Poultry Chicken Feather Derived Biodegradable Multifunctional

Subscriber access provided by FLORIDA ATLANTIC UNIV

Article

Poultry chicken feather derived biodegradable multifunctional additives for lubricating formulations Suman L. Jain, Padma Latha, Raj Kumar Singh, Aruna Kukreti, Mukesh Bhatt, and Rakesh C. Saxena ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.5b01071 • Publication Date (Web): 11 Feb 2016 Downloaded from http://pubs.acs.org on February 12, 2016

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Sustainable Chemistry & Engineering is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

Poultry chicken feather derived biodegradable multifunctional additives for lubricating formulations P. Padma Latha,a Raj Kumar Singh,a Aruna Kukrety,a Rakesh C. Saxena,a Mukesh Bhatta and Suman L. Jaina* a

Chemical Sciences Division, CSIR-Indian Institute of Petroleum, Mohkampur, Dehradun-

248005 (India)

Tel. 91-135-2525788; Fax: 91-135-2660202; Email: [email protected] *Corresponding author: Suman L. Jain

1 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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


Page 2 of 25

Page 3 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


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



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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 (Scheme 1). 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.


Page 4 of 25

Page 5 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Scheme 1: Synthesis of acylated (CF-APTMS-SB) from CF

Material and Methods Materials Chicken feather was supplied by local poultry farm, APTMS, 3, 5-di-tert-butyl-4hydroxybenzaldehyde,

and

DMAP

were

purchased

from

Sigma-Aldrich.

N,N-

Dimethylacetamide (DMAc), lauroyl chloride and ethanol were purchased from Merck. Acetic 5 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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 325 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 a 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 roundbottom flask. The mixture was stirred for 1h at 80 °C and then cooled to 50 °C. Lauroyl chloride


Page 6 of 25

Page 7 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(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.

Figure 1: a) CF; b) CF-APTMS; c) CF-APTMS-SB and d) acylated CF-APTMS-SB.

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.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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. 8 ACS Paragon Plus Environment

Page 8 of 25

Page 9 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


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.

Corrosion Rate =

Wt.Loss * ×15.5 = mg /( sq.dm)(day) or mdd ( Area)(Time)

(1)

By taking density of carbon steel (7.8 g/cm3) into account penetration rate was also calculated according to the equation 2.

Penetratio n Rate =

Wt . Loss * ×22 .3 = mils / year or mpy ( Area )(Time )( Metal Density ) 9 ACS Paragon Plus Environment

(2)


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 25

Where wt. loss is taken in mg; area in sq. inches of metal surface exposed; time in days exposed; density in g/cm3. 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


Page 11 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


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).



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 2: FTIR spectra of a) CF; b) CF-APTMS; c) CF-APTMS-SB and d) acylated (CF-APTMS-SB).

TGA TG curves of CF, CF-APTMS, CF-APTMS-SB, and acylated (CF-APTMS-SB) are shown in Figure 3. As shown in Figure 3a, the first mass loss (6%) of CF from 100-150 °C was probably due to the loss of water. The second weight loss occurred from 222 to 392 °C with a decrease in fiber mass ranging from 10 to 79% was associated to a general rupture of disulfide and peptide bonds. Owing to the strong inter- and intramolecular hydrogen and di sulfide bonds and close 12 ACS Paragon Plus Environment

Page 12 of 25

Page 13 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


packing of polypeptide chains in the form of β-sheets, CF showed the thermal degradation (Td) at 225°C. The APTMS grafted on CF (Figure 3b) showed a small weight loss around 150 °C owing to the loss of adsorbed water molecules. The second major mass loss started from 250 °C was due to the decomposition of APTMS moieties. TGA curve of the amino functionalized chicken feather Schiff base exhibited an exothermic major weight loss over a wide range of temperature (150-500 °C), indicating the slow decomposition of the Schiff base due to the obstruction of closely packed feather structure in the presence of additional functional groups on the feather surface (Figure 3c). The Td for CF-APTMS-SB was found to be at 219 °C. It is obvious that the introduction of a more functional group obstructs the chain packing causing loosening of packing structure which in turn causes the reduction of degradation temperature (Td). In case of acylated (CF-APTMS-SB), the Td was found to be at 153 °C which is lower than that of CF and CF-APTMS, due to the increase in substitution chain length (Figure 3d).

