Nigeria Journal of Engineering and Applied Sciences (NJEAS) Vol. 3, No.

1, 2016

Case Hardening of Mild Steel Using Animal Bone, Charcoal and Sea Shells as
Carburizers

R.A. Muriana 1, Bori Ige2, O.K Abubakre1, J.O Abu2 and C.E Sani1
1
Materials and Metallurgy Engineering Department, Federal University of Technology, Minna,
Nigeria
2
Mechanical Engineering Department, Federal University of Technology, Minna, Nigeria
E-mail: [email protected],

Abstract
Samples of Mild steel were treated in carburizing media which included animal bone, wood
charcoal and sea shells at varied temperatures. Micro structural analyses, chemical
composition tests, and mechanical properties tests were carried out on the carburized
samples. Results indicated that the treated samples could be used in local production of some
engineering components such as gears in place of imported components where hardness is
considered together with toughness. The case hardening of the mild steel with charcoal
granules gave the highest carburization of 0.905% on the surface with the highest hardness
value of 69.3 HRA.
Keywords: Gears, carbon, energizer, carburization, mild steel.

Introduction high carbon steel as described by Wellyn

Metals are heat treated to obtain better (1997).
properties for better engineering The traditional method of applying the
performances (Higgins, 2010). Different carbon to the surface of the iron involved
heat treatment methods including case packing the iron in a mixture of ground bone
hardening help in micro structural and charcoal or a combination of leather,
rearrangement of metal atoms which in turn hooves, all inside a well-sealed box (Rajan
causes controllable changes in the metals et al., 2001). This carburizing package is
properties. Iron melting made of bloomeries heated to a high temperature for a length of
produced two layers of metal: one with a time, usually between 900-920˚C, Sanjibku
very low carbon content that could be (2009). The longer the package is held at the
worked into wrought iron, and the rest a high temperature, the deeper the carbon will
high carbon cast iron. Since the high carbon diffuse into the surface. Different depths of
iron is hot short, meaning it fractures and hardening are desirable for different
crumbles when forged (Craig, 2006); it purposes: sharp tools need deep hardening to
always needs further treatment. The wrought allow grinding and re-sharpening without
iron, with nearly no carbon in it is very exposing the soft core, while machine parts
malleable and ductile, but not hard. Case like gears might need only shallow
hardening involves packing the low-carbon hardening for increased wear resistance. The
iron within a substance with high carbon, resulting case hardened part may show
then heating this pack to encourage carbon distinct surface discolourations, the steel
migration into the surface of the iron. This darkens significantly and shows a mottled
forms a thin surface layer of higher carbon pattern of black, blue and purple, caused by
steel, with the carbon content gradually the various compounds formed from
decreasing deeper from the surface. The impurities in the carbonaceous materials.
resulting product combines much of the This work investigated case hardening of the
toughness of a low-carbon steel core with locally obtained mild steel using charcoal
the hardness and wear resistance of the outer (Ch), sea shells (Ss) and animal bone (Ab)
as carburizers. Machines and automobile
parts that are used where high impact

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 Case Hardening of Mild Steel Using Animal Bone, Charcoal and Sea Shells as Carburizers

