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A Comparative Study on Commercial Grade and Laboratory Grade of

TiO2 particle in Nanofluid for Quench Medium in Rapid Quenching
Process
To cite this article: C.A Ramadhani et al 2019 IOP Conf. Ser.: Mater. Sci. Eng. 622 012017

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3rd MRS-ID meeting 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 622 (2019) 012017 doi:10.1088/1757-899X/622/1/012017

A Comparative Study on Commercial Grade and Laboratory

Grade of TiO2 particle in Nanofluid for Quench Medium in
Rapid Quenching Process

C.A Ramadhani, W.N. Putra*, D. Rakhman, L. Oktavio, S. Harjanto

Department of Metallurgy & Materials, Faculty of Engineering, Universitas Indonesia,
Depok, Indonesia
*
Corresponding author: wahyuaji@metal.ui.ac.id

Abstract. Heat treatment of material particularly quenching requires a high thermal conductivity
quench medium. Hardenability of material, dimension, and geometry of the component are
considerate on choosing quench medium. The cooling rate of quenching affects the properties
and microstructures by creating specific phase transformation to occur. Enhancing the quench
medium by accelerating the cooling rate can be attained by the addition of nanoparticle which
has higher thermal conductivity. This nanoparticle-added medium is commonly termed as
nanofluid. Commercial and laboratory grade of TiO2 was used as the nanoparticle to distilled
water as the nanofluid base to acquired higher conductivity on the heat treatment process. In this
experiment, a top-down method was done to obtain TiO2 particles by grounding using a planetary
ball mill for 15 hours at 500 rpm. Nanofluid quench medium was mixed with TiO2 in various
concentration of 1%, 5% and 10% with a volume of 100 ml each. Samples of AISI 1045 or JIS
S45C carbon steel were used to obtain different cooling rate on a different type of TiO2 particles.
Samples were heat treated by austenizing at 1000oC for 1 hour, followed by rapid quenching in
nanofluid quench medium with the addition of agitation as quenching variable. Observation of
particle morphology and size, material composition, and the change of surface ere measured by
Field-Emission Scanning Electron Microscope (FE-SEM), and Energy Dispersive X-Ray
Spectroscopy (EDX). Initial characterization showed that the TiO2 particle size was at 150 nm
range, and roughly free from any impurities. Martensite microstructures have the most
significant area and the amount at laboratory-grade TiO2 in 0.2 wt% composition, followed by
commercial-grade at 0.3 wt% composition.

Keywords: Nanofluid, TiO2, Quenching

1. Introduction
Heat treatment is one of the major processes used in engineering applications in order to achieve
improved properties of the material. Desired and better microstructures in steel are obtained by
quenching process that involves heating it to austenite temperature then holding followed by rapid
cooling by immersion into fluids. Cooling rate and fluids affect significantly on the properties of the
material as well as the microstructure[1]. The ability of heat transfer is necessary for the fluid or
quenchants since it directly connected to the cooling rate. The outcome of a fast cooling rate is martensite
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3rd MRS-ID meeting 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 622 (2019) 012017 doi:10.1088/1757-899X/622/1/012017

structure with desirable high hardness value. Nanofluids have been common to be researched as
quenchants as it owns the ability to increase heat transfer in quenching [2].
Titanium dioxide in the form of powder is extensively used in many industries, from food to the
cosmetic industry. Visible and ultraviolet light cannot pass TiO2 regarding its opacity [3]. In the food
industry, it contributes to longer the lifetime of the food preventing early degradation. On the other hand
in the cosmetic industry, it helps to absorb ultraviolet light in the sun thus becoming sunscreen [4].
Possessing a white and bright colour, TiO2 benefit the use of coating and painting as pigments [5]. Not
only the coating of the paint, but it also used on coating paper producing brighter and cleaner paper. In
the previous paper, the beneficiation of TiO2 is also applied to protect the metal from corrosion regarding
its high specific surface area and suitable hydrophobicity property [6]. Having a high chemical and
thermal stability and wideband energy TiO2 is also used as light harvesting material in dye-sensitized
solar cells [7].
TiO2 particles in nanometer-sized can be dispersed in liquid suspensions in a base fluid resulting
nanofluids. In nanofluid synthesis, a surfactant is added to avoid agglomeration of suspended particles
because the more significant surface area that can worsen the heat transfer in nanofluid as quench
medium [8-9].
The objective of this research is to know the characteristics of TiO2 nanofluid as quench medium in
quenching after heat treatment and study the difference of the use of laboratory and commercial grade
nano-sized TiO2 that obtained by planetary ball mill on microstructure, composition, and hardness.

