76] adopted organic waste materials as carbon
materials. It also suggests the advantage of preferring oil to water as a sources in a bid to enhance the surface properties of mild steel by
quenching medium due to the degree of carburization. The conclusion carburization. It was found that the tensile strength and hardness of
across different research findings indicates that the hardness property of carburized steel increased with increasing carburizing temperature
carburized material decreases towards the core as a result of retained while ductility was on the decline. Other authors have also established
austenite and more martensite at prolonged holding time [33,72,74]. the potential of this category of energizers for efficient carbon diffusion
According to Liew et al. [21], the surface layers of the carburized steel into the surface [62,77]. Findings according to Aondona and Azoro, [62]
are dominated by retained austenite and this reduces towards the core as indicated that natural and organic energizers from plant and animal
the amount of martensite increases. The amount of cementite in the sources are now preferred to industrial chemical energizers. Waste
grain boundaries and the size of retained austenite likewise increase as materials like sugar cane bagasse, rice husks, eggshells, melon shells,
holding time increases. As a result, the load-bearing capacity of the Aceraceae flower droppings, and charcoal are prominent among non-
carburized layer is improved alongside the adhesive and abrasive wear chemical energizers used [33]. A comparison of the impact energy of
resistance of low-carbon steel when the holding time is extended. This CaCO3, one of the commonest industrial chemical energizers, and
affects, significantly, the overall performance of the materials. eggshell showed that the latter performed better on leaf-spring steel at
Fig. 3 illustrates the changes to hardness and young modulus of the carburizing temperatures of 950 and 1000 ◦ C with the carburizing
carburized steel through case depth as a function of carburizing time. times of 1 h and 1½ h, respectively.
Hardness properties are reduced from the surface of the materials to the
core. The effect on the microstructure of the materials is also illustrated
3.3. Dynamics of carbon diffusion
Table 3 Fick’s law of diffusion describes carbon diffusion within the part to
Case depth for gas carburizing temperature and time. be carburized. Since the diffusion flux and the concentration gradient
Time (h) Case depth in mm around the surface respond to time as a result of carbon accumulation, it
870 ◦ C 900 ◦ C 927 ◦ C 955 ◦ C is considered a non-steady-state diffusion, and can be expressed by
Fick’s second law (Eq. 28). Ignoring the dependence of D on carbon
1 0.46 0.53 0.64 0.74
2 0.64 0.76 0.89 1.04 content, Eq. (28) is revised to yield Eq. (29). Certain boundary condi
4 0.98 1.07 1.27 1.30 tions are specified while surface carbon concentration is assumed to be
8 1.27 1.52 1.80 2.11 constant and the part is thick enough relative to the case depth. Eq. (29)
12 1.55 1.85 2.21 2.59 can be further expressed as Eq. (30) where C is the concentration at
16 1.80 2.13 2.54 2.97
depth x after time t. The parameter, Cs is defined as the concentration at
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Fig. 3. (a) Hardness as a function of penetration time (b) Hardness and young modulus of steel for different carburizing times [72].
Fig. 4. Microstructure of the surface at various depths (a) surface after slight polishing (b) subsurface 5 mm beneath the surface (c) subsurface 10 mm beneath the
surface (d) subsurface 20 mm beneath the surface, (e) subsurface 100 mm beneath the surface [21]
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Table 4
Summary of studies on the pack carburization process using organic energizers.
Ref Carburizer Carburizer Holding Carburizing Focus of study Findings
type time temperature
the surface at time t and the expression erf(x/(2√Dt)) is termed the sufficiently clear that the difference between the environmental carbon
Gaussian error function. and its concentration on the metal surface drives carbon diffusion into
( ) the steel from the gas phase [78]. The measurement of carbon concen
∂C ∂ ∂C
= D (28) tration and influx is, therefore, vital to the control of the carburizing
∂t x ∂t
process. Activation energy, an important thermodynamic parameter
that influences surface thickness with regard to temperature and time,
∂C ∂2 C
=D 2 (29) provides insights into determining satisfactory process conditions for
∂t ∂x effective carburizing [35,43]. The management of the diffusion process
C − Co
(
x
) is a lot easier when using the gas-related carburizing technique. As a
= 1 − erf √̅̅̅̅̅ (30) result, Wang et al. [78] concluded that carbon flux is crucial to the
Cs − Co 2 Dt
regulation of the time of penetration and dissemination in each pulse of
The dynamics of carbon flux is the main parameter that influences carbon flow. They did a comparison of carburizing pressure and carbon
the microstructure evolution during the carburizing treatment accord flux of three different alloy steels in similar carburizing conditions as
ing to Yang et al. [66]; hence, the quality of case-hardening. It is illustrated in Fig. 5. The study covered changes in surface carbon
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Fig. 5. Effect of carburizing pressure on (a) mass increment, (b) average carbon flux, and (c) segmented average carbon flux for 12Cr2Ni4A steel at 950 ◦ C [78].