strength is needed often experience fatigue if size range -90 µm to increase the surface
not well treated before usage (Zamba and area. Finally, three stainless steel boxes were
Sumansdi, 2004; Rajput, 2008). With the fabricated to accommodate the carburizing
recent Automobile Policy of the Federal media.
Government, the need for sustained and Table 1: Characterization of Carbon
locally manufactured automobile parts such Materials
S/N Carburizers Percentage Moisture Ash Volatile
as axles, gears, cam shafts and crank shafts Fixed- Content Content Matter
arises. A good way to solve this problem is Carbon (%) (%) (%) (%)
1 Ab 85.61 0.07 8.29 6.10
through case hardening of mild steel used 2 Ch 76.43 0.024 7.20 16.37
for the needed parts, whereby, carbon is 3 Ss 78.86 0.058 7.70 13.44
introduced into the surface of the mild steel
in which the inner core of the mild steel
remains soft and tough. Table 2 Chemical Composition of the Mild
In carburization, an amount of carburizer is Steel before Heat Treatment
packed into carburizing box and 20% of C Mn Cr Ni Mo V Si Fe
0.193 0.7 <0.0001 0.032 <0.0001 <0.0001 0.062 98.92
Barium trioxocarbonat (V) oxide (Ba₂CO₃)
is mixed thoroughly with carburizer in the Sample Preparation
box. The Ba₂CO₃ acts as an energizer and The mild steel rod was machined to tests
promotes formation of carbon (IV) oxide sizes of 25 mm diameter and 20 mm
(CO₂) gas, which in turn reacts with the thickness for hardness and microstructure
excess carbon in the media to produce tests respectively. The surfaces of the
carbon II oxide (CO). The CO then reacts samples were all polished into mirror-like
with the low carbon steel surface to form surfaces with progressive grinding on grades
atomic carbon which diffuses into the steel, of silicon carbide (SiC) impregnated emery
as shown in equations 1 -5. paper (240-600grits) sizes. Samples were
BaCO₃ (s) BaO + CO₂ (g) (1) then pre-polished with 1000grit silicon-
CO₂ (g) + C (s) 2CO (g) (2) carbide powder. A rotating cloth pad
impregnated with 1μm size alumina
Reaction of cementite with carbon
polishing powder (APP) was used in
monoxide
polishing with light pressure. Final polishing
2CO + 3Fe Fe₃C + CO₂ (3) was carried out using 0.05μm APP
CaCO₃ CaO + CO₂ (4) suspended in distilled water (Norman,
C + CO₂ 2CO (5) 2007).
Carburization then followed, whereby
Methodology carburizers were packed into the stainless
The materials used for this work included steel boxes and 20% of Barium
formulated carburizers (animal bone, wood trioxocarbonat (V) oxide (Ba₂CO₃) of mass
charcoal, and sea shells), barium carbonate, 140g was mixed thoroughly with each
mild steel of 0.193% C, stainless steel medium in each of the boxes. The Ba₂CO₃
boxes. Mild steel rod of 32 mm diameter acts as an energizer and promotes formation
was obtained from Universal Steels Limited, of carbon (IV) oxide (CO₂) gas, which in
Ogba - Lagos and analysed using a turn reacts with the excess carbon in the
spectrometric analyser to obtain the media to produce carbon II oxide (CO). The
chemical composition of elements present in CO then reacts with the low carbon steel
the steel, Tables 1 and 2. A total of twenty surface to form atomic carbon which
one (21) samples of this steel were then diffuses into the steel. Finally, the prepared
prepared, while the various carburizing mild steel samples were buried completely
media – animal bone, wood charcoal, and in the pulverized animal bone, wood
sea shells were obtained and pulverized in a charcoal or sea shells inside the boxes.
ball milling machine into fine powder of

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 R.A. Muriana , Bori Ige, O.K Abubakre, J.O Abu and C.E Sani

