Synthesis of New Bio-Based Solid Polymer Electrolyte Polyurethane-LiClO4 via Prepolymerization Method: Effect of NCO/OH Ratio on Their Chemical, Thermal Properties and Ionic Conductivity

Novel bio-based polymer electrolyte was synthesized with LiClO4 as the main source of charge carrier. Initially, polyurethane-LiClO4 polymer electrolytes were synthesized via prepolymerization method with different NCO/OH ratios and labelled them as PU1, PU2, PU3 and PU4. Fourier transform infrared (FTIR) analysis indicates the co-ordination between Li+ ion and polyurethane in PU1. Differential scanning calorimetry (DSC) analysis indicates PU1 has the highest glass transition temperature (Tg) corresponds to the most abundant urethane group which is the hard segment in PU1. Scanning electron microscopy (SEM) shows the good miscibility between lithium salt and the polymer. The study found that PU1 possessed the greatest ionic conductivity and the lowest activation energy, Ea. All the polyurethanes exhibited linear Arrhenius variations indicating ion transport via simple lithium ion hopping in polyurethane. This research proves the NCO content in polyurethane plays an important role in affecting the ionic conductivity of this polymer electrolyte.

Nonlinear Adaptive PID Control for a Semi-Batch Reactor Based On an RBF Network

Control of a semi-batch polymerization reactor using an adaptive radial basis function (RBF) neural network method is investigated in this paper. A neural network inverse model is used to estimate the valve position of the reactor; this method can identify the controlled system with the RBF neural network identifier. The weights of the adaptive PID controller are timely adjusted based on the identification of the plant and self-learning capability of RBFNN. A PID controller is used in the feedback control to regulate the actual temperature by compensating the neural network inverse model output. Simulation results show that the proposed control has strong adaptability, robustness and satisfactory control performance and the nonlinear system is achieved.

RBF Modelling and Optimization Control for Semi-Batch Reactors

This paper presents a neural network based model predictive control (MPC) strategy to control a strongly exothermic reaction with complicated nonlinear kinetics given by Chylla-Haase polymerization reactor that requires a very precise temperature control to maintain product uniformity. In the benchmark scenario, the operation of the reactor must be guaranteed under various disturbing influences, e.g., changing ambient temperatures or impurity of the monomer. Such a process usually controlled by conventional cascade control, it provides a robust operation, but often lacks accuracy concerning the required strict temperature tolerances. The predictive control strategy based on the RBF neural model is applied to solve this problem to achieve set-point tracking of the reactor temperature against disturbances. The result shows that the RBF based model predictive control gives reliable result in the presence of some disturbances and keeps the reactor temperature within a tight tolerance range around the desired reaction temperature.

Nanofibrous Ion Exchangers

The main goal of this study was to find simple and industrially applicable production of ion exchangers based on nanofibrous polystyrene matrix and characterization of prepared material. Starting polystyrene nanofibers were sulfonated and crosslinked under appropriate conditions at the same time by sulfuric acid. Strongly acidic cation exchanger was obtained in such a way. The polymer matrix was made from polystyrene nanofibers prepared by NanospiderTM technology. Various types postpolymerization reactions and other methods of crosslinking were studied. Greatly different behavior between nano- and microsize materials was observed. The final nanofibrous material was characterized and compared to common granular ion exchangers and available microfibrous ion exchangers. The sorption properties of nanofibrous ion exchangers were compared with the granular ion exchangers. For nanofibrous ion exchangers of comparable ion exchange capacity was observed considerably faster adsorption kinetics.