Figure 3: TGA curves of CF; CF-APTMS; CF-APTMS-SB and acylated (CF-APTMS-SB).



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 25

NMR Studies 1

H NMR spectra of unmodified feather and modified feather i.e., acylated (CF-APTMS-

SB) are shown in panels a and b of Figure 4, respectively. Compared to the spectrum of unmodified feather (Figure 4a), new chemical linkages were found in acylated (CFAPTMS-SB) (Figure 4b). In case of acylated (CF-APTMS-SB), a strong signal appeared at 0.88 ppm was attributed to the terminal methyl group proton of lauroyl fatty chain (C18). The signal for the methylene protons of longer alkyl chain (C10-C17) appeared in the region 1.1-1.4 ppm. The signals for the protons of second adjacent carbon next to ester and amide group (C9 and C19 protons) of fatty alkyl chain appeared at 1.5 ppm. A low intensity peak of second carbon proton of imine group (C5) appeared at 1.7 ppm. As the amount of 3, 5-di-tert-butyl-4-hydroxybenzaldehyde was very low relative to the lauroyl chloride, the intensity peaks appeared relatively weak. The signal for the first carbon proton next to amide group (C8) and first carbon proton next to imine group (C4) appeared at 2.2pm. The signal at 2.5 ppm appeared due to the water in DMSO-d6. The signal at 3.4 ppm appeared due to the DMSO-d6 and methoxy protons (C7). The signal at 7.2 ppm attributed to the C2 protons of the aromatic ring. The signal at 9.1 ppm is the characteristic signal of the C1 proton (imine C-H) as shown in Figure 4b. These analysis results further confirmed the successful formation of acylated (CF-APTMS-SB).


Page 15 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 4: NMR spectra of a) CF and b) acylated (CF-APTMS-SB).

Figure 5: Acylated (CF-APTMS-SB) solubility in polyol base oil.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 25

Antioxidant activity After the characterization of the acylated (CF-APTMS-SB), it was evaluated as antioxidant additive in polyol base. Three different samples were prepared by varying the acylated (CFAPTMS-SB) concentration as 500, 1000 and 1500 ppm in the polyol base oil. It can be concluded from results of RBOT test shown in Figure 6 that acylated (CF-APTMS-SB) at 500 ppm concentration enhances the RBOT time of reference polyol from 6 min 43 sec up to 10 min 6 sec. It remains almost same at 1000 ppm i.e. 10 min 7 sec while at 1500 ppm it drops to a value of 9 min 3 sec. So the optimum doping concentration is 500 ppm at which oxidative stability increases by 50%. The reason could easily be revealed as chicken feather and hydrolysates are reported to have some inherent antioxidant property due to high levels of cysteine amino acid.2426

Along with the polypeptide chicken feather framework, the acylated (CF-APTMS-SB) also

have the hindered phenolic moieties, a well established lubricant antioxidant27 which are introduced

by

the

schiff

coupling

of

CF-APTMS

with

the

3,

5-di-tert-butyl-4-

hydroxybenzaldehyde. It also creates imine bonds which could increase the metal chelating abilities and so may imparts the additional antioxidant property to the acylated (CF-APTMS-SB) by depressing the metal catalyzed oxidation.


Page 17 of 25

11 10 min 6 sec

10 min 7 sec

10 9 min 3 sec

RBOT Time (min.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


9

8

7

6 min 43 sec

6

5 Blank

500

1000

1500

Additive Concentration, ppm

Figure 6: Eﬀect of increasing acylated (CF-APTMS-SB) concentration in the polyol on the RBOT time.

