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STUDY OF POLY ETHYLENE CO-VINYL

ACETATE AND ZDDP AS ADDITIVES FOR
BIOLUBRICANT FORMULATIONS IN
KARANJA OIL.
D. Mahipal1, A. R. Nithin2, N. H. Jayadas3
1
Assosiate professor, 2PG Scholar, 3Professor
123
Department of Mechanical Engineering,
12
Government Engineering College, Thrissur, Kerala, India-680009
3
School Of Engineering, Cochin University of Science and Technology, Kochi, Kerala, India-682022

Abstract : The principal objective of this study is to evaluate the lubricant properties of karanja oil with and without additives. The
lubricating properties such as viscosity, pour point and the parameters influencing environmental effects viz. biodegradability and
toxicity of the samples are evaluated and compared with that of SAE 20W40. The karanja oil is mixed with various proportions of Zinc
Dialkyl Dithio Phosphates (ZDDP) and Ethyl Vinyl Acetate (EVA). The addition of ZDDP is found to improve the viscosity of karanja
oil marginally whereas addition of EVA improves the viscosity of karanja oil by about 109%. With the addition of EVA, the pour point
of the oil samples is found to improve marginally. The experimentally observed variation of viscosity with temperature shows good
agreement with trend predicted using Walther equation. The improvement in lubricating properties and ecofriendly nature of the karanja
oil with additives indicate that this bio-lubricant is a promising option for industrial applications.

Keywords: Biodegradability; EVA; Karanja; Toxicity; Viscosity; ZDDP

I. INTRODUCTION
Most of the conventional lubricating oils are mineral based, primarily obtained from petroleum derivatives. Ma-jor
applications of these fluids include automotive engine and transmission systems, and other industrial purposes [1]. The detrimental
impact on environment caused by the min-eral oils is of a grave concern from environmental sustaina-bility view point. This has
become the motivation to car-ryout research studies to propose suitable alternatives for mineral based lubricating fluids [2]. The
diminishing oil reserves, non-biodegradability and toxicity further empha-size the need to focus on development of bio lubricant for-
mulations. Vegetable oils on the other hand has many in-herent advantages such as low toxicity, high flash and fire points,
biodegradability [3,4], high viscosity indices and so on. However the low oxidative stability, low corrosive re-sistance, small viscosity
range and high pour point, limits their applicability as suitable alternative to mineral based lubricating fluids.
Several research studies have been reported on the scope of using different vegetable oils as bio-lubricant candidates. This includes
studies conducted on rapeseed oil, castor oil, sunflower oil, coconut oil etc. [5,6,7]. Qingye Gong et al.[8] investigated the anti-wear and
anti-friction properties of synthetic thiophosphates as additive in rapeseed oil. Alexandro Ruggiero et al. [4] compared the tribological
performance of hydrotreated vegetable oil obtained from raw rapeseed oil, raw Jathropa curcas and fatty acid methyl ester using a ball
on flat reciprocatory tribometer. All tested samples showed low coefficient of friction (CoF), among these the lowest CoF was shown
by Jathropa curcas oil and lowest wear by hydro treated rapeseed oil.
For a lubricant, viscosity is one of the key parameter. Low viscosity causes failure of oil film at high loads and high temperatures,
resulting in increased wear. Whereas high viscosity results in viscous heating which in turn results in oxidation of the oil and high loads
on the mating surfaces. The viscosity range of vegetable oils are generally lower compared to mineral oils. Many polymers and chemicals
can be used to improve the viscosity of vegetable oil. Rani et al. [9] found that EVA co-polymer can be used as a good viscosity modifier
for rice bran oil and addition of low density poly ethylene act as a viscosity index modifier for rice bran oil. ZDDP is a popular anti-wear
additive. It stabilizes the lubricant film by adsorbing on to the metal surface and chemical reactions [10,11]. M. A. Azhari et al. [12]
analysed anti-wear and anti-friction properties of corn oil by adding ZDDP. It was observed that the ZDDP improves the anti-wear
property. It also resulted in the lowering of CoF of base oil.
Rani [13] studied the biodegradability of rice bran oil in a bacterial growth medium by observing the increase in turbidity of oil
sample. It was found that the formulated oil is more biodegradable than SAE 20W40. Joseph Babu et al. [14] studied the reduction of
pour point of coconut oil after alkali esterification and he also demonstrated the non-toxicity of formulated oil by disk diffusion
techniques.
Karanja oil is derived from seeds of Millettia pinnata. It is used in soap making, in leather tanning and used as lamp oil. It is also
used as a natural insecticide. Studies have been reported using karanja oil as potential base stock for biolubricant [12]. In this paper, the
viscosity, viscosity index, pour point, biodegradability and toxicity of karanja oil mixed with EVA and ZDDP separately were evaluated
and compared with SAE 20W40.