Functionalized PU Foam for Water Filtration

Polyurethane foam is functionalized with Sulfonic acid groups to remove lead ions (Pb2+) from drinking water through a cation exchange process. The synthesis is based on addition polymerization of the -NCO groups of an isocyanate with the –OH groups of a polyol to form the urethane. Toluene-diisocyanateis reacted with Polypropylene glycol to form a linear pre-polymer, which is further polymerized using a chain extender, N, N-bis(2-hydorxyethyl)-2-aminoethane-sulfonic acid (BES). BES acts as a functional group site to exchange Pb2+ ions. A set of experiments was designed to study the effect of various processing parameters on the performance of the synthesized foam. The maximum Pb2+ ion exchange capacity of the foam was found to be 47ppb/g from a 100ppb Pb2+ solution over a period of 60 minutes. A multistage batch filtration process increased the lead removal to 50-54ppb/3g of foam over a period of 90 minutes.

Preparation and Properties of Biopolymer from L-Lactide (LL) and ε-Caprolactone (CL)

Biopolymers have gained much attention as ecofriendly alternatives to petrochemical-based plastics because they are biodegradable and can be produced from renewable feedstocks. One class of biopolyester with many potential environmentally friendly applications is polylactic acid (PLA) and polycaprolactone (PCL). The PLA/PCL biodegradable copolyesters were synthesized by bulk ring-opening copolymerization of successively added Llactide (LL) and ε-caprolactone (CL) in the presence of toluene, using 1-hexanol as initiator and stannous octoate (Sn(Oct)2) as catalyst. Reaction temperature, reaction time and amount of catalyst were evaluated to obtain optimum reaction conditions. The results showed that the %conversion increased with increases in reaction temperature and reaction time, but after a critical amount of catalyst was reached the %conversion decreased. The yield of PLA/PCL biopolymer achieved 98.02% at the reaction temperature 160 °C, amount of catalyst 0.3 mol% and reaction time of 48 h. In addition, the thermal properties of the product were determined by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

Graft Copolymerization of Methyl Methacrylate onto Cellulose in Homogeneous Medium – Effect of Solvent and Initiator

Homogeneous graft copolymerization of methyl methacrylate (MMA) onto cellulose was carried out in N, N – dimethyl acetamide/LiCl (DMAc/LiCl) and dimethyl sulfoxide/ paraformaldehyde (DMSO/PF) solvent system taking ceric ammonium nitrate (CAN), benzoyl peroxide (BPO) and tin (II)-2-ethyl hexanoate [Sn(Oct)2] as initiators. Different grafting parameters like graft yield (GY), grafting efficiency (GE) and total conversion of monomer to polymer (TC) were evaluated at different reaction conditions of temperature, time, and variation of the amount of monomer and initiator. The viscosity average molecular weight of grafted PMMA and number of grafts per cellulose chain were also calculated. The products were characterized by FT-IR and 1H-NMR analyses and possible reaction mechanisms were deduced. Thermal degradation of the grafted products was also studied by thermo-gravimetric analysis (TG) and differential thermo-gravimetry (DTG).

Manufacturing Process of a Novel Biomass Composite Inspired from Cellular Structure of Wood

A novel biomass composite inspired from wood porous structure was manufactured by impregnating vinyl monomer into wood cellular structure under vacuum conditions, and initiating the monomer for in situ polymerization through a thermal treatment. The vacuum condition was studied, and the mechanical properties of the composite were also tested. SEM observation shows that polymer generated in the wood porous structure, and strongly interacted with wood matrix; and the polymer content increased with vacuum value increasing. FTIR indicates that polymer grafted onto wood matrix, resulting chemical complex between them. The rate of monomer loading increased with increasing vacuum value and time, accordance with rate of polymer loading. The compression strength and modulus of elasticity linearly increased with the increasing rate of polymer loading. Results indicate that the novel biomass composite possesses good mechanical properties capable of applying in the fields of construction, traffic and so forth.

