Search results for: crosslinking density

Authors: A. E. Delgado, W. Aperador

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This study evaluated the incidence of concentrated natural fibre, as well as the effects of adding a crosslinking agent on the torque when those components are mixed with low density polyethylene (LDPE). The natural fibre has a particle size of between 0.8-1.2mm and a moisture content of 0.17%. An internal mixer was used to measure the torque required to mix the polymer with the fibre. The effect of the fibre content and crosslinking agent on the torque was also determined. A change was observed in the morphology of the mixes using SEM differential scanning microscopy.

Keywords: WPC, DCP, LDPE, natural fibre, torque

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Authors: Jae Seo Lee, Il Keun Kwon

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In the last decades, keratin-based on natural extracts has considerably increased interest as a skin tissue regeneration. However, most parts of keratin had a limitation to 3D scaffolds due to low biological affinity and general low mechanical properties. To create a 3D structure, a facile bioink was designed with a photocurable crosslinking stage system using natural polymer-based human keratin. Keratin-based bioink enables the crosslinking more quickly through two types of photo and ion crosslinking for module engineering assembly. Rheological results showed that keratin-based bioink with high concentration possessed superior mechanical rigidity for 3D bioprinting. Different 3D geometrically constructs were successfully fabricated with optimal bioprinting parameters through the 3D printer with X-Y-Z controlled UV laser system. The presented study has offered a distinct advantage for 3D printing of keratin-based hydrogel into 3D complex-shaped biomimetic constructs. Thus, keratin-based bioink opens up new avenues in bioprinting to directly substitute tissue or organs.

Keywords: human keratin, hydrogel, ion-crosslinking, 3D bioprinting

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Authors: Sperisa Distantina, Fadilah, Mujtahid Kaavessina

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Crosslinked konjac glucomannan and kappa carrageenan film were prepared by chemical crosslinking using glutaraldehyde (GA) as the crosslinking agent. The effect crosslinking on the swelling degree was investigated. Konjac glucomanan and its mixture with kappa carragenan film was immersed in GA solution and then thermally cured. The obtained crosslinked film was washed and soaked in the ethanol to remove the unreacted GA. The obtained film was air dried at room temperature to a constant weight. The infrared spectra and the value of swelling degree of obtained crosslinked film showed that glucomannan and kappa carrageenan was able to be crosslinked using glutaraldehyde by film immersion and curing method without catalyst. The crosslinked films were found to be pH sensitive, indicating a potential to be used in drug delivery polymer system.

Keywords: crosslinking, glucomannan, carrageenan, swelling

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Authors: Shiraz M. Mammadov, Elvin M. Aliyev, Adil A. Garibov

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The role of the disulfochloride benzene in unsaturated rubbers (SKIN, SKN-26) which is in the systems of SKIN+disulfochloride benzene and SKN-26+disulfochloride benzene was studied by the radiation exposure. By the usage of physical, chemical and spectral methods the changes in the molecular structure of the rubber were shown after irradiation by y-rays at 300 kGy. The outputs and the emergence of the crosslinking in the elastomers for each system depending on absorbed dose were defined. It is suggested that the mechanism of radiation occurs by the heterogeneous transformation of elastomers in the presence of disulfochloride benzene.

Keywords: acrylonitrile-butadiene rubber, crosslinking, polyfunctional monomers, radiation, sensitizier, vulcanization

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Authors: Reyhan Özdoğan, Mithat Çelebi, Özgür Ceylan, Mehmet Arif Kaya

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Super absorbent polymers (SAPs) are defined as materials that can absorb huge amount of water or aqueous solution in comparison to their own mass and retain in their lightly cross-linked structure. SAPs were produced from water soluble monomers via polymerization subsequently controlled crosslinking. SAPs are generally used for water absorbing applications such as baby diapers, patient or elder pads and other hygienic product industries. Crosslinking density (CD) of SAP structure is an essential factor for water absortion capacity (WAC). Low internal CD leads to high WAC values and vice versa. However, SAPs have low CD and high swelling capacities and tend to disintegrate when pressure is applied upon them, so SAPs under load cannot absorb liquids effectively. In order to prevent this undesired situation and to obtain suitable SAP structures having high swelling capacity and ability to work under load, surface crosslinking can be the answer. In industry, these superabsorbent gels are mostly produced via solution polymerization and then they need to be dried, grinded, sized, post polymerized and finally surface croslinked (involves spraying of a crosslinking solution onto dried and grinded SAP particles, and then curing by heat). It can easily be seen that these steps are time consuming and should be handled carefully for the desired final product. If we could synthesize desired final SAPs using less processes it will help reducing time and production costs which are very important for any industries. In this study, synthesis of SAPs were achieved successfully by inverse suspension (Pickering type) polymerization and subsequently in-situ surface cross-linking via using proper surfactants in high boiling point solvents. Our one-pot synthesis of surface cross-linked SAPs invovles only one-step for preparation, thus it can be said that this technique exhibits more preferable characteristic for the industry in comparison to conventional methods due to its one-step easy process. Effects of different surface crosslinking agents onto properties of poly(acrylic acid-co-sodium acrylate) based SAPs are investigated. Surface crosslink degrees are evaluated by swelling under load (SUL) test. It was determined water absorption capacities of obtained SAPs decrease with the increasing surface crosslink density while their mechanic properties are improved.