2. Materials and methods

2.1. Preparation of TiO2 Nanofluids

Laboratory and commercial grade TiO2 powder were prepared by planetary ball mill with a top-down
method in order to obtain nano-sized particles for 15 hours at 500 rpm.
The addition of 0.1%, 0.2%, 0.3%, 0.4% and 0.5% of TiO2 were used to the quenchants of distilled
water until 100ml. Nanofluid preparation then obtained by dispersing TiO2 nano-sized particles in
distilled water with ultrasonic agitation for 480 seconds.

2.2. Material for Quenching Experiments

Steel S45C was prepared by cutting the material in 15mm x 10mm x 10mm dimension manually by saw.
Heat treatment was carried out in above austenizing temperature 600oC for 15 minutes for pre-heating,
then heated at 1000oC for one hour followed by quenching in TiO2 nanofluids.

2.3. Experimental
Microstructure figure was observed by metallography preparation followed by etching with Nital 3%
then followed by microscope examination. Hardness measurement was obtained by a Vickers hardness
test with a 300gf load. Field Emission Scanning Electron Microscope (FE-SEM) from Field Electron
and Ion Company (FEI), model type F50 and Energy Dispersive X-Ray (EDX) from Energy Dispersive
Analysis X-Ray Company (EDAX), model Apollo X examination were done at Centre for Material
Processing and Failure Analysis (CMPFA) Universitas Indonesia.

3. Results and discussion

3.1. FE-SEM and EDX Examination

Figure 1 and 2 showed the result of FE-SEM examination of TiO2 laboratory and commercial grade.
Figure 1a, 2a showed the magnification of 25000X, and figure 1b,2b showed the magnification of
50000X. Figure 2 showed the result of FE-SEM examination of the TiO2 commercial grade. Commercial
grade TiO2 had slightly bigger dimension at roughly 160 nm than laboratory grade TiO2 which in range
of 150 nm.

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3rd MRS-ID meeting 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 622 (2019) 012017 doi:10.1088/1757-899X/622/1/012017

Figure 1. FE-SEM image of laboratory-grade Figure 2. FE-SEM image of commercial-grade

TiO2 with (a) 2500x magnification and (b) TiO2 with (a) 25000x magnification and (b)
50000x magnification. 5000x magnification

Table 1. EDS Test result for chemical composition (wt %) of TiO2 particles.

Sample Ti Si P S Cl K
Laboratory Grade Powder 99.06 - 0.43 - 0.51 -
Commercial Grade Powder 97.76 0.52 0.45 0.37 0.33 0.57

Table 1 showed the distribution of the elements in laboratory-grade and commercial-grade TiO2. The
element distribution shows that the purity of laboratory grade was higher than in the commercial grade
TiO2. On both powder, however, no significant metal contaminant was found.

3.2. Microstructure Observation

Figure 3 showed the microstructure of steel quenched in distilled water. The martensite structure was
observed from the dark area. Figure 4 a-e showed the 0.1wt% - 0.5wt% composition of laboratory
grade.Laboratory-grade TiO2 in 0.2 wt% composition showed a larger area of martensite structures than
the rest of the composition, and it was shown on Figures 4. 0.3, 0.4 and 0.5 (wt.%) shows a smaller area
of martensite structure than in 0.2 wt% composition.In microstructures, carbon has been spotted
sputtering out marked by a black spot in microstructures. It could be caused by decarburization because
S45C steel was medium carbon steel and react in austenizing temperature when heat and hold at 1000 oC
[10-11].