Monte Carlo Simulation of Copolymer Heterogeneity in Atom Transfer Radical Copolymerization of Styrene and N-Butyl Acrylate

A high-performance Monte Carlo simulation, which simultaneously takes diffusion-controlled and chain-length-dependent bimolecular termination reactions into account, is developed to simulate atom transfer radical copolymerization of styrene and nbutyl acrylate. As expected, increasing initial feed fraction of styrene raises the fraction of styrene-styrene dyads (fAA) and reduces that of n-butyl acrylate dyads (fBB). The trend of variation in randomness parameter (fAB) during the copolymerization also varies significantly. Also, there is a drift in copolymer heterogeneity and the highest drift occurs in the initial feeds containing lower percentages of styrene, i.e. 20% and 5%.

Polyisoprene-coated Silica/Natural Rubber Composite

The commercial white tyres are usually used for forklifts in food and medicine industries. Conventionally, silica is used as reinforcement in the tyres. However, the adhesion between silica particles and rubber is remarkably poor. To improve the problem of adhesion and hence enhance wear resistance, modification of silica surface is one of the solutions. In this work, the natural rubber compound blending with polyisoprene-coated silica prepared by admicellar polymerization technique was studied to compare with the natural rubber compound of unmodified silica. The surface characterization of modified silica was also examined by SEM, FTIR, and TGA. The results show that polyisoprene-coated silica/natural rubber compound gave better overall mechanical properties, especially wear resistance with the improvement of the adhesion between silica and natural rubber matrix that can be seen in the SEM micrograph.

Study on the Atomic-Oxygen-Protection Film Preparation of Organic Silicon and Its Properties

Materials used on exterior spacecraft surfaces are subjected to many environmental threats which can cause degradation, atomic oxygen is one of the most threats. We prepared organic silicon atomic-oxygen-protection film using method of polymerization. This paper presented the effects on the film structure and its durability of the preparation processing, and analyzed the polymerization theory, the film structure and composition of the film. At last, we tested the film in our ground based atomic oxygen simulator, and indicated that the film worked well.

Effect of Transglutaminase Cross Linking on the Functional Properties as a Function of NaCl Concentration of Legumes Protein Isolate

The effect of cross linking of the protein isolates of three legumes with the microbial enzyme transglutaminase (EC 2.3.2.13) on the functional properties at different NaCl concentration was studied. The reduction in the total free amino groups (OD340) of the polymerized protein showed that TGase treatment cross-linking the protein subunit of each legume. The solubility of the protein polymer of each legume was greatly improved at high concentration of NaCl. At 1.2 M NaCl the solubility of the native legumes protein was significantly decreased but after polymerization slightly improved. Cross linked proteins were less turbid on heating to higher temperature as compared to native proteins and the temperature at which the protein turns turbid also increased in the polymerized proteins. The emulsifying and foaming properties of the protein polymer were greatly improved at all concentrations of NaCl for all legumes.

Generalized Predictive Control of Batch Polymerization Reactor

This paper describes the application of a model predictive controller to the problem of batch reactor temperature control. Although a great deal of work has been done to improve reactor throughput using batch sequence control, the control of the actual reactor temperature remains a difficult problem for many operators of these processes. Temperature control is important as many chemical reactions are sensitive to temperature for formation of desired products. This controller consist of two part (1) a nonlinear control method GLC (Global Linearizing Control) to create a linear model of system and (2) a Model predictive controller used to obtain optimal input control sequence. The temperature of reactor is tuned to track a predetermined temperature trajectory that applied to the batch reactor. To do so two input signals, electrical powers and the flow of coolant in the coil are used. Simulation results show that the proposed controller has a remarkable performance for tracking reference trajectory while at the same time it is robust against noise imposed to system output.