Keywords: inverse suspension polymerization, polyacrylic acid, super absorbent polymers (SAPs), surface crosslinking, sodium polyacrylate

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Authors: G. Roshan Deen, J. S. Pedersen

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Temperature-responsive poly(N-isopropyl acrylamide) PNIPAM microgels crosslinked with a new hydrophobic chemical crosslinker was prepared by surfactant-mediated precipitation emulsion polymerization. The temperature-responsive property of the microgel and the influence of the crosslinker on the swelling behaviour was studied systematically by light scattering and small-angle X-ray scattering (SAXS). The radius of gyration (Rg) and the hydrodynamic radius (Rh) of the microgels decreased with increase in temperature due to the volume phase transition from a swollen to a collapsed state. The ratio of Rg/Rh below the transition temperature was lower than that of hard-spheres due to the lower crosslinking density of the microgels. The SAXS data was analysed by a model in which the microgels were modelled as core-shell particles with a graded interface. The model at intermediate temperatures included a central core and a more diffuse outer layer describing pending polymer chains with a low crosslinking density. In the fully swollen state, the microgels were modelled with a single component with a broad graded surface. In the collapsed state they were modelled as homogeneous and relatively compact particles. The polymer volume fraction inside the microgel was also derived based on the model and was found to increase with increase in temperature as a result of collapse of the microgel to compact particles. The polymer volume fraction in the core of the microgel in the collapsed state was about 60% which is higher than that of similar microgels crosslinked with hydrophilic and flexible cross-linkers.

Keywords: microgels, SAXS, hydrophobic crosslinker, light scattering

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Authors: D. Zujur, J. Moret, D. Rodriguez, L. Cruz, J. Lira, L. Gil, E. Dominguez, J. F. Alvarez-Barreto

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In this work, chitosan (CH) has been used to produce a novel coating for Ti6Al4V, the most widely used alloy in orthopedic implants, so as to improve the biological tissue response at the metallic surface. The Ti6Al4V surface was sandblasted with alumina particles and observed by SEM. Chitosan was chemically modified, via crodiimide chemistry, with lactobionic and 4-azidebenzoic acid to make it soluble at physiological pH and photo-crosslinkable, respectively. The reaction was verified by FTIR, NMR, and UV/vis spectroscopy. Ti6Al4V surfaces were coated with solutions of the modified CH and exposed to UV light, causing the polymer crosslinking, and formation of a hydrogel on the surface. The crosslinking reaction was monitored by FTIR at different exposure times. Coating morphology was observed by SEM. The coating´s cytocompatibility was determined in vitro through the culture of rat bone marrow´s mesenchymal stem cells, using an MTT assay. The results show that the developed coating is cytocompatible, easy to apply and could be used for further studies in the encapsulation of bioactive molecules to improve osteogenic potential at the tissue-implant interface.

Keywords: chitosan, photo-crosslinking, Ti6Al4V, bioactive coating, hydrogel

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Authors: M. D. Stelescu, E. Manaila, G. Craciun, D. Ighigeanu

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The goal of the paper is to present the results regarding the influence of the irradiation dose and amount of multifunctional monomer trimethylol-propane trimethacrylate (TMPT) on ethylene-propylene-diene terpolymer rubber (EPDM) mixtures irradiated in electron beam. Blends, molded on an electrically heated laboratory roller mill and compressed in an electrically heated hydraulic press, were irradiated using the ALID 7 of 5.5 MeV linear accelerator in the dose range of 22.6 kGy to 56.5 kGy in atmospheric conditions and at room temperature of 25 °C. The share of cross-linking and degradation reactions was evaluated by means of sol-gel analysis, cross-linking density measurements, FTIR studies and Charlesby-Pinner parameter (p₀/q₀) calculations. The blends containing different concentrations of TMPT (3 phr and 9 phr) and irradiated with doses in the mentioned range have present the increasing of gel content and cross-linking density. Modified and new bands in FTIR spectra have appeared, because of both cross-linking and chain scission reactions.