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II. Experiments
2.1 Materials
Karanja oil extracted from karanja seeds obtained locally was procured from Ganesh traders Coimbatore, India. Ethyl vinyl acetate
pellets with a vinyl acetate content of 40%, melt index 57 g/10 min and ZDDP were supplied by Sigma Aldrich.

2.2 Preparation of lubricating oil formulations

The two samples of karanja oil were prepared with EVA and ZDDP separately. ZDDP was added in proportions ranging from 0.5%
to 2% by weight. The karanja and ZDDP were mixed using a sonicator, Vibra-Cell VCX750. A clear homogenous mixture was obtained
after 10 minutes.
EVA was mixed with karanja oil in proportions ranging from 0.5% to 2% by weight. EVA pellets in the correct proportions were
mixed with the oil and heated up to 85oC using an overhead stirrer at 300 rpm for 5 to 8 hours depending upon the concentration. The
mixing is carried out till a clear homogenous mixture was obtained.
ZDDP was found to segregate after a period of one week and mixtures with EVA turns cloudy after a period of three months.

2.3 Measurement of viscosity

The dynamic viscosity of karanja oil with EVA and ZDDP was measured using Brookfield LVDV2T viscometer as per ASTM
D2983-09 standards. The viscosity index of the samples were determined as per ASTM D2270. Walther equation was used to validate
the viscosities at various temperatures. Triplication of measurements were carried out to minimize errors.
Walther equation is the popular method used to determine the viscosity of oil and gives the basis for ASTM viscosity–temperature chart
loglog CA Blog T
In this equation, η, viscosity values of the lubricant at temperatures of 40°C and 100°C must be considered. The constant C is considered
as 0.6 or 0.7. This information helps us to determine the constants A and B. Normally, Walther’s equation has a constant value of C =
0.7 for all lubricants.

2.4 Estimation of Pour point

The pour point of the samples, karanja+2% ZDDP and karanja+2% EVA were estimated using differential scanning calorimetry
(DSC). In DSC experiment, oil sample is cooled to -50°C and then heated at the rate of 10°C per minute, while the thermogram is
recorded. DSC is found to be more accurate in determining the pour point of vegetable oil compared to ASTM D97 method since
the phase transition temperature of vegetable oils remains unaffected on different heating rates [15] but changes with different
cooling rates.

2.5 Biodegradability
The main feature of any bio-lubricant formulation is its biodegradability. In this study, the bio-lubricant test was conducted in a
bacterial growth medium. Here, Pseudomonas aeruginosa is cultivated in the mixture of oil sample and dimethyl sulphoxide
(DMSO) at a concentration of 1000 µg/ml. The samples were kept incubated at 28 ºC and 49% RH. Bacteria multiplies by oxidizing
the carbon chains contained in the oil sample, which is indicated by increase in turbidity. The turbidity measurements were taken
at every 24 hours for 5 days using a digital nephelometer.

2.6 Toxicity
The toxicity of the oil samples were estimated by disk diffusion technique. A petri dish containing an agar medium was spread
plated with bacterial culture containing Pseudomonas aeruginosa (24 hours old). Three pits of 5 mm diameter and 2 mm depth was
carved on every agar plate for holding the sample, gram positive and gram negative control solutions. Gram positive strain was taken
as silver nitrate solution and gram negative was taken as demineralized water. The silver nitrate solution being highly toxic to the
bacterial growth result in a large clear zone after incubation compared with demineralized water which is passive towards bacterial
growth. Hence by comparing the diameter of the clear zone produced by sample solution with that of the silver nitrate solution,
toxicity can be assessed.

III. RESULTS AND DISCUSSION

The viscosity of samples were evaluated using Brookfield LVDV2T viscometer as per ASTM D2983-09 standard. Viscosity
readings were taken at every 5ºC increment starting from 40ºC to 100ºC. The variation of viscosity with temperature of karanja
oil with different weight percentages of EVA are shown in Fig.1 to 4. Figures 5 to 9 display the variation of viscosity with
temperature of karanja oil with different % of ZDDP.
Walther equation was used to evaluate the experimental values of viscosity as shown in figures 1-4. It can be seen that theoretically
predicted values of viscosities using Walther equation in karanja oil with EVA shows similar values with that of the experimental
values.

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Fig. 1 Temperature vs Viscosity for karanja + 0.5% EVA

Fig. 2 Temperature vs Viscosity for karanja + 1% EVA

Fig. 3 Temperature vs Viscosity for karanja + 1.5% EVA

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Fig. 4 Temperature vs Viscosity for karanja + 2% EVA

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Fig. 5 Viscosity Index of karanja + EVA

Fig. 6 Temperature vs Viscosity for karanja + 0.5% ZDDP

Fig. 7 Temperature vs Viscosity for karanja + 1% ZDDP.