enrichment, changes in average carbon flux as well as its segmented of carburizing pressure on surface carbon diffusion. The plots in Figs. 5-
average carbon flux for the three alloys at a carburizing temperature and 7: show these relationships for 12Cr2Ni4A steel.
pressure of 950 ◦ C, and 100–300 Pa, respectively to establish the effect In the boost stage of 12Cr2Ni4A steel, mass is observed to increase
Fig. 6. Effect of carburizing pressure on (a) mass increment, (b) average carbon flux, and (c) segmented average carbon flux for 16Cr3NiWMoVNbE steel at
950 ◦ C [78].
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Fig. 7. Effect of carburizing pressure on (a) mass increment, (b) average carbon flux, and (c) segmented average carbon flux for 18Cr2Ni4WA steel at 950 ◦ C [78].
linearly from 0 to 60 s. Subsequently, the slope becomes less steep as used, particularly in the pack carburizing process. However, the need to
mass gradually decreases, approaching zero after 120 s. The segmented ensure the safety of both the environment and personnel through the use
average carbon flux value, which is 5.98 × 10− 6 and 7.7 × 10− 6 at 90 s, of more sustainable manufacturing procedures has necessitated in
respectively are also seen to increase from 1.04 × 10− 5 to 1.36 × 10− 5 at vestigations into alternative materials to replace inorganic energizers.
30 s, and 8.11 × 10− 6 to 9.58 × 10− 6 at 60 s [78]. From 120 to 150 s, this This has yielded impressive results as the suitability of some organic
remained nearly identical at the three pressures, displaying compara waste materials like palm kernel shells, animal bones, egg shells, peri
tively insignificant flux values. The relationship between carburizing winkle and sea snail shells as carburizing media has proven to be
pressure and carbon flux of the three medium-high alloy steels demon adequate for the exercise. Ramli et al. [79] reported that the choice of
strate that the three parameters of carbon mass enrichment, average and the right carburizing media contributes significantly to the quality of the
segmented carbon flux of the alloys exhibit similar trend under similar optimum carburizing performance and hence, the improvement of the
carburization temperature of 950 ◦ C and carburizing pressures of 100, mechanical properties of carburized surfaces. This section examines
200, and 300 Pa [78]. different organic carburizing media for successful surface modification
For the three materials discussed in this sub-section, the value of of mild steel.
carbon flux was the smallest at the lowest carburizing pressure consid The studies summarized in Table 4 are focused on the deployment of
ered. At higher carburizing pressure, however, relative density proves organic solid waste materials as additives for the carburization of low-
significant for effective carbon flux and the pumping rate decreases as carbon steel. The unanimous submission of the authors points to the
the flow rate contributes insignificantly to the gas exchange rate. So, the fact that organic additives have been established as more sustainable
gas stays longer on the surface of the part, thereby raising the relative and eco-friendly alternatives in steel carburation. This will not only lead
density. However, at the highest carburizing pressure, the value of to cost reduction but will also contribute immensely to the preservation
carbon flux was close to that under 200 Pa, indicating that flow rate and of the environment in furtherance of United Nations Sustainable
relative effective density attained equilibrium. Therefore, it can be Development Goal #12 (UN’s SDGs) on sustainable production and
concluded that in actual gas carburizing, a pressure of 300 Pa will have consumption [22]. Ramli et al. [79] appear to be one of the most
relatively little effect on the process. prominent among the researchers who have attempted to improve the
mechanical properties of steel surfaces via carburization using coconut
4. Advances in organic additives in carburization processes shell powder as an additive. Some of the works carried out by other
authors who investigated the suitability of organic carbon additives and
Carburizing additives play significant roles in determining the energizers are also set out in the table. The eco-friendly nature of those
quality of surface hardening of low-carbon steel [77]. As far as could be materials was identified as the major reason why future players in steel
ascertained, inorganic activators are the most widely used in carburizing processes should look in the direction of plant and animal
manufacturing processes with tremendous success as reported in some solid wastes as reliable sources of carbon for surface hardening of low-
studies [22,77]. Barium, sodium, and calcium carbonates are the carbon steel [62,79]. The researchers mentioned in Table 4 agree with
commonly reported inorganic energizers that have been successfully the relationship between carburizing temperature and holding time.