Keywords: electron beam irradiation, EPDM rubber, crosslinking density, gel fraction

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Authors: Sahin Yakut, H. Kemal Ulutas, Deniz Deger

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Plasma Assisted Physical Vapor Deposition (PAPVD) method used to produce Poly(ethylene oxide) (pPEO) thin films. Depositions were progressed at various plasma discharge powers as 0, 2, 5 and 30 W for pPEO at 500nm film thicknesses. The capacitance and dielectric dissipation of the thin films were measured at 0,1-107 Hz frequency range and 173-353 K temperature range by an impedance analyzer. Then, alternative conductivity (σac) and activation energies were derived from capacitance and dielectric dissipation. σac of conventional PEO (PEO precursor) was measured to determine the effect of plasma discharge. Differences were observed between the alternative conductivity of PEO’s and pPEO’s depending on plasma discharge power. By this purpose, structural characterization techniques such as Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) were applied on pPEO thin films. Structural analysis showed that density of crosslinking is plasma power dependent. The crosslinking density increases with increasing plasma discharge power and this increase is displayed as increasing dynamic glass transition temperatures at DSC results. Also, shifting of frequencies of some type of bond vibrations, belonging to bond vibrations produced after fragmentation because of plasma discharge, were observed at FTIR results. The dynamic glass transition temperatures obtained from alternative conductivity results for pPEO consistent with the results of DSC. Activation energies exhibit Arrhenius behavior. Activation energies decrease with increasing plasma discharge power. This behavior supports the suggestion expressing that long polymer chains and long oligomers are fragmented into smaller oligomers or radicals.

Keywords: activation energy, dielectric spectroscopy, organic thin films, plasma polymer

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Authors: Nurudeen Afolami Ayeni, Kasali Bello

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Methylolmelamine with increasing degree of methylol substitution and the phosphates derivatives were used to resinate cotton fabric (CF). The resination was carried out at different curing time and curing temperature. Generally, the results show a reduction in the flame propagation rate of the treated fabrics compared to the untreated cotton fabric (CF). While the flame retardancy of methylolmelamine-treated fibre could be attributed to the degree of crosslinking of fibre-resin network which promotes stability, the methylolmelamine phosphate-treated fabrics show better retardancy due to the intumescences action of the phosphate resin upon decomposition in the resin – fabric network.

Keywords: cotton fabric, flame retardant, methylolmelamine, crosslinking, resination

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Authors: Natarajan Ramasamy, Gurulingamurthy Haralur, Ramesh Nivarthu, Nikhil Kumar Singha

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Elastomers are polymeric materials with varied backbone architectures ranging from linear to dendrimeric structures and wide varieties of monomeric repeat units. These elastomers show strongly viscous and weakly elastic when it is not cross-linked. But when crosslinked, based on the extent the properties of these elastomers can range from highly flexible to highly stiff nature. Lightly cross-linked systems are well studied and reported. Understanding the nature of highly cross-linked rubber based upon chemical structure and architecture is critical for varieties of applications. One of the critical parameters is cross-link density. In the current work, we have studied the highly cross-linked state of linear, lightly branched to star-shaped branched elastomers and determined the cross-linked density by using different models. Change in hardness, shift in Tg, change in modulus and swelling behavior were measured experimentally as a function of the extent of curing. These properties were analyzed using varied models to determine cross-link density. We used hardness measurements to examine cure time. Hardness to the extent of curing relationship is determined. It is well known that micromechanical transitions like Tg and storage modulus are related to the extent of crosslinking. The Tg of the elastomer in different crosslinked state was determined by DMA, and based on plateau modulus the crosslink density is estimated by using Nielsen’s model. Usually for lightly crosslinked systems, based on equilibrium swelling ratio in solvent the cross link density is estimated by using Flory–Rhener model. When it comes to highly crosslinked system, Flory-Rhener model is not valid because of smaller chain length. So models based on the assumption of polymer as a Non-Gaussian chain like 1) Helmis–Heinrich–Straube (HHS) model, 2) Gloria M.gusler and Yoram Cohen Model, 3) Barbara D. Barr-Howell and Nikolaos A. Peppas model is used for estimating crosslink density. In this work, correction factors are determined to the existing models and based upon it structure-property relationship of highly crosslinked elastomers was studied.

Keywords: dynamic mechanical analysis, glass transition temperature, parts per hundred grams of rubber, crosslink density, number of networks per unit volume of elastomer

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Authors: S. B. Provost, Hossein Zareamoghaddam

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A univariate density approximation technique whereby the derivative of the logarithm of a density function is assumed to be expressible as a rational function is introduced. This approach which extends Pearson’s curve system is solely based on the moments of a distribution up to a determinable order. Upon solving a system of linear equations, the coefficients of the polynomial ratio can readily be identified. An explicit solution to the integral representation of the resulting density approximant is then obtained. It will be explained that when utilised in conjunction with sample moments, this methodology lends itself to the modelling of ‘big data’. Applications to sets of univariate and bivariate observations will be presented.

