The formation of diamond like carbon on

carbon steel using plasma of argon-liquified

petrolium gas mixing
Cite as: AIP Conference Proceedings 2014, 020022 (2018); https://doi.org/10.1063/1.5054426
Published Online: 21 September 2018

Suprapto, Tjipto Sujitno, Wiwien Andriyanti, and Bangun Pribadi

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© 2018 Author(s).
 The Formation of Diamond Like Carbon on Carbon Steel
Using Plasma of Argon-Liquified Petrolium Gas Mixing

Suprapto1,a), Tjipto Sujitno1, b), Wiwien Andriyanti1, c) andBangun Pribadi2, d)

1
Center for Accelerator Science and Technology, BATAN
Jl. Babarsari 21, P.O.Box 6101 ykbb, Yogyakarta 55281, Indonesia
2
Polytechnic Institute of Nuclear Technology- National Nuclear Energy Agency of Indonesia
Jl. Babarsari 21, P.O.Box 6101 ykbb, Yogyakarta 55281, Indonesia
a)
praptowh@batan.go.id or praptowh2000@yahoo.com
b)
tjiptosujitno@batan.go.id
c)
wiwien@batan.go.id
d)
bangunpribadisttn@gmail.com

Abstract.Diamond like carbon (DLC) is very important materials for mechanical industryespeciallycutting tools,
automotive and production machines components.Formation of DLC on metal surface usually use a mixture of
hydrocarbon/Ar plasma, such asCH4/Ar, C2H6/Ar, and C2H4/Arplasma.These materials are expensive.Therefore, the aim
of this study is to replace the hydrocarbon/Arwith the carbon source of LPG/Ar mixture because it is cheaper and easy to
get in the market. The formation of DLC wasconducted by using home madeDC plasma glow discharge device, and
carbon sourceof LPG/Ar gasmixture with ratio 9: 1. The formation was carried out with pressure variation of 1.4 mbar,
1.6 mbar, 1.8 mbar, 2 mbarand time variation of 2 hours, 3 hours, 4 hours, and 5 hours at constant temperature 400
o
C.The DLC formation was analyzed byusingVickers hardness test, wear test, corrosion test and microstructure test
(SEM-EDS and XRD).The optimum hardness and wear resistance are225.3 VHN and 1.7 × 10-8 mm2/kg,and this was
achievedrespectively,at 1.6 mbar and a 4 hours. Meanwhile, the un-coated materials are 115.5 VHN and 1.4 × 10-7
mm2/kg. The results show that hardness and wear resistance increase ifcompared to the un-coated materials.The
microstructure observed using SEM-EDS show that thickness of hard layer is about one 5 μm.From XRD analyzed show
that the formed phase is Fe2C phase. Based on these results it is expected that the formingDLC can be applied for the
machine components and can increase the life time and mechanical efficiency so that the operation is more efficient
because the friction losses become smaller.

INTRODUCTION
Utilization of steel material for machinery and other purposes such as for machining technology (cutting tools,
automotive and production machines components)are growing very rapidly. Based on the carbon contents, carbon
steel is generally divided into three categories such as: low carbon steel, medium carbon steel and high carbon steel.
Medium carbon steels is widely used as engine components such as gears, shafts and other engine components[1].
In general, the properties of materials especially steel required for machining technology are: tough, wear and
corrosion resistants. This material should be easy to be done by machine or other technique such as casting and
besides that this material is cheap in price and production [2,3]. The tough materials, corrosion and wear resistants,
are expensive and difficult to be done either machining or by others, so the cost of production will be expensive.
The problems for materials that meet these requirements is expensive, including the cost of production, for cheap
materials are usually not enough tough, low corrosion and low wear resistants. The low wear and low corrosion

International Conference on Science and Applied Science (ICSAS) 2018

AIP Conf. Proc. 2014, 020022-1–020022-9; https://doi.org/10.1063/1.5054426
Published by AIP Publishing. 978-0-7354-1730-4/$30.00