Antiwear and antifriction activity Some previous studies reveals that organic schiff compounds have anti-wear and friction reducing additive properties as schiff base reacts with the metal surface to form a surfacecomplex film leading to the hindered metal contact.28 Apart from the imine groups, acylated (CFAPTMS-SB) have many polar ester groups introduced due to acylation. Peptide bonds and many polar side chains like unmodified -OH and -NH2, -SH, -COOH etc may also contribute in to the surface interactions. Accordingly the additive was found to have some antiwear property however the antifriction property is not found up to a significant extent. The results of the four ball test reveals that at 1000 ppm concentration of the additive, the WSD and average friction coefficient decreases to a value of 0.815 mm and 0.070 respectively from the value of 0.992 mm and 0.080 for blank polyol base oil. This is a 17.8 % decrease in the WSD. The additive is also tested at higher concentrations but no significant improvement is observed in the antiwear and antifriction properties (Figure 7). Complex structure of the CF proteins causing the unstable



surface film formation on the surface may be the reason for the poor antifriction property of the acylated (CF-APTMS-SB).

1200

Wear Scar Diameter (WSD), µm

WSD Fri. Coeff.

0.10

1100 0.08 1000 0.06 900 0.04

Average friction coefficient

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 25

800 0.02 Blank

1000

500

1500

Additive Concentration, ppm

Figure 7: Reduction in the WSD and the average friction coeﬃcient with increasing concentration of acylated (CFAPTMS-SB) in polyol base oil.

Anticorrosion test Schiff bases are reported to have the anticorrosion tendency too especially for steel-steel contact as they react with the metal surface to form a surface-complex film.28, 29-32 So the acylated (CFAPTMS-SB) was also tested for the anticorrosion property. It can be easily revealed from the performed anti corrosion test results given in the Table C1 that the synthesized acylated (CFAPTMS-SB) shows the anticorrosion activity when 1000 ppm concentration was used, which enhances when increased concentration of 2000 ppm was used. At 2000 ppm concentration the values for the weight loss, corrosion rate and penetration rate decrease to 0.10 mg, 0.10 mdd and 0.01 mpy from the original values of 25.40 mg, 26.25 mdd and 3.37 mpy for the polyol base. The 18 ACS Paragon Plus Environment

Page 19 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


acylated (CF-APTMS-SB) does not show any increased anti corrosion activity at higher concentrations however it is better than the polyol up to tested 5000 ppm level. So the optimum concentration is 2000 ppm as far as the anticorrosion activity is concerned (Figure 8). Table 1. Corrosion behaviour of carbon steel in polol base oil and various blends of additive acylated (CF-APTMS-SB) in it

Samples

Weight Loss (mg)

Corrosion Rate (mdd)

Penetration rate (mpy)

Polyol base oil (Blank)

25.40

26.25

3.37

1000 ppm acylated(CF-APTMS-SB)

12.00

12.40

1.59


0.10

0.10

0.01


2.60

2.69

0.35


3.40

3.51

0.45


3.80

3.93

0.50



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(a)

(b)

Page 20 of 25

(c)

Figure 8: Anticorrosion test: (a) Test Steel Specimen (Fresh); (b) Test Steel Specimen in Polyol base oil; (c) Test Steel Specimen in 2000 ppm additive in Polyol.

Conclusion We have demonstrated the first successful application of poultry waste chicken feathers in the development of multi functional lubricant additives. For this purpose, chicken feathers were first subjected to three step chemical functionalization by treating them with APTMS, after that 3,5di-tert-butyl-4-hydroxybenzaldehyde to give corresponding Schiff base which subsequently reacted with lauroyl chloride to give corresponding acylated (CF-APTMS-SB). FT-IR, TG and 1H NMR analyses confirmed the successful synthesis of the material. The developed material was evaluated as multifunctional lubricant additives in polyol and found to be a good antioxidant as it increases the oxidative stability of the polyol by 1.5 times. The additive was found to be a good anticorrosive; however performance as an antiwar additive was moderate and does not shows any antifriction property to the significant extent. We believe that the results reported in this work will open new avenues for developing cost effective, biodegradable and green additives for multipurpose applications for lubricating formulations in a sustainable manner.