Synthesis and Characterization of Plasma Polymerized Thin Films Deposited from Benzene and Hexamethyldisiloxane using (PECVD) Method

Polymer-like organic thin films were deposited on both aluminum alloy type 6061 and glass substrates at room temperature by Plasma Enhanced Chemical Vapor Deposition (PECVD) methodusing benzene and hexamethyldisiloxane (HMDSO) as precursor materials. The surface and physical properties of plasma-polymerized organic thin films were investigated at different r.f. powers. The effects of benzene/argon ratio on the properties of plasma polymerized benzene films were also investigated. It is found that using benzene alone results in a non-coherent and non-adherent powdery deposited material. The chemical structure and surface properties of the asgrown plasma polymerized thin films were analyzed on glass substrates with FTIR and contact angle measurements. FTIR spectra of benzene deposited film indicated that the benzene rings are preserved when increasing benzene ratio and/or decreasing r.f. powers. FTIR spectra of HMDSO deposited films indicated an increase of the hydrogen concentration and a decrease of the oxygen concentration with the increase of r.f. power. The contact angle (θ) of the films prepared from benzene was found to increase by about 43% as benzene ratio increases from 10% to 20%. θ was then found to decrease to the original value (51°) when the benzene ratio increases to 100%. The contact angle, θ, for both benzene and HMDSO deposited films were found to increase with r.f. power. This signifies that the plasma polymerized organic films have substantially low surface energy as the r.f power increases. The corrosion resistance of aluminum alloy substrate both bare and covered with plasma polymerized thin films was carried out by potentiodynamic polarization measurements in standard 3.5 wt. % NaCl solution at room temperature. The results indicate that the benzene and HMDSO deposited films are suitable for protection of the aluminum substrate against corrosion. The changes in the processing parameters seem to have a strong influence on the film protective ability. Surface roughness of films deposited on aluminum alloy substrate was investigated using scanning electron microscopy (SEM). The SEM images indicate that the surface roughness of benzene deposited films increase with decreasing the benzene ratio. SEM images of benzene and HMDSO deposited films indicate that the surface roughness decreases with increasing r.f. power. Studying the above parameters indicate that the films produced are suitable for specific practical applications.

A Study on Polymer Coated Colour Pigments for Water-Based Ink

The pigments covered by film-forming polymers have opened a prospect to improve the quality of water-based printing inks. In this study such pigments were prepared by the initiated polymerization of styrene and methacrylate derivative monomers in the aqueous pigment dispersions. The formation of polymer films covering pigment cores depends on the polymerization time and the ratio of pigment to monomers. At the time of 4 hours and the ratio of 1/10 almost pigment particles are coated by the polymer. The formed polymer covers of pigments have the average thickness of 5.95 nm. The size increasing percentage of the coated particles after a week is 4.5 %, about fourteen-fold lower than of the original ones. The obtained results indicate that the coated pigments are improved dispersion stability in water medium along with a guarantee for the optical colour.

Design a Biodegradable Hydrogel for Drug Delivery System

In this article, we synthesize a novel chitosan -based superabsorbent hydrogel via graft copolymerization of mixtures acrylic acid (AA) and N-vinyl pyrollidon onto chitosan backbones. The polymerization reaction was carried out in an aqueous medium and in the presence of ammonium persulfate (APS) as an initiator and N,N'-methylene bisacrylamide (MBA) as a crosslinker.The hydrogel structures were confirmed by FTIR spectroscopy. The swelling behavior of these absorbent polymers was also investigated in various salt solutions. Results indicated that the swelling capacity decreased with an increase in the ionic strength of the swelling medium. Furthermore, the swelling of superabsorbing hydrogels was examined in solutions with pH values ranging between 1.0 and 13.0. It showed a reversible pH-responsive behavior at pHs 2.0 and 8.0. This on-off switching behavior makes the synthesized hydrogels as an excellent candidate for controlled delivery of bioactive agents.