020022-1
resistants can be improved by diamond like carbon (DLC) coating on their surface using plasma of Argon (Ar)–
LiquifiedPetroliumGas (LPG mixing).
Kano, M has conducted research on the application of DLC coatings on automotive components contacted each
other, the result showed that there are a significant decrease in the coefficient of friction [4]. Moriguchi, H reported
that the diamond like carbon (DLC) has a hard properties and capable of self lubrication and has a stable chemical
properties, and this can also be used to reduce fuel consumption of automotive due to its reduction of the coefficient
of friction [5]. Bewilogua, K reported that diamond like carbon (DLC) is a diamond coating known for its
exceptional properties such as low coefficient of friction, high hardness and high wear resistance, stable chemical
properties, transparent optical properties in the range of infrared spectra and low electrical conductivity so in the
future, DLC applications are very widely especially in automotive industries [6]. Ceschini, L. et al reported that the
diffusion of carbon atoms at low temperatures around 450 ˚C of temperature into the surface of austenite stainless
steels gives a significant effect in increasing of hardness [7]. Related research has also carried out by Silva, WM et
al, they had treated the surface of 6150 steel using a mixture of methane, hydrogen and nitrogen gas at 475 ˚C of
temperature for 2 hours and continued using a mixture of methane and hydrogen for 0.5 hours, the result showed
that there is an increasing in hardeness by 2 times [8].
The gas usually used in the formation of a DLC thin film using glow discharge plasma is a mixture of
hydrocarbon gas with argon (Ar) or helium (He). Some of the most widely used hydrocarbon gases include methane
(CH4), ethane (C2H6), propane (C3H6), butane (C4H10) and benzene (C6H6) [9]. In this case CH4 is more effective
than C2H2 to form denser film.The reason why we use a LPG gas is cheap and easy to get in the market. The 97.5 %
of LPG gas is a mixture of of propane (C3H8) and butane (C4H10), and the others is hydrocarbons for example ethane
(C2H6) and pentane (C5H12) and other impurities with very low levels[10].
Based on the above description, a hard layer of diamond like carbon (DLC) coated on the surface of low/medium
carbon steel using mixture of an argon-methane and/or argon-propane-butane (from Liquified Petroleum Gas/LPG)
plasma as well as their surface properties. The main purpose in this research is to improve the surface quality of
carbon steel using a mixture of Argon (Ar) and liquefied petroleum gas (LPG) plasma.

METHODOLOGY
The material used for specimen in a surface treatment process is a medium/low carbon steel with the name of the
shaft steel trademark. Geometry specimens of shaft steel material 20 mm in diameter and 1000 mm in length, the
material is cut to become a piece of shape with a 14 mm of diameter and a 5 mm of thickness. The specimens in the
piece of shape are smoothed on the surface using abrasive paper from 100 mesh up to 5000 mesh and polished using
metal polish. Dirt from residual polishing on the surface of the specimen was cleaned/washed using an ultrasonic
cleaner machine, washing in detergent and then in water and alcohol and dried using a blow dryer.
The equipment used is DC plasma glow discharge device, Matsuzawa MMT-X7 micro hardness tester, wear test
equipment Ogoshi High Speed Universal Wear Testing Machine, potentiostat corrosion type PGS-201T device,
SEM-EDS and XRD test equipment.
DLC coating process is done by using home madeDC plasma glow discharge device, as carbon source, a mixture
of argon gas and liquified petroleum gas (LPG), with ratio 9: 1. The coating process is carried out with variation of
pressure and time at constant temperature 400 oC. Pressure variation were 1.4 mbar, 1.6 mbar, 1.8 mbar and 2 mbar
whereas time variation were 2 hours, 3 hours, 4 hours, and 5 hours.
Tests performed to determine the results of DLC coatings include: Vickers hardness test, wear test, corrosion
test, microstructure test (SEM-EDS and XRD). Vickers hard test using Matsuzawa MMT-X7 microhardness tester,
to know the surface hardness of DLC coating with indentor load selected 10 gf and indentation time 10 seconds.
Wear testing is done to determine the wear resistance of the surface, wear resistance can indicate the life time of the
machine components because component damage starting from the surface such as wear and tear. The test in Gajah
MadaUnivercity laboratory in Yogyakarta uses the wearing test tool Ogoshi High Speed Universal Wear Testing
Machine. Corrosion testing is done to determine the surface corrosion resistance, corrosion resistance associated
with damage caused by environmental conditions. The test at CAST-NNEA of Indonesia Chemical Laboratory uses
potentiostat type PGS-201T. The surface microstructure test of the coating results is carried out to determine the
surface structure changes which can be used to analyze the change in properties due to the coating process.
Microstructural tests were performed by observing the micrograph surface composition with SEM-EDS and the
formed compounds were observed with XRD. The flow diagram of this research is shown in Figure 1 which
informs briefly from beginning to end of the research.

