Lubricant Degradation and Related Wear of a Steel Pin in Lubricated Sliding Against a Steel Disc

In lubricated sliding contacts, components wear out and the lubricating oil ages with time. The present work explores the interactive influence between lubricant aging and component wear. The flat face of a steel pin is slid against a rotating steel disk under near isothermal conditions while the contact is immersed in a reservoir of lubricant (hexadecane). The chemical changes in the oil with time are measured by vibrational spectroscopy and gas chromatography. The corresponding chemistry of the pin surface is recorded using X-ray photoelectron spectroscopy while the morphology of the worn pins; surface and subsurface, are observed using a combination of focused ion beam milling and scanning electron 5 microscopy. When compared to thermal auto-oxidation of the lubricant alone, steel on steel friction and wear are found to accentuate the decomposition of oil and to reduce the beneficial impact of antioxidants. The catalytic action of nascent iron, an outcome of pin wear and disk wear, is shown to contribute to this detrimental effect. Over long periods of sliding, the decomposition products of lubricant aging on their own, as well as in conjunction with their products of reaction with iron, generate a thick tribofilm that is highly protective in terms of friction and wear.

Kinetics of catalytic degradation of polycarbonate in benzene

The degradation kinetics of polycarbonate [poly(bisphenol A carbonate)] in benzene catalyzed by commercial (rutile) TiO2 (BET surface area = 11 m(2)/g), anatase TiO2 (156 m(2)/g), and 1 atom % Pt/TiO2 (111 m2/g), prepared by the solution combustion technique, was investigated at various temperatures (230-280 degreesC) and 50 atm. The time evolution of the molecular weight distribution (MWD) was determined by gel permeation chromatography (GPC) and modeled with continuous distribution kinetics to obtain the degradation rate coefficients. The rate coefficients for the catalytic degradation of polycarbonate increased by factors of 20, 3.5, and 1.3 compared to the rate coefficients for thermal degradation when catalyzed by nanosized TiO2 anatase, Pt/TiO2 anatase, and commercial TiO2, respectively, at 280 degreesC. The increased catalytic activity of combustion for synthesized TiO2 and 1% Pt/TiO2 might be due to the increased acidity and BET surface area. The activation energies, determined from the temperature dependencies of the rate coefficients, were 16.3, 21.5, and 39.1 kcal/mol for commercial TiO2, combustion-synthesized Pt/TiO2, and anatase TiO2, respectively.

Understanding the building-up process of three dimensional open-framework metal phosphates: Acid degradation of the 3D structures to lower dimensional structures

Acid degradation of 3D zinc phosphates primarily yields a one-dimensional ladder compound, an observation that is significant considering that the latter forms 3D structures on heating in water.

Synthesis, characterization, degradation of biodegradable castor oil based polyesters

A new family of castor oil based biodegradable polyesters was synthesized by catalyst free melt condensation reaction between two different diacids and castor oil with D-mannitol. The polymers synthesized were characterized by NMR spectroscopy, FF-IR and the thermal properties were analysed by DSC. The results of DSC show that the polymer is rubbery in physiological conditions. The contact angle measurement and hydration test results indicate that the surface of the polymer is hydrophilic. The mechanical properties, evaluated in the tensile mode, shows that the polymer has characteristics of a soft material. In vitro degradation of polymer in PBS solution carried out at physiological conditions indicates that the degradation goes to completion within 21 days and it was also found that the rate of degradation can be tuned by varying the curing conditions. (C) 2011 Elsevier Ltd. All rights reserved.

Synthesis, Characterization, and Degradation of Biodegradable Poly(mannitol citric dicarboxylate) Copolyesters

Three groups of poly(mannitol citric dicarboxylate) [p(MCD)] copolyesters were synthesized by catalyst-free melt condensation of mannitol with acids. The resulting copolyesters were designated as poly(mannitol citric succinate) [p(MCSu)], poly(mannitol citric adipate) [p(MCA)], poly(mannitol citric sebacate) [p(MCS)]. The polymers were characterized by FTIR, (1)H NMR, and DSC analysis. The synthesized p(MCD) polymers exhibit glass transition temperatures ranging from 16.5 to 58.58 degrees C. The mechanical, degradation properties, and the drug-releasing characteristics of these polymers were investigated. It was observed that the mechanical properties of the p(MCD) polymers cover a wide range with Young's modulus of the polymer varying from 12.25 to 660 MPa. Hydrolytic degradation of all polymers was investigated by incubating polymer discs in PBS and the hydrolytic degradation of p(MCD) polymers followed the order, p(MCSu) > p(MCA) > p(MCS). This was attributed to the number of -CH(2)(units in the dicarboxylic monomers. The release of model drug compounds from the p(MCD) polymer discs was also studied. POLYM. ENG. SCI., 51:2035-2043, 2011. (C) 2011 Society of Plastics Engineers