Pack Carburizing Processes Characterization of the Carburizers

The mild steel samples were buried Proximate analysis of the carbon materials
completely in the carburizing packages, for the case hardening process was carried
placed in the three stainless steel boxes in out to know the carbon percentages, the
the heat treatment muffle furnace at the volatile matter, the ash contents and the
foundry shop of Federal Institute of moisture contents. The results are shown in
Industrial Research Oshodi- FIIRO, Lagos Table 1.
where they were heated and held at 750 oC
up to 950 oC in step of 50 oC, as shown in Hardness Test
Table 3 and 4. The furnace was allowed to The hardness tests were all carried out using
cool before the samples were removed. The Indentec Universal Hardness Tester, with
carburized samples were then hardened by diamond cone (120˚) indentor, Rockwell
quenching in water, followed by tempering HRA, minor load 10kg and total load 60kg,
at 200˚C for one hour. This was done to in the Metallurgical and Materials
relieve the internal stresses built up during Engineering Department of Ahmadu Bello
quenching, and to increase the toughness in University (ABU) Zaria, at two different
the core of the mild steels samples. indentations. For the untreated As-Received
steel sample, 43.7 HRA was obtained, while
Chemical Test for the tempered steel samples, the different
The chemical analysis of the samples was results obtained were all recorded on a scale
carried out at Universal Steels Limited of A.
Ogba, Lagos State, using Spark Test
Spectrometry at two different sparks, in Results and Discussion
order to determine the chemical composition The mild steel case hardened with animal
of the steel and to determine specifically, the bone in the temperature range of 750-850 oC
amount of carbon content present in the increased in hardness up to 55.3 HRA as
steel. This is to classify the steel either as a against the original value of 43.7 HRA, and
low-carbon or high carbon-steel. This test then decreased to 48.9 HRA at 950 ˚C
showed that the steel contained 0.193 %C, (Table 5). Also, the case hardened steel
confirming that it is a low carbon steel. using charcoal granules, increased in
After the complete heat treatment of all the hardness from 46 – 69.3 HRA at
samples, the chemical analysis was also temperatures of 750 – 950 ˚C, and these
carried out at two sparks each, and the hardness values lie between the acceptable
results obtained are shown in Table 4. hardness values of spur gears ( 50 to 60 HR,
Table 3: Carburizing Temperature Variation ASM standard, 2000.). Case hardened mild
S/N Temperature Holding Time steel using sea shells granules, increased in
(˚C) (Hours) hardness up to 56.5 HRA at 950 ˚C, and
1 750 6 then decreased to 39 HRA at 900 ˚C.
2 800 5 The mixture of animal bone and sea shells
3 850 4 granules gave hardness value of 44.5 HRA
4 900 3 at 950 ˚C, charcoal and sea shells granules
5 950 2 gave a hardness value of 44.8 HRA, and
Table 4: Carburization Sample Distribution finally the three mixtures gave a hardness
Time 6 5 4 3 2 result of 46.4 HRA. It should be noted that
Hours Hours Hours Hours Hours the results of the mixtures hardness value
Temperature 750 800 850 900 950
(˚C)
were greatest at the three mixtures, Table 5.
Ab 1 2 3 4 5 From Table 6, decarburization of the steel
Ch 1 2 3 4 5 samples was experienced at 750oC in all the
Ss 1 2 3 4 5
three media while a gain in iron was

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 Case Hardening of Mild Steel Using Animal Bone, Charcoal and Sea Shells as Carburizers

recorded because at this temperature, commenced. Manganese content generally

penetration of atomic carbon into the decreased below initial 0.7 % as carbon
interstices of the iron atoms had not diffused into the steels. The case hardened
steels increased in toughness and wear
resistant properties.

Table 5: Hardness Values of Steel Samples after Case Hardening

Temperature (˚C) Steel Samples Hardness
Results (Hra)
750 Ab 52.1
800 Ab 54.7
850 Ab 55.3
900 Ab 53.5
950 Ab 48.9
750 Ch 46.0
800 Ch 48.4
850 Ch 61.9

900 Ch 58.3
950 Ch 69.3
750 Ss 45.6
800 Ss 40.4
850 Ss 40.9
900 Ss 39.0
950 Ss 56.5
950 50% Ab + 50%Ss 44.5

950 50% Ch + 50% Ss 44.8

950 Ab + Ch + Ss(33.3% 46.4

each)

