2

Abstract
The present paper describes the first successful application of poultry waste
chicken feathers in the development of green, biodegradable and eco-friendly
lubricant additives. The additive was synthesized through three step chemical
functionalization of chicken feathers. First step involves the reaction between
chicken feather powder (CF) and (3-Aminopropyl)trimethoxysilane (APTMS) to
synthesis CF-APTMS, second step involves the synthesis of CF-Schiff base by
reacting CF-APTMS with 3,5-di-tert-butyl-4-hydroxybenzaldehyde and in the
third step, esterification with lauroyl chloride catalyzed by 4-
(dimethylamino)pyridine (DMAP) afforded the final product acylated chicken
feather Schiff base. The applicability of this CF derived additive as biodegradable
and ecofriendly lubricating oil additive was investigated by testing the
antioxidant, lubricity and anticorrosion properties in polyol which was taken as
reference base fluid. Rotatary bomb oxidation test (RBOT) was used to evaluate
the antioxidant characteristics while four ball test for the tribological properties.
The additive is found to be very effective as antioxidant and anticorrosive additive
but as antiwear additive its potential is moderate.

Keywords: Waste management, biodegradable additive, chicken feather, lubricant

additive, sustainable synthesis

Introduction
Lubricants play a vital role in the automotive sector so efforts have been made to
develop new generation bio based, nontoxic and biodegradable lubricants which
can replace the conventional mineral based oils. These new lubricants not only
addressing the depleting conventional oil sources but also deal up with the
emerging stringent environmental regulations.1,2 Along with this there is always
a drive for reduced emissions, increased durability, increased service intervals and
the constant drive to reduce friction, which leads to reductions in energy usage.
For a lubricants to be completely ecofriendly, biodegradable and non-toxic,
additives must also be environment friendly because its toxicity also plays a very
important role in the lubricant although their concentration in remains low in
comparison to the base oil. Therefore, across the globe substantial amount of
research work has been carried out in the past to develop new lubricant additive
from renewable materials which can work well with the evolving eco-friendly
base stocks.3,4 e.g. additives have even been made by condensation of various
amines with di(alkylpenyl)-phosphorodithioic acid, derived from renewable
material cashew nutshell liquid.5 Saga et al.6 prepared antioxidant additive for
the vegetable oils from micro crystalline cellulose. To obtain high viscosity index,
as well as pour point depressant Ghosh et al.7 Synthesized homopolymer of
sunflower oil and soybean oil. Many reports have been published on the use of
modified chitosan as lubricant oil additive, like chitosan gallate and chitosan
ester.8-12 On the basis of the above-cited literature, we believe that there exists
an immense scope to work on the utilization of renewable chicken feather
material. Chicken feather, a poultry waste is produced worldwide 8.5 billion
tonnes annually from feather meal industry.13 It is a cheapest, biodegradable and
natural biopolymer having 91% keratin protein.14,15 Many pendant functional
groups such as –OH, -COOH, -NH2 and –SH are present along with the
polypeptide chains of feather keratin. As suggested in the literature,16-18 keratin
has a high content of cysteine amino acid, consisting of sulfur–sulfur (disulfide)
linkages and helps in stabilizing the keratin by forming network structure through
joining of adjacent polypeptides by disulfide cross-links. It is widely known fact
that disulfides moiety improve the tribological properties as it is supposed to help
in surface film formation. In order to utilize this fact, in the present paper we
report for the first time, the development of lubricating oil additive from poultry
waste chicken feather. The synthesis of a new chicken feather Schiff base ester
has been synthesized in three steps (Scheme1). Its characterization was done by
FT-IR, 1H NMR, and TG. The applicability of this CF derivative as ecofriendly
lubricating oil additive was explored by testing the antioxidant, antiwear,
antifriction and anticorrosion properties in polyol which was taken as reference
base fluid.