Ultrasonic degradation of butadiene, styrene and their copolymers

Ultrasonic degradation of commercially important polymers, styrene-butadiene (SBR) rubber, acrylonitrile-butadiene (NBR) rubber, styrene-acrylonitrile (SAN), polybutadiene rubber and polystyrene were investigated. The molecular weight distributions were measured using gel permeation chromatography (GPC). A model based on continuous distribution kinetics approach was used to study the time evolution of molecular weight distribution for these polymers during degradation. The effect of solvent properties and ultrasound intensity on the degradation of SBR rubber was investigated using different pure solvents and mixed solvents of varying volatility and different ultrasonic intensities. (C) 2011 Elsevier B.V. All rights reserved.

Photocatalytic degradation of dimethoate using LbL fabricated TiO2/polymer hybrid films

Degradation of dimethoate under UV irradiation using TiO2/polymer films prepared by the layer-by-layer (LbL) method was investigated. The thin films were fabricated on glass slides and the surface morphology and roughness of the thin films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effect of lamp intensity, catalyst loading in the layers, number of bilayers, pH and initial dimethoate concentration on the degradation of dimethoate was systematically studied. The degradation was monitored using high performance liquid chromatography (HPLC) analysis and total organic carbon (TOC) measurements as a function of irradiation time, to see the change in concentration of dimethoate and mineralization, respectively. Complete degradation of dimethoate was achieved under TiO2 optimum loading of 4 g/L at an UV irradiation time of 180 min. Increase in the lamp intensity, catalyst loading and number of bilayers increased the rate of degradation. At a pH of 4.62, complete degradation of dimethoate was observed. The degradation efficiency decreased with increase in initial dimethoate concentration. The degradation byproducts were analyzed and confirmed by gas chromatography-mass spectra (GC-MS). Toxicity of the irradiated samples was measured using the luminescence of bacteria Vibrio fischeri after 30 min of incubation and the results showed more toxicity than the parent compound. Catalyst reusability studies revealed that the fabricated thin films could be repeatedly used for up to ten times without affecting the photocatalytic activity of the films. The findings of the present study are very useful for the treatment of wastewaters contaminated with pesticides. (C) 2011 Elsevier B.V. All rights reserved.

Photo, thermal, and ultrasonic degradation of EGDMA-crosslinked poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Superabsorbent polymers (SAPs) based on acrylic acid (AA), sodium acrylate (SA), and acrylamide (AM) were synthesized by inverse suspension polymerization using ethylene glycol dimethacrylate as the crosslinking agent. The equilibrium swelling capacities and the rates of swelling of SAPs varied with the AM content and followed first-order kinetics. The photodegradation of SAPs in their equilibrium swollen state was carried out by monitoring their swelling capacity and the residual weight fraction. The SAPs degraded in two stages, wherein the swelling capacity increased to a maximum and then subsequently decreased. Thermogravimetric analysis of the SAPs indicated that the copolymeric superabsorbents had intermediate thermal stability between the homopolymeric superabsorbents. The activation energies of SAPs with 0, 20, and 100 mol % AM content were determined by Kissinger method and were found to be 299, 248, and 147 kJ mol-1, respectively. The ultrasonic degradation of the superabsorbents was carried out in their equilibrium swollen state, and the change in the viscosity with ultrasonication time was used to quantify the degradation. The ultrasonic degradation of AA/SA superabsorbent was also investigated at various ultrasound intensities. The degradation rate coefficients were found to increase with the intensity of ultrasound. The ultrasonic degradation of AA/SA/AM (20% AM) was also carried out, and degradation rate was found to be more than that of the AA/SA superabsorbent. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Remarkable photocytotoxicity of curcumin in HeLa cells in visible light and arresting its degradation on oxovanadium(IV) complex formation

Curcumin (Hcur) as a cellular imaging and PDT agent shows remarkable photocytotoxicity in HeLa cells in visible light of 400-700 nm giving IC50 = 8.2 +/- 0.2 mu M and its degradation is arrested on formation of photocytotoxic dipyridophenazine (dppz) complex VO(cur)(dppz)Cl] (IC50 = 3.3 +/- 0.4 mu M), while both are less toxic in the dark.