Table 6: Chemical Composition of Steel Samples after Case Hardening

Tempera-ture (˚C) Carburizer C Mn Cr Ni Mo V Si Fe

Untreated 0.193 0.700 <0.0001 0.032 <0.0001 <0.0001 0.062 98.92
steel
750 Ab 0.142 0.697 <0.0001 0.005 <0.0001 <0.0001 0.032 99.038
800 Ab 0.230 0.698 <0.0001 0.013 <0.0001 <0.0001 0.035 98.928
850 Ab 0.211 0.699 <0.0001 0.012 <0.0001 <0.0001 0.036 98.831
900 Ab 0.122 0.701 <0.0001 0.011 <0.0001 <0.0001 0.034 99.039
950 Ab 0.123 0.707 <0.0001 0.009 <0.0001 <0.0001 0.033 99.035
750 Ch 0.013 0.299 0.048 0.018 <0.0001 0.008 0.070 99.443
800 Ch 0.699 0.294 0.044 0.012 <0.0001 <0.0001 0.062 98.75
850 Ch 0.78 0.255 0.045 0.013 <0.0001 <0.0001 0.065 98.70
900 Ch 0.844 0.069 0.044 0.014 <0.0001 <0.0001 0.069 98.662
950 Ch 0.905 0.332 0.039 0.009 <0.0001 <0.0001 0.039 98.572
750 Ss 0.129 0.689 <0.0001 0.012 <0.0001 <0.0001 0.034 99.043
800 Ss 0.028 0.294 0.046 0.007 <0.0001 <0.0001 0.065 99.471
850 Ss 0.349 0.290 0.041 0.001 <0.0001 <0.0001 0.063 99.178
900 Ss 0.006 0.297 0.044 0.002 <0.0001 <0.0001 0.062 99.508
950 Ss 0.118 0.698 <0.0001 0.021 <0.0001 <0.0001 0.041 99.02
950 Ab + Ss 0.065 0.292 0.047 0.029 <0.0001 <0.0001 0.067 99.368
950 Ch + Ss 0.349 0.290 0.041 0.001 <0.0001 <0.0001 0.063 99.178
950 Ab + Ch + Ss 0.241 0.294 0.048 0.012 <0.0001 <0.0001 0.070 99.246

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 R.A. Muriana , Bori Ige, O.K Abubakre, J.O Abu and C.E Sani

During the carburizing process, carbon

was released and subsequently absorbed
by the steel samples in different degrees.
Highest release and absorption was
recorded at 950oC, using charcoal as the
carburizing medium. This is in agreement
with findings by Panda et al., (2014).
Animal bone and sea shells performances
were far below charcoal performance as
carburizers at all the considered
temperatures, except 800˚C and 850˚C for Plate 1: Microstructure of the mild steel
animal bone. Also, at 850˚C, sea shell before heat treatment × 400; Ferrite (Whitish)
performed a little bit better than animal and iron carbide (Fe3C) phases clearly shown
bone by raising the carbon level from in an intermixed assemblage.
0.193 to 0.349. These performances are in
agreement with Oyetunji and Adeosun
(2012), as well as Fatoba et al., (2013).
The mixture of charcoal with sea shell
however, gave improved performance as
against sea shell alone as a medium at
950˚C. Here, the sea shell acted as an
energizer (Fatoba et al., 2013), while the
carbon from the charcoal diffused into the

steel. The silicon content in the untreated

sample was 0.062. The uptake of carbon Plate 2: Micro graph after case hardening with
thereby changed the respective percentages animal bone at 950 0C at magnification of 600,
and two hours soaking time. Ferrite is still
of silicon and iron levels in particular.
distinctly seen untransformed.
Manganese content remains relatively the
same in samples treated with animal bone.
This was however different in samples
treated with charcoal. As more carbon
diffused into the steel, manganese level
reduced automatically, relative to iron
content. The implication of this at
industrial level is that different
combinations of the carburizer/energizers
can be predesigned to give desired results
on the mild steel for specific industrial
application.