Page 21 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


References 1.

Spikes, H. A. The history and mechanisms of ZDDP. Tribol. Lett. 2004, 17 (3), 469−489.

2.

Nicholls, M. A.; Do, T.; Norton, P. R.; Kasrai, M.; Bancroft, G. M. Review of the lubrication of metallic surfaces by zinc dialkyldithiophosphates. Tribol. Int. 2005, 38 (1), 15−39.

3.

Maleque, M. A.; Masjuki, H. H.; Sapuan, S. M. Vegetable-based biodegradable lubricating oil additives. Ind. Lubr. Tribol. 2003, 55 (3), 137−143.

4.

Ertugrul, D.; Filiz, K. Using of cottonseed oil as an environmentally accepted lubricant additive. Energy Sources 2004, 26, 611−625.

5.

Swami, K. K.; Prakash, S.; Sarin, R.; Tuli, D. K.; Bhatnagar, A. K. Development of ashless multifunctional additives from cashew nutshell liquid. Lubr. Sci. 2003, 15 (4), 361−368.

6.

Saga, L. C.; Rukke, E. O.; Liland, K. H.; Kirkhus, B.; Egelandsdal, B.; Karlsen, J.; Volden, J. Oxidative stability of polyunsaturated edible oils mixed with microcrystalline cellulose. J. Am. Oil Chem. Soc. 2011, 88 (12), 1883−1895.

7.

Karmakar, G.; Ghosh, P. Green Additives for Lubricating Oil. ACS Sustainable Chem. Eng., 2013, 1, 1364-1370.

8.

Pasanphan, W.; Buettner, G. R.; Chirachanchai, S. Chitosan gallate as a novel potential polysaccharide antioxidant: An EPR study. Carbohydr. Res. 2010, 345, 132−140.

9.

Mejia, L. I.; Luna, A. L.; Gimeno, M.; Shirai, K.; Barzana, E. Enzymatic grafting of gallate ester onto chitosan: evaluation of antioxidant and antibacterial activities. Int. J. Food Sci. Technol. 2013, 48, 2034-2041.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

10.

Page 22 of 25

Pasanphan, W.; Chirachanchai, S. Conjugation of gallic acid onto chitosan: An approach for green and water-based antioxidant. Carbohydr. Polym. 2008, 72, 169-177.

11.

Cho, Y. S.; Kim, S. K.; Ahn, C. B.; Je, J. Y. Preparation, characterization, and antioxidant properties of gallic acid-graftedchitosans. Carbohydr. Polym. 2011, 83, 16171622.

12.

Raj, K. S.; Aruna, K.; Alok, K. C.; Gananath, D. T.; Gajendra, M. B.;, Sandeep, S.; Dilip, K. A.; Neeraj, A. Use of an Acylated Chitosan Schiff Base as an Ecofriendly Multifunctional Biolubricant Additive. Ind. Eng. Chem. Res. 2014.

13.

(http://www.thepoultrysite.com/poultrynews/18275/new-solution-found-to-disposal-offeather-waste).

14.

Lederer, R. Integument, Feathers, and Molt Ornithology: The Science of Birds. http://www.ornithology.com.

15.

Sarvanan, K.; Dhurai B. Exploration on Amino acid Content and Morphological Structure in chicken feather Fiber. J. Text. Apparel Technol. Manage. 2012, 7, 1-6.

16.

Onifade, A. A.; Al-Sane, N. A.; Al-Musallam, A. A.; Al-Zarban, S. A review: Potentials for biotechnological applications of keratin-degrading microorganisms and their enzymes for nutritional improvement of feathers and other keratins as livestock feed resources. Bioresour. Technol. 1998, 66, 1–11.

17.

Arai, K. M.; Takahashi, R.; Yokote, Y.; Akahane, K. E. Amino-Acid Sequence of Feather Keratin from Fowl. J. Biochem. 1983, 132, 501–507.