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Fig. 8 Temperature vs Viscosity for karanja + 1.5% ZDDP.

Fig. 9 Temperature vs Viscosity for karanja + 2% ZDDP

Fig. 10 Temperature vs Viscosity for SAE20W40

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The viscosity improvement of the base oil at 40 ºC with 2% EVA is about 209% more than that of the viscosity of the base oil with
2% ZDDP. It is evident that viscosity variation of the formulated oil samples depends mainly on the concentration of additives in the
base oil. At 40ºC, karanja oil with 2% EVA shows better viscosity improvement than that of SAE 20W40. ZDDP being an anti-wear
additive, did not provide a prominent improvement in viscosity.

Fig 11. DSC Curve of karanja oil, karanja +2% ZDDP and karanja +2% EVA

Variation of viscosity index of karanja oil with EVA is shown in Fig. 5. It is evident that the addition of EVA reduces the viscosity
index of the base oil. Even though the viscosity improvement of karanja oil on the addition of EVA is very high, V.I of the oil
decreases with EVA concentration [9].The validation of the experimental values of viscosity was done using Walther equation and
Similar trends were obtained.

Table 1. Pour point of karanja oil, karnaja oil+ 2%EVA and karanja oil+2% ZDDP

SAMPLE ENDOTHERMIC PEAK(POUR

POINT) (°C)

KARANJA OIL 6.4

KARANJA+2%ZDDP 4.2

KARANJA+2%EVA 2.2

DSC was used to access the pour point of karanja oil with additives. It can be observed that the pour point of karanja oil has been
reduced by adding additives. Fig. 11 shows DSC curves of karanja oil, karanja + 2 % ZDDP and karanja + 2 % EVA. The pour
point values of base oil and formulated oils are given in Table 1. From the Table it is evident that karanja + 2 % EVA formulation
exhibit low value of pour point when compared to that of base oil and karanja + 2 % ZDDP.

One of the main parameter of the biolubricant is its biodegradability. The biodegradability of oil samples were estimated as the
increase in turbidity of the bacterial growth medium mixed with the oil samples [13, 16, 17]. The results of biodegradability test
are shown in Fig 12. Vigorous microbial growth is observed in case of plain karanja oil. The addition of additives in to the oil
reduces the turbidity by a small percentage. It is also observed that, in general, the addition of polymeric material EVA in to the
vegetable oil resulted in lowering of turbidity than the base oil containing ZDDP. This may attribute to the non-biodegradable nature
of EVA mixed in the karanja oil. At the same time, the turbidity curve of SAE 20W40 oil is having the lowest increase rate. This
clearly states that the mineral oil have very low biodegradability.

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Fig. 12 Percentage increase in Turbidity

The toxicity of oil is an important factor for an ecofriendly lubricant. If a lubricant oil is toxic, it can affect the metabolism of any
living organism. It may also leads to the accumulation of toxic substances through food chains. The toxicity of the lubricant oils is
demonstrated using disc diffusion technique. The agar plates with bacterial culture and oil samples were kept incubated for 24 hours
and bacterial growth can be observed as cloudiness over the agar plate. If the sample taken is toxic to the bacteria, the bacterial
growth will be inhibited to a certain region around it, which will be visible as clear zone. The clear zone diameter of the sample is
compared to the clear zone diameter of gram positive strain (silver nitrate solution) which is heavily inhibits the growth of bacteria
around it. The toxicity is represented as percentage inhibition of the sample to that of gram positive strain .

Fig.13 Toxicity percentage inhibition

From the graph, we can see that the karanja oil is little toxic to bacterial growth which can be attributed to the inherent anti-microbial
effect. But the addition of ZDDP lowers the toxicity of karanja oil. At the same time, the addition of EVA results in increase of
toxicity. This may be due to the polymeric nature of EVA
IV. Conclusions
Even though the karanja oil is identified as the base oil for bio lubricant, the viscosity range of oil was low. The viscosity can be
sufficiently improved by mixing EVA into the base oil in small quantities. But, the addition of EVA reduces the viscosity index of base
oil to a small extent. The pour point of lubricant oil samples were estimated using differential scanning calorimetry. It may be observed
that addition of EVA reduces the pour point of base oil considerably. The non-toxicity and the biodegradability of the formulated oils
were established through the disc diffusion technique and turbidity test respectively. It may be concluded that, on further improvement
of parameters, the karanja oil may be developed into a good biolubricant oil.

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