Novel D- glucose Based Glycomonomers Synthesis and Characterization

In the last decade, carbohydrates have attracted great attention as renewable resources for the chemical industry. Carbohydrates are abundantly found in nature in the form of monomers, oligomers and polymers, or as components of biopolymers and other naturally occurring substances. As natural products, they play important roles in conferring certain physical, chemical, and biological properties to their carrier molecules.The synthesis of this particular carbohydrate glycomonomer is part of our work to obtain biodegradable polymers. Our current paper describes the synthesis and characterization of a novel carbohydrate glycomonomer starting from D-glucose, in several synthesis steps, that involve the protection/deprotection of the D-glucose ring via acetylation, tritylation, then selective deprotection of the aromaticaliphatic protective group, in order to obtain 1,2,3,4-tetra-O-acetyl- 6-O-allyl-β-D-glucopyranose. The glycomonomer was then obtained by the allylation in drastic conditions of 1,2,3,4-tetra-O-acetyl-6-Oallyl- β-D-glucopyranose with allylic alcohol in the presence of stannic chloride, in methylene chloride, at room temperature. The proposed structure of the glycomonomer, 2,3,4-tri-O-acetyl-1,6-di- O-allyl-β-D-glucopyranose, was confirmed by FTIR, NMR and HPLC-MS spectrometry. This glycomonomer will be further submitted to copolymerization with certain acrylic or methacrylic monomers in order to obtain competitive plastic materials for applications in the biomedical field.

Surface Charge Based Rapid Method for Detection of Microbial Contamination in Drinking Water and Food Products

Microbial contamination, most of which are fecal born in drinking water and food industry is a serious threat to humans. Escherichia coli is one of the most common and prevalent among them. We have developed a sensor for rapid and an early detection of contaminants, taking E.coli as a threat indicator organism. The sensor is based on co-polymerizations of aniline and formaldehyde in form of thin film over glass surface using the vacuum deposition technique. The particular doping combination of thin film with Fe-Al and Fe-Cu in different concentrations changes its non conducting properties to p- type semi conductor. This property is exploited to detect the different contaminants, believed to have the different surface charge. It was found through experiments that different microbes at same OD (0.600 at 600 nm) have different conductivity in solution. Also the doping concentration is found to be specific for attracting microbes on the basis of surface charge. This is a simple, cost effective and quick detection method which not only decreases the measurement time but also gives early warnings for highly contaminated samples.

Compressive Strength and Interfacial Transition Zone Characteristic of Geopolymer Concrete with Different Cast In-Situ Curing Conditions

The compressive strength development through polymerization process of alkaline solution and fly ash blended with Microwave Incinerated Rice Husk Ash (MIRHA) is described in this paper. Three curing conditions, which are hot gunny curing, ambient curing, and external humidity curing are investigated to obtain the suitable curing condition for cast in situ provision. Fly ash was blended with MIRHA at 3%, 5%, and 7% to identify the effect of blended mixes to the compressive strength and microstructure properties of geopolymer concrete. Compressive strength results indicated an improvement in the strength development with external humidity curing concrete samples compared to hot gunny curing and ambient curing. Blended mixes also presented better performance than control mixes. Improvement of interfacial transition zone (ITZ) and micro structure in external humidity concrete samples were also identified compared to hot gunny and ambient curing.

Optical Limiting Characteristics of Core-Shell Nanoparticles

TiO2 nanoparticles were synthesized by hydrothermal method at 180°C from TiOSO4 aqueous solution with1m/l concentration. The obtained products were coated with silica by means of a seeded polymerization technique for a coating time of 1440 minutes to obtain well defined TiO2@SiO2 core-shell structure. The uncoated and coated nanoparticles were characterized by using X-Ray diffraction technique (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) to study their physico-chemical properties. Evidence from XRD and FTIR results show that SiO2 is homogenously coated on the surface of titania particles. FTIR spectra show that there exists an interaction between TiO2 and SiO2 and results in the formation of Ti-O-Si chemical bonds at the interface of TiO2 particles and SiO2 coating layer. The non linear optical limiting properties of TiO2 and TiO2@SiO2 nanoparticles dispersed in ethylene glycol were studied at 532nm using 5ns Nd:YAG laser pulses. Three-photon absorption is responsible for optical limiting characteristics in these nanoparticles and it is seen that the optical nonlinearity is enhanced in core-shell structures when compared with single counterparts. This effective three-photon type absorption at this wavelength, is of potential application in fabricating optical limiting devices.