18.

Ullah, A.; Vasanthan, T.; Bressler, D.; Elias, A. L.; Wu, J. Bioplastics from Feather Quill. Biomacromolecules 2011, 12, 3826–3832.


Page 23 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


19.

ASTM D 2272-11, Standard test method for oxidation stability of steam turbine oils by rotating pressure vessel. In: Annual Book of ASTM Standards, ASTM International: West Conshohocken, PA, 2011.

20.

ASTM D4172-94, Standard Test Method for Wear Preventive Characteristics of Lubricating Fluid (Four-Ball Method). In Annual Book of ASTM Standards, ASTM International: West Conshohocken, PA, 2010.

21.

Champion, F. A. (Ed.), Corrosion Testing Procedure, Champion & Hall, 1964, 66.

22.

Ailor, W. H. (Ed.) Handbook of Corrosion Testing and Evaluation, John Wiley Sci. Inc., 1971, 119.

23.

Sunil, K. A.; Arun, K. P.; Singh, S. P.; Pratima, R. S.; Manoj K. P.; Monika, D.; Bansi, D. M. Cholesterol biosensor based on N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane self-assembled monolayer. Analytical Biochem. 2007, 363, 210–218.

24.

Flaczyk, E.; Amarowicz, R.; Korczak, J. Antioxidant activity of protein hydrolyzates from by-products of the food industry. Journal of Food Lipids 2003, 10, 129-140.

25.

Stuart, H.; Carlene S.; Stephen S. Two Week Keratin-Based Protein Supplementation is Comparable in Gastrointestinal Handling to a Milk-Based Equivalent. J. Hum. Nutr. Food Sci. 2014, 2(5), 1047.

26.

Mukesh K. D. J.; Lavanya, S.; Priya, P. Immaculate, N. R.; Balakumaran, M. D.; Kalaichelvan, P. T. Production of Feather Protein Concentrate from Feathers by In vitro Enzymatic Treatment, its Biochemical Characterization and Antioxidant Nature. Middle East J. Sci. Res. 2012, 11 (7), 881-886.

27.

Rudnick, L. R. Lubricant additives: chemistry and applications, 2nd ed.; CRC Press, Taylor & Francis 2009.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

28.

Page 24 of 25

Wan, Y.; Liu, W. M.; Xue, Q. The tribological properties and action mechanism of Schiff base as a lubricating oil additive. Lubrication Science 1995, 7, 187-194.

29.

Agarwala, V. S.; Rajan, K. S.; Sen, P. K. Synthetic Lubricating Oil Greases Containing Metal, Chelates of Schiff Bases. US patent 5147567 1992.

30.

Gopi, D.; Govindaraju, K. M.; Kavitha, L. Investigation of triazole derived Schiff bases as corrosion inhibitors for mild steel in hydrochloric acid medium. Journal of Applied Electrochemistry 2010, 40, 1349-1356.

31.

Emregül, K. C.; Akay, A. A.; Atakol, O. Corrosion inhibition of steel with Schiff base compounds in 2M HCl. Mater. Chem. Phys. 2005, 93, 325.

32.

Shokry, H.; Yuasa, M.; Sekine, I.; Issa, R. M.; El-baradie, H. Y.; Gomma, G. K. Corrosion inhibition of mild steel by schiff base compounds in various aqueous solutions. Corrosion Science 1998, 40, 2173-2186.


Page 25 of 25

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


For Table of content entry

Poultry chicken feather derived biodegradable multifunctional additives for lubricating formulations P. Padma Latha, Raj Kumar Singh, Aruna Kukrety, Rakesh C. Saxena, Mukesh Bhatt and Suman L. Jain*

In order to add more economic value to chicken feather, a waste material of the poultry industry, it has been used to develop novel, low cost and high performance multi functional lubricant additives.


Poultry Chicken Feather Derived Biodegradable Multifunctional

Recommend Documents