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 FIGURE 1.Flow Diagram of Research

RESULTS AND DISCUSSION

The specimens were prepared from local carbon steel with a shaft steel trademark with an elemental composition
based on composition test shown in Table 1. Based on the composition test (Table 1), the specimen from the shaft
steel can be classified as low carbon steel [11], with the average hardness of raw material is 115.52 VHN.

TABLE 1.Composition of carbon steel.

Element Fe C Si Mn P S Cr Mo Al Cu Sn V
Quantity 98.46 0.245 0.286 0.532 0.005 0.01 0.114 0.017 0.05 0.071 0.004 0.01

Analysis of the hardness test

The influence of pressure variation on the hardness of coated materials surfaces is showed on Figure 2. From
Figure 2, showed that the optimum hardness is 225.3 VHN. This optimum hardness was achieved at 1.6 mbar of
pressure. The influence of pressure on the hardness of carbon steels coated for 4 hours and at constants time.DLC
coating conducted by Ward L, using C2H2 gas as a carbon source deposited for 45 minutes of coating, found that for
higher pressure and higher bias voltage resulted a higher deposition rate and thicker layer[12].According to
Bewilogua K and Hofmann D., there are 3 (three) types of interaction during formation of DLC that are (a) directly,
(b) indirectly and (c) subplantations[9].

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 250

225

Hardness (VHN)
200

175

150

125

100
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2
Pressure(mbar)

FIGURE 2.The influence of pressure on the hardness of carbon steels coated for 4 hoursof coating time.

The formation of DLC hard layers during interactions, either directly or indirectly, are likely sp3 and sp2 bonds, but
for subplantation the possibility form are sp3, sp2 and a-C:H bonds.The formed DLC layer usually consists of a
mixture of hybrid carbon atoms sp2 and sp3, where the ratio of sp3 and sp2 composition greatly influences its
characteristics. Furlan KP et al explained in the phase diagram that there are different types of carbon bonds in the
DLClayer according to the number of sp3 and sp2 formed [13]. Compositionratio of formed sp3 and sp2 bonds can
improve the properties of DLC layer near diamond or graphitic properties.
The formed DLC produced by coating process of pressure variation at 400 °C and 4 hours coating time indicates
that the higher pressure of the coating process the higher hardness (from 1.2 mbar to 1.6 mbar). However, after 1.6
mbar of pressure,the hardness decreasethough thecoating pressureincreasefrom 1.6 mbar to 2.0 mbar.
Correlation between pressure and formed plasma during coating process is higher pressure, much more formed
ions/molecules. Formed ions during coating process are C+, Ar+ and CxHy+, these ions are as mains contributor in
formation of diamond like carbon coating according to the formation of DLC[9].
The rate of DLC layer formation is greatly influenced by the amount of forming ions and based on this research
it’s found that the optimum condition (the highest hardness) was achieved at 1.6 mbar pressure (Figure 2). The
hardness decrease for coating process above 1.6 mbar of pressure that is 1.8 mbar and 2.0 mbar. Based on the
bonding structure of the DLC layer formed, the optimum hardness will be obtained if the bonding structure formed
on the DLC layer is sp3. Usually the bond structure formed in the DLC layer is a mixture of sp2, sp3 and hydrogen,
the higher the percentage of sp3 bond structure, the harder the formed DLC layer. Moriguchi H et al classifies the
percentage relationship of sp3, sp2 and hydrogen bond structure in DLC layer[5]. Based on the classification, DLC
layers can be classified into several types and if the percentage of sp3 is higher then the DLC layer that is formed get
near to the diamond structure.
The DLC bond structure can be analyzed by using Raman spectroscopy method, this is a good spectroscopy to
obtain a detailed DLC bond structure and can be used to characterize the quality of non-destructive carbon bonding
structures [14]. However, this study has not yet tested the DLC bonding structure due to the limited available
facilities. To get the optimum conditions of the parameters of time, experiments has been done from 2 hours to 5
hours with 1-hour of increments at 1.4 mbar and 1.6 mbar of coating process pressures.Hardness test of the DLC
coated materials are shown in Figure 3.Based on these results, for 1.6 mbar coating pressure the optimum time for
coating is 4 hours and optimum hardness is 225.3 VHN, while for 1.4 mbar of pressure the optimum hardness is
171.7 VHN.