Material and Methods

Materials
Chicken feather was supplied by local poultry farm, APTMS, 3, 5-di-tert-butyl-4-
hydroxybenzaldehyde, and DMAP were purchased from Sigma-Aldrich. N,N-
Dimethylacetamide (DMAc), lauroyl chloride and ethanol were purchased from
Merck. Acetic 6 acid and methanol was purchased from RFCL (formerly Ranbaxy
Fine Chemicals Limited, India). All other chemicals were of the highest available
grade and were used without further purification. Chicken feathers were grinded
by RETSCH planetary ball mill and we used 32 mesh size sieve for separation of
fine CF particles. Grafting of 3-aminopropyltrimethoxysilane (APTMS) The
chemical modification of CF was carried out by using the APTMS as a grafting
agent. In typical experiment, grafting process was carried out in a 100 ml three-
neck round bottom flask equipped with magnetic bead and condenser. Chicken
feather (2 gm) was added to dried flask and then toluene (40 ml) and 5.0 g of
APTMS were added. The reaction mixture was refluxed for 24 h with the
continuous stirring under the nitrogen atmosphere. The modified CF were
recovered by filtration and subjected to a Soxhlet extraction with dichloromethane
to remove unreacted APTMS for 24 h. The obtained material was dried in vacuum
oven at 50 °C. Synthesis of amino functionalized chicken feather Schiff base (CF-
APTMS-SB) 1 g of Amino functionalized chicken feather (CF-APTMS) and 0.2
g catalytic amount of acetic acid were dissolved in 20 mL methanol. The mixture
was stirred for1 h at room temperature, and then the solution of 1.64 g (∼7 mmol)
of 3, 5-di-tert-butyl-4-hydroxybenzaldehyde in 10 mL of methanol was added
drop wise. The mixture was refluxed for 10 h, and then the product was obtained
in the form of a yellow powder which was filtered. The physically adsorbed
aldehyde was extracted successively with ethanol and ether for 2days. The final
product was dried in vacuum oven at 50 °C. Synthesis of acylated chicken feather
Schiff base (CF-APTMS-SB) 0.75 g of above synthesized CF-APTMS-SB and 15
mL of DMAc was taken in a 100mL round- bottom flask. The mixture was stirred
for 1h at 80 °C and then cooled to 50 °C. Lauroyl chloride (5g, 22.8 mmol)
dissolved in DMAc (15 mL) was added drop wise into the reaction mixture within
1 h, and then 0.5 g of DMAP was added into it. The temperature was gradually
increased to 90 °C with stirring. The reaction was carried out during 3 h.
Afterward, the content was cooled down to room temperature without stirring and
poured into 100 mL of a cooled water taken in a beaker. The dark brown product
was filtered and then washed twice with 0.2 M NaHCO3 and several times with
ethanol. The semisolid light brown product was dried in vacuum oven at 50 °C
overnight.

Characterization
The synthesized compounds were characterized using various analytical
techniques. The Fourier transform infra red (FT-IR) spectra were recorded by the
KBr method with a PerkinElmer spectrometer between 500 and 4000 cm−1.
Thermal decomposition of developed catalyst was probed using a Diamond TG-
DTA analyzer (Perkin-Elmer). All samples were analyzed in the temperature
range of 30 to 500 °C under nitrogen flow. The 1H NMR spectra was recorded on
a Bruker Avance 500 Spectrometer in DMSO-d6 (0-11 ppm for 1H) as a standard
and the chemical shifts are expressed in δ parts per million relative to
tetramethylsilane (TMS) as the internal standard.

RBOT Test
In order to evaluate the antioxidant property of acylated (CF-APTMS) in polyol
(pentaerythritol tetraoleate) base oil as additive, tests were conducted on a rotating
bomb oxidation test (RBOT) apparatus manufactured by Stan-hope Seta, U.K.
following the ASTM D2272.19 The temperature was kept 150 oC as TG analysis
revealed that the acylated(CF-APTMS-SB) was fairly stable at this temperature
too. Blends were prepared by doping different concentration of additive in base
oil. Samples were measured near to 50.0 ± 0.5 g and 5.0 ml of reagent water added
to the sample. The copper catalyst was measured and cleaned with 220 grit
silicone carbide sand paper and was used immediately. The wire was converted
into spring-coil shape having an outside diameter of 44–48 mm, weight of 55.6 ±
0.3 g and height of 40–42 mm. The bomb was assembled and slowly purged twice
with oxygen. The bomb was charged with 90.0 ± 0.5 w (620 kPa) of oxygen then
tested for leakage by immersing in water. The test was considered completed after
the pressure dropped more than 175 kPa from the original pressure.

Four-ball Test

Four-ball test machine from Ducom, India was used for evaluating the antiwear
and antifriction properties in terms of wear scar diameter (WSD and) average
friction coefficient as per the ASTM D4172B standard test method.20 For these
tests, the typical 12.7 mm steel balls were used where one upper ball under the
load is rotated against three stationary steel balls clamped in the holder. Different
samples were prepared by adding different concentrations of additives acylated
(CF-APTMS-SB) in polyol reference base oil and four balls were covered by them
and tests were performed at a rotating speed of 1200 rpm; 392 N load; 75 °C
temperature and for 60 min duration.