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3rd MRS-ID meeting 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 622 (2019) 012017 doi:10.1088/1757-899X/622/1/012017

Figure 3. Microstructures of S45C as-cast in (a) 100x magnification and (b) 200x magnification.

The result of after-quenched steel immersed in commercial-grade TiO2 can be seen in Figure 5.
Carbon had been spotted sputtering out in figure 5a and figure 5d. A martensitic structure can be
observed by the brown area. Figure 5c showed the largest martensitic structure area resulting in the
highest hardness value obtained by commercial grade TiO2. Figure 5d showed less amount of martensite
structure known from the lesser area of a dark color[12-13].

Figure 4. Microstructures of laboratory-grade TiO2 as quench medium. (A) 0.1% vol (B) 0,2% vol.
(C) 0.3% vol. (D) 0.4% vol. (E) 0.5% vol. taken at 100X magnification

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3rd MRS-ID meeting 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 622 (2019) 012017 doi:10.1088/1757-899X/622/1/012017

Figure 5. Microstructures of commercial-grade TiO2 as quench medium. (A) 0.1% vol. (B) 0,2%
vol. (C) 0.3% vol. (D) 0.4% vol. (E) 0.5% vol. taken at 100X magnification

3.3. Hardness Measurements

Hardness values were compared between steel quenched in laboratory-grade and commercial grade TiO2
nanofluids. Table 2 showed the value of the hardness in HV. Addition of nano-sized particles in 0.1%
has affected the hardness of the steel quite significantly than in 0% nanofluid or distilled water.
Laboratory-grade TiO2 0.1wt.% was harder than in commercial-grade TiO2 nanofluids. Highest hardness
values are owned by laboratory-grade TiO2 nanofluid in 0.2 wit% composition, followed by
commercial-grade TiO2 nanofluid in 0.3wt% composition.

Table 2. The hardness value of laboratory grade

800
Lab. Grade and commercial grade TiO2 in various
Commercial Grade composition.
750
Hardness (HV)

700

650

600

0,1 0,2 0,3 0,4 0,5

TiO2 (%)

Figure 6. Hardness value comparison of

laboratory grade and commercial grade TiO2 in
various composition.

Laboratory-grade TiO2 peaked at 0.2wt% composition while commercial grade TiO2 peaked at 0.3
wt% composition. Commercial grade TiO2 showed a relatively steady chart while laboratory grade TiO2
shows a fluctuating line with a decrease of hardness value in 0.3wt% composition shown in Figure 6.
The fluctuating hardness might because of agglomeration occurred in this particular composition. In
general, however, laboratory grade powder had better thermal conductivity compared with the

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3rd MRS-ID meeting 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 622 (2019) 012017 doi:10.1088/1757-899X/622/1/012017

commercial one. This result was different from our previous result where laboratory grade carbon had
lower conductivity compared with commercial carbon powder [14].

4. Conclusion
Laboratory-grade and commercial-grade TiO2 powder were grounded until reaching nano-sized particle
then use as quenchants in nanofluids. The addition of 0.1%, 0.2%, 0.3%, 0.4% and 0.5% were added to
distilled water as quench medium. Microstructures of the steel after a quench in nanofluid showed a
greater amount of martensite structure than without the addition of TiO2 powder. The highest hardness
value of 758.44HV was obtained with laboratory-grade TiO2 in 0.2wt% composition and followed by
commercial-grade TiO2 in 0.3wt% composition which was 749.19 HV. It can be concluded that, in
general, laboratory-grade TiO2 had bigger hardness value than commercial-grade TiO2. The reason can
be assumed because of the difference of Titanium element in laboratory and commercial grade that does
not differ remotely. The largest area of martensite microstructures showed at laboratory-grade TiO2 in
0.2wt% composition, followed by commercial-grade 0.3wt% composition. It can be concluded that
addition of nanofluid can improve the hardness of the material and the most optimum composition is
0.2-0.3wt% composition.

Acknowledgement
The authors would like to thank Ms. Ghiska Ramahdita for the fruitful discussion, and gratefully
acknowledged the financial support from Hibah PITTA 2018 funded by DRPM Universitas Indonesia
No. 2537/UN2.R3.1/HKP.05.00/2018.

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