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 240

220 p = 1,4 mbar

p = 1,6 mbar

Hardness (VHN)
200

180

160

140

120

100
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5
Coating time (hours)

FIGURE 3.The influence of coating time on the hardness coated and uncoted materials.

Wear resistance analysis

Wear resistance analysis of DLC coated and uncoated materials were carried out using Ogoshi High Speed
Universal Wear Testing Machine.From the wear resistance we can calculate the wear rate of the surfaces. The wear
rate is very useful in predicting of surface damage of the material surfacesespecially related to wear and tear. In
machining application, indication of damage of components contacted each other is determined the wear surface rate
of the components. Wear test results indicated the wear rate of the film for various of coating time at 1.4 mbar and
1.6 mbar of pressure are shown Figure 4. Based on the test results, it was found that the minimum wear rate is 2.134
× 10-8 mm2/kg for 4 hours coating time and at 1.4 mbar of pressure and 1.701 × 10-8 mm2/kg for 4 hours coating
time and at 1.6 mbar of pressure, while for raw material is 1,443 × 10-7 mm2/kg. Compare to un-coating, there is a
significant increasing wear resistance, 6.8 times for 1.4 mbar of coating pressure and 8.5 times for 1.6 mbar of
coating pressure. This mean, that DLC coating can be applied to machine components especially for components
that contacted each other.
The research conducted by Banerji, A., et al. reported about the mechanism of friction reduction between cast
iron and DLC coatings shows, that it can decrease the coefficient of friction so that it can improve mechanical
efficiency of the machine [15]. Based on this research, the DLC coating can be applied to friction machine
components and can increase the life time and mechanical efficiency so that the operation is more efficient because
the friction losses become smaller.

1.6E-07

p = 1,4 mbar
Wear rate (mm2/kg)

1.2E-07
p = 1,6 mbar

8.0E-08

4.0E-08

0.0E+00
0 1 2 3 4 5 6
Coating time (hours)

FIGURE 4.The influence of coating time on the wear rate fo 1.4 mbarr and 1.6 mbarr of pressure.

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 Corrosion analysis
Corrosion test of coated and uncoated specimen were conducted usingpotentiostat of PGS-201T. Direct
information from corrosion test is current density (µA/cm2). From current density we can know the corrosion
resistance of the materials and also can calculate the corrosion rate. The corrosion test results are shown in Table 5
or Figure5.

TABLE 2.Corrosion current of DLC surface coating for various of coating time at 1.4 mbar and 1.6 mbar of
pressures.
Corrosion current (µA/cm2)
Time (hours)
p = 1.4 mbar p = 1.6 mbar
Raw 172 172
2 340 381
3 342 387
4 358 391
5 226 319

500
p = 1,6 mbar
Corrosion current (µA/cm2)

p = 1,4 mbar
400

300

200

100

0
0 1 2 3 4 5 6
Coating time (hours)

FIGURE 5.The influence of coating time on corrosion current density for 1.4 mbar of pressureand 1.6 mbar of pressure.