Thermal degradation kinetics of poly(trimethylol propane triacrylate)/poly(hexane diol diacrylate) interpenetrating polymer network

Interpenetrating polymer networks (IPNs) of trimethylol propane triacrylate (TMPTA) and 1,6-hexane diol diacrylate (HDDA) at different weight ratios were synthesized. Temperature modulated differential scanning calorimetry (TMDSC) was used to determine whether the formation resulted in a copolymer or interpenetrating polymer network (IPN). These polymers are used as binders for microstereolithography (MSL) based ceramic microfabrication. The kinetics of thermal degradation of these polymers are important to optimize the debinding process for fabricating 3D shaped ceramic objects by MSL based rapid prototyping technique. Therefore, thermal and thermo-oxidative degradation of these IPNs have been studied by dynamic and isothermal thermogravimetry (TGA). Non-isothermal model-free kinetic methods have been adopted (isoconversional differential and KAS) to calculate the apparent activation energy (E a) as a function of conversion (α) in N 2 and air. The degradation of these polymers in N 2 atmosphere occurs via two mechanisms. Chain end scission plays a dominant role at lower temperature while the kinetics is governed by random chain scission at higher temperature. Oxidative degradation shows multiple degradation steps having higher activation energy than in N 2. Isothermal degradation was also carried out to predict the reaction model which is found to be decelerating. It was shown that the degradation of PTMPTA follows a contracting sphere reaction model in N 2. However, as the HDDA content increases in the IPNs, the degradation reaction follows Avrami-Erofeev model and diffusion governed mechanisms. The intermediate IPN compositions show both type of mechanism. Based on the above study, debinding strategy for MSL based microfabricated ceramic structure has been proposed. © 2012 Elsevier B.V.

Photo and Thermal Degradation of a Cationic Superabsorbent Polymer

A cationic superabsorbent polymer (SAP) was synthesized by carrying out the polymerization of 2-(methacryloyloxy)ethyl] trimethyl ammonium chloride) with N,N'-methylenebisacrylamide as the cross-linking agent. The SAP was subjected to degradation in dry and the equilibrium swollen state by thermo gravimetric analysis and exposure to ultraviolet radiation, respectively. The photodegradation was monitored by measuring changes in the swelling capacity and the dry weight of the SAP. The thermal degradation of the SAP occurred in three stages after the initial removal of moisture and the activation energies of the decomposition were determined.

Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

Reversible addition-fragmentation chain transfer polymerization at 70 A degrees C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by H-1 NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r (NIPAM) = 0.838 and r (DMA) = 1.105, respectively, by the extended Kelen-Tudos method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

Synthesis, characterization and thermal degradation of dual temperature- and pH-sensitive RAFT-made copolymers of N,N-(dimethylamino)ethyl methacrylate and methyl methacrylate

Poly{(N,N-(dimethylamino)ethyl methacrylate]-co-(methyl methacrylate)} copolymers of various compositions were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization at 70 degrees C in N,N-dimethylformamide. The polymer molecular weights and molecular weight distributions were obtained from size exclusion chromatography, and they indicated the controlled nature of the RAFT polymerizations; the polydispersity indices are in the range 1.11.3. The reactivity ratios of N,N-(dimethylamino)ethyl methacrylate (DMAEMA) and methyl methacrylate (MMA) (rDMAEMA = 0.925 and rMMA = 0.854) were computed by the extended KelenTudos method at high conversions, using compositions obtained from 1H NMR. The pH- and temperature-sensitive behaviour were studied in aqueous solution to confirm dual responsiveness of these copolymers. The thermal properties of the copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The kinetics of thermal degradation were determined by Friedmann and Chang techniques to evaluate various parameters such as the activation energy, the order and the frequency factor. (c) 2012 Society of Chemical Industry