11
O. Adedipe et al. Sustainable Materials and Technologies 38 (2023) e00723
Arthur and Azeko [22] varied the carburizing temperature between 6. Conclusions
800 ◦ C and 950 ◦ C and found similar trends with those reported by
Ramli et al. [79], which revealed that significant carburizing could Different potentials of numerous organic additives have been
hardly take place at 850 ◦ C, considering holding time as a major factor. assessed in this study, most of which can be harnessed to achieve higher
A higher holding time reportedly favored a harder surface zone [77]. quality carburization, while spending less than when inorganic additives
According to Aondora and Azoro [62], energizers could meaningfully or single organic additives were to be deployed. Most of the organic
reduce the holding time of carburizing, with natural energizers having additives are simply organic wastes that would ordinarily have had a
an edge in terms of carbon potential; except that they cannot be used as a negative impact on the environment as a result of possible indiscrimi
good source of activated carbon [79]. nate disposal or burning. The cost of spending less on raw materials and
These organic materials are applicable in pack carburizing processes putting waste materials into productive use is not only a current trend in
where they are packed around specimens to be carburized. Several re modern manufacturing, but also the future compliance with sustainable
searchers have also compared the effect of single and hybrid organic production and consumption, as well as the United Nations’ sustainable
carburizing media on the overall carburizing efficiency and quality of development goals. Furthermore, while inorganic additives are not
surfaces. Kolawole et al. [76] observed that better carburizing properties readily accessible and have to be sourced deliberately, organic additives
were achievable with hybrid carburizing media (coconut and palm are ubiquitous and sometimes constitute environmental hazards from
kernel shells). The tensile strength and hardness of the specimens were mishandling in many sub-Saharan African cities. Eggshells, palm kernel
significantly improved when the carburizing additives were combined shells, coconut shells, and wood are oftentimes burnt in the open space
and used for the same purpose under the same conditions. This agrees which pollutes the environment and adding no value to production. The
with what Ihom et al. [80] reported earlier about how hybrid carbu future lies, therefore, in harnessing all the readily available raw mate
rizing compares favorably with single carburizing. With the results rials for creating a controlled carbonaceous atmosphere for carburiza
summarized in Table 4 and a host of other works on organic energizers, tion purposes.
it can be concluded, with a caveat for further investigations, that organic In summary, increasing advocacy for cleaner production necessitates
energizers are cheaper, more eco-friendly, and preferable alternatives to the increased search for cleaner sources of carbonaceous environments
the likes of BaCO3, Na2CO3, and other inorganic energizers during for steel carburization. This study has revealed the mechanisms of
carburizing processes [81]. different methods of carburization, factors affecting carburization
quality, and organic additives for carburization. The research efforts in
5. Future perspectives of organic additives-based mild steel this review has also provided insightful backing for organic energizers,
carburization and their benefits to both the users and the environment. This paper
strongly recommends the deployment of hybrid organic additives
Organic sources of carbon for carburizing steel are attracting through simple and less expensive environment-friendly techniques that
tremendous attention from the scientific community for many industrial would contribute to solving the world’s perennial energy and pollution
applications [86]. Recent advancements in engineering call for material crises.
modifications for improved design and reliability. Its prominence and
preference in the manufacture of bearing notwithstanding, high-carbon
Declaration of Competing Interest
chromium steel requires surface modification to improve its service life
as a bearing material [87]. In the same vein, plain carbon and low alloy
The authors declare no conflict of interest.
steels are indispensable for many structural and industrial applications.
The peculiarity of certain applications, therefore, necessitates their
Data availability
surface treatments by some thermodynamic processes in order not to
compromise core toughness and strength. Therefore, parts manufac
Data will be made available on request.
tured from these steels are used only after being sufficiently carburized
[63]. Salawu et al. [88] reported that the increasing demand for super
hard alloys for advanced engineering applications prompts the need to Acknowledgment
develop materials of superior mechanical properties for such applica
tions as gear, bearings, sprockets, and housings. Advancement in surface Authors acknowledge the financial support given by the National
engineering is said to have assumed significant importance, especially in Research Fund (NRF) under the aegis of the Tertiary Education Trust
the last few decades with a promising potential in sundry technological Fund (TETFund), Nigeria, (TETF/ES/DR&D-CE/NRF2020/SETI/87/
applications including aerospace, marine, automobile, energy, textiles, VOL.1).
and chemical among others [89]. The above argument forms the basis
for this review article which is focused on organic carbon sources for References
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