This corrosion test was done in 0.5% NaCl media. Based on the results of this test, it’s showed the current
density for all DLC coated specimens using plasma mixture of argon and LPG gas increase, it mean that corrosion
resistance decrease. This condition is not expected because the corrosion resistance decrease, whereas the expected
is that corrosion resistance of coated materials increase (has a higher corrosion resistance). Reduction in corrosion
resistance is may be caused by the impurity of the hydrocarbon in LPG gas used for coating.

Microstructure analysis
Cross-section microstructure DLC film on carbon steels surfaces are presented on Figure 6and Figure 7. Figure
6.a. and Figure 7.a show the cross-section microstructure of sample coated for 1.6 mbar of pressure and 2 hours and
4 hours of coating time respectively, while Figure 8.a shows surface morphology of DLC film coated for 1.6 mbar
of coating pressure and 4 hours of coating time.The chemical composition of coated materials for 1.6 mbar of
pressure and 2 hours of coating time analyzed by using SEM-EDS presented on Figure 6.From this condition,
detected carbon content is 11.07 at%. The process of forming the DLC layer has been explainedby Bewilogua K
and Hofmann D.[9], besides that during DLC coating forming parts of carbon react with iron atom to form iron
carbide (FeC) as compound layer and some of parts diffuse into deeper site as interstitial atoms[16].Based on the
DLC layer forming process and the interstition diffusion process it is possible to form two hard layers on the surface

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of the DLC layer and the FeC layer as shown in the cross-sectional view of the hard layer due to DLC coating. The
thickness of the hard layer in both the DLC layer and the FeC layer is about 5 μm (Figure 6.a).Based on elemental
analysis using EDSshown in Figure 6.b, shown that carbon content at cross-section surface coated at 1.6 mbar of
pressure for 2 hours of time coating (Figure 6.b) is 11.07 at%.While carbon content of the surface material, coated at
1.6 mbar of pressure for4 hours of time coating (Figure 7.b) is 31.82 at%. Based on these results for 31.82 at% of
carbon content the hardness is optimum.

(a) Cross-section microstructure. (b) Chemical composition of surface layer.

FIGURE 6.Chemical composition of cross-section microstructure coated for 1.6 mbar of pressureand 2 hours of coating time
analyzed by using SEM-EDS.

(a) The surface microstructure of materials surfaces (b) Surface composition of layer.
coated for 1.6 mbar of pressure and 4 hours of
coating time.
FIGURE 7.Chemical composition of coated material for 1.6 mbar of pressure and 4 hoursof coating time analyzed by using
SEM-EDS.

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 XRD TEST RESULTS
Formed phases during coating process was analyzed using XRD, Figure 8 show the XRD pattern for materials
coated for 1.6 mbar of pressure and of 4 hours of coating time. From XRD analysed, it’s found that formed phase is
Fe2C. This phase appear at 2θ 42,823 (JCPDF No. 03-1012).

FIGURE 8.The results of XRD test from a DLC coated steel shaft specimenat a pressure of 1.6 mbar and a time of 4 hours.

CONCLUSION
Based on experiment done, it can be concluded that,the optimum hardness and wear resistance are225.3 VHN
and 1.7 × 10-8 mm2/kg, respectively,at 1.6 mbar and 4 hours. Meanwhile, the un-coated materials are 115.5 VHN
and 1.4 × 10-7 mm2/kg. The results show that hardness and wear resistance increase in comparison to the un-
coated.The microstructure observed using SEM-EDS showed that thickness of hard layer is about 5 μm.From XRD
analyzed showed that the formed phase is Fe2C phase. Based on these results it is expected that DLC formed can be
applied for the machine components and can increase the life time and mechanical efficiency so that the operation is
more efficient because the friction losses become smaller.

ACKNOWLEDGEMENTS
The authors are grateful to Centre for Accelerator Science and Technology-National Nuclear Energy Agency
(CAST-NNEA) of Indonesia for the funding and facilitaties in this research as well as Mr. Sayono, Mr. Ihwanul
Aziz and Mrs. VikaArwida for the given assistance during this research.

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