Anticorrosion test
The anticorrosion activity of the synthesized acylated (CF-APTMS-SB) was
evaluated using the standard corrosion testing procedure.21,22 At first the carbon
steel metal was cut into small pieces of size 15 mm × 10 mm × 2 mm (area 0.6 sq.
inches) by machining and milling. After machining and milling these metal pieces
were hand polished using carborundum emery paper grade number C 201 AH
extra fine. Afterwards, these metal pieces were degreased using xylene–
isopropanol mixture (1:1). These coupons were weighed up to an accuracy of 0.1
mg before exposing in base oil and various blends of additive in the base oil. These
degreased and preweighed metal specimens were suspended using teflon thread
separately in base oil and various blends of additive in the base oil contained in
stopped measuring cylinders. These static immersion studies were carried out for
a period of 25 days (600 h) at 110 °C maintained in an air oven. The test metal
specimens were evaluated after 25 days for quantitative estimation of corrosion.
After the test duration the metals were derusted using derusting solution (36%
HCl containing 5% Sb2O + 4% SnCl2) and finally weighed up to an accuracy of
±0.1 mg. The weight loss of each test metal was recorded and the corrosion rate
was calculated according to the equation 1

Anticorrosion test
The anticorrosion activity of the synthesized acylated (CF-APTMS-SB) was
evaluated using the standard corrosion testing procedure.21,22 At first the carbon
steel metal was cut into small pieces of size 15 mm × 10 mm × 2 mm (area 0.6 sq.
inches) by machining and milling. After machining and milling these metal pieces
were hand polished using carborundum emery paper grade number C 201 AH
extra fine. Afterwards, these metal pieces were degreased using xylene–
isopropanol mixture (1:1). These coupons were weighed up to an accuracy of 0.1
mg before exposing in base oil and various blends of additive in the base oil. These
degreased and preweighed metal specimens were suspended using teflon thread
separately in base oil and various blends of additive in the base oil contained in
stopped measuring cylinders. These static immersion studies were carried out for
a period of 25 days (600 h) at 110 °C maintained in an air oven. The test metal
specimens were evaluated after 25 days for quantitative estimation of corrosion.
After the test duration the metals were derusted using derusting solution (36%
HCl containing 5% Sb2O + 4% SnCl2) and finally weighed up to an accuracy of
±0.1 mg. The weight loss of each test metal was recorded and the corrosion rate
was calculated according to the equation 1.
RESULTS AND DISCUSSION
Characterization of the acylated CF-APTMS-SB
FTIR
FTIR spectrum shows that unmodified CF and modified CF in panels a-d of
Figure 2. The FTIR spectrum of bare CF (Figure 2a) exhibited two absorption
bands at 1644 and 1535cm-1 were attributed to the N–H bending vibration and
C–N stretching in amide group, respectively. A broad band appeared at 3430 cm-
1 was due to the N–H and -OH stretching, revealing the presence of many
hydroxyl and amine groups on the surface of CF, which are major grafting sites
for APTMS. The two bands at 2958 and 2917 cm-1 were assigned to the aliphatic
C−H symmetric and asymmetric stretching vibrations respectively. Figure 2b
showed two additional peaks at 1124.4 and 1036.6 cm-1 were due to the stretching
vibration of C−NH2 and Si–O stretching confirming the siloxane bond formation
between APTMS and CF respectively. The other significant evidence observed
was the increased intensity of the C–N stretching and N–H bending vibration
bands at 1643 and 1515 cm−1 along with the reduced intensity of the −OH
stretching band at 3277 cm−1. It further suggested the APTMS had been
successfully grafted on the CF. Further, the appearance of characteristic imine
(C=N) stretching band at 1627 cm−1 in the CF-APTMS-SB confirmed the
successful synthesis of corresponding Schiff base from the reaction of CF-
APTMS with the 3, 5-di-tert-butyl-4-hydroxybenzaldehyde. Aromatic C=C and
C−H stretching bands appeared at 1515 and 2956 cm−1, respectively in Figure 2c
further confirmed the formation of Schiff base.23 A band at 1217 cm−1 attributed
to the C−O stretching 11 band of the hindered phenolic group was appeared. In
case of acylated (CF-APTS-SB); Figure 2d, the increased intensity of C-N
stretching of amide group was observed which was assumed due to the reaction
between lauroyl chloride and amine group. Another significant evidence observed
is the additional characteristic C=O stretching peak at 1737 cm−1 due to the
successful ester linkages between CF and lauroyl chain. Moreover the increased
intensity of the asymmetric and symmetric C−H stretching (CH2 and CH3 groups)
bands at 2977 and 2856 cm−1 along with the reduced intensity of the −OH and
−NH stretching band at 3440 and 3274 cm−1, respectively confirmed the
successful synthesis of the desired acylated (CF-APTMS-SB).