Microstructural Analyses Plate 3: Micro graph after case hardening

with charcoal at 900 0C at magnification of
The samples surface microstructures 600, and three hours soaking time.
before and after heat treatment are given in Transformation of Ferrite to iron carbide
the micrographs (Plates 1-7). was favoured by significant uptake of
more carbon from the charcoal.

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 Case Hardening of Mild Steel Using Animal Bone, Charcoal and Sea Shells as Carburizers

Plate 7: Micro graphs after case hardening

with the mixture of charcoal and sea shells
Plate 4: Micro graphs after case hardening at 950 0C at magnifications of 600, and
with sea shells at 900 0C ×600, and two hours soaking time. Ferrite
holding time of three hours. Coarser grains transformation also favoured with finer
of Ferrite with interstitial iron carbide. grains.

Microstructure of the steel in Plate 1

clearly shows the hypoeutectic nature of
the low carbon steel. Ferrite (whitish) and
iron carbide coexisted. Ferrite dominated
the field. Very little carbon penetration
was recorded with animal-bone case
hardening, Ferrite is still conspicuously
seen separated from iron carbide as
pearlite (Plate 2). Case structure of Plate 3
presents remarkable carburization
Plate 5: Micro graphs after case hardening efficiency. Good phase transition from
with sea shells at 950 0C at magnification ferrite in Plate 1, to pearlite was recorded
of 600, and holding time of two hours. when charcoal was used as the carburizer
Ferrite grains with interstitial carbide. (Plate 3), this particular sample gave the
highest hardness value of 69.3 HRA in
Table 6.
The performance of sea shell alone as
carburizer was similar to that of animal
bone in terms of poor carbon intake; ferrite
is still clearly separated from iron carbide
as shown in Plate s 4 and 5, this was also
responsible for low hardness values of
these samples as presented in Table 5.
However, there was improvement in
carbon intake when charcoal was mixed
Plate 6: Micrographs after case hardening with each of animal bone and sea shell.
with the mixture of animal bone, charcoal Here, both animal bone and sea shell were
and sea Shells at 950 0C at magnification considered as energizer, while charcoal
acted as the real carburizer, Plates 6 and 7.
of 600, and two hours soaking time. Finer
Systematic intake of carbon was therefore
grains with few transformation from ferrite recorded, which also led to improved
to iron carbide favoured by carbon uptake. hardness values. Consequently, the work
has confirmed the efficacy of using

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 R.A. Muriana , Bori Ige, O.K Abubakre, J.O Abu and C.E Sani

charcoal, animal bone and sea shell in mild Higgins, R.A. (2010). Materials for
steel carburization to achieve desired Engineers and Technicians, Newnes
hardness property. Publisher, UK. 5th edition,179 – 188
Conclusions Llewellyn D.T. (1997). Steel Metallurgy
The case hardened mild steel samples and Applications, Butterworth-
showed significant improvement in their nd
Heinemann, UK. 2 edition
mechanical properties, a proof of
effectiveness of the carburizers to induce Norman, E. D. (2007). Mechanical
higher hardness values in the steel
Behaviour of Materials, Pearson,
samples. These samples could then be
utilized in different industrial mild steel London. 3rd edition, 422.
applications, like gears as alternatives to
imported ones. Highest carbon Oyetunji, A. and Adeosun, S.O (2012).
concentration on the surface of the steel Effects of Carburizing Process
was 0.905% C using charcoal granules, Variables on Mechanical and
with highest hardness value of 69.3 HRA. Chemical Properties of Carburized
Mild Steel. Journal of Basic and
Acknowledgement
Applied Sciences, Ontario, L5R0B6,
Supports from Mr Simon Al-hassan and Canada Vol.8, 319-324.
the entire staff of Federal Institute of
Industrial Research Oshodi (FIIRO), Panda, R.R., Mohanty, A.M and Mohanta,
Lagos, Nigeria, in making this work a
D.K. (2014). Mechanical and wear
success is appreciated.
Properties of Carburized Low
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