Keywords: density estimation, log-density, moments, Pearson's curve system

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Authors: Nilay K. Doshi

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A theoretical probe describing the excited energy states of the electron density surrounding a nanoparticle (NP) is presented. An electromagnetic (EM) wave interacts with a NP much smaller than the incident wavelength. The plasmon that oscillates locally around the NP comprises of excited conduction electrons. The system is based on the Jellium model of a cluster of metal atoms. Hohenberg-Kohn (HK) equations and the variational Kohn-Sham (SK) scheme have been used to obtain the NP electron density in the ground state. Furthermore, a time-dependent density functional (TDDFT) theory is used to treat the excited states in a density functional theory (DFT) framework. The non-interacting fermionic kinetic energy is shown to be a functional of the electron density. The time dependent potential is written as the sum of the nucleic potential and the incoming EM field. This view of the quantum oscillation of the electron density is a part of the localized surface plasmon resonance.

Keywords: electron density, energy, electromagnetic, DFT, TDDFT, plasmon, resonance

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Authors: Ko-Shao Chen, Yun Tsao, Chia-Hsuan Tsen, Chien-Chung Chen, Shu-Chuan Liao

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Electrospun microtube array membranes (MTAMs) made of PLLA (poly-L-lactic acid) have wide potential applications in tissue engineering. However, their surface hydrophobicity and poor biocompatability have limited their further usage. In this study, the surface of PLLA MTAMs were made hydrophilic by introducing extra functional groups, such as peroxide, via an acetic acid plasma (AAP). UV-graft polymerization of acrylic acid (G-AAc) was then used to produce carboxyl group on MTAMs surface, which bonded covalently with chitosan through EDC / NHS crosslinking agents. To evaluate the effects of the surface modification on PLLA MTAMs, water contact angle (WCA) measurement and cell compatibility tests were carried out. We found that AAP treated electrospun PLLA MTAMs grafted with AAc and, finally, with chitosan immobilized via crosslinking agent, exhibited improved hydrophilic and cell compatibility.

Keywords: plasma, EDC/NHS, UV grafting, Chitosan, microtube array membrane (MTAMs)

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Authors: Andi Syahputra, R. H. Jatmiko, D. R. Hizbaron

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Land surface temperature (LST) in an area is influenced by conditions of vegetation density, building density, and the number of inhabitants who live in the area. Medan City is one of the largest cities in Indonesia, with a high rate of change from vegetation to developed land. This study aims to identify the relationship between the percentage of building density and land surface temperature in Medan City. Pixel image analysis method is carried out to obtain the value of building density in pixel images of Landsat 8 images with the help of WorldView-2 satellite imagery. The results showed the highest land surface temperature in 2018 of 35, 4°C was found in Medan Perjuangan District, and the lowest was 22.5°C in Medan Belawan District. Building density samples with a density level of 889.17 m were also found in Medan Perjuangan District, while the lowest building density sample was found in Medan Timur District. Linear regression analysis of the effect of building density with land surface temperature obtained a correlation (R) was 0.64, and a coefficient of determination (R²) was 0.411 and modeling of building density based on the LST has a correlation (R), and a coefficient of determination (R²) was 0.72 with The RMSE obtained 0.853.

Keywords: land surface temperature, Landsat, imagery, building density, vegetation, density

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Authors: Peter O. Osifo, Hein W. J. P. Neomagus, Hein V. D. Merwe

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Chitosan materials from different sources of raw materials were characterized in order to determine optimal preparation conditions and parameters for membrane production. The membrane parameters such as molecular weight, viscosity, and degree of deacetylation were used to evaluate the membrane performance for zinc ion adsorption. The molecular weight of the chitosan was found to influence the viscosity of the chitosan/acetic acid solution. An increase in molecular weight (60000-400000 kg.kmol-1) of the chitosan resulted in a higher viscosity (0.05-0.65 Pa.s) of the chitosan/acetic acid solution. The effect of the degree of deacetylation on the viscosity is not significant. The effect of the membrane production parameters (chitosan- and acetic acid concentration) on the viscosity is mainly determined by the chitosan concentration. For higher chitosan concentrations, a membrane with a better adsorption capacity was obtained. The membrane adsorption capacity increases from 20-130 mg Zn per gram of wet membrane for an increase in chitosan concentration from 2-7 mass %. Chitosan concentrations below 2 and above 7.5 mass % produced membranes that lack good mechanical properties. The optimum manufacturing conditions including chitosan concentration, acetic acid concentration, sodium hydroxide concentration and crosslinking for chitosan membranes within the workable range were defined by the criteria of adsorption capacity and flux. The adsorption increases (50-120 mg.g-1) as the acetic acid concentration increases (1-7 mass %). The sodium hydroxide concentration seems not to have a large effect on the adsorption characteristics of the membrane however, a maximum was reached at a concentration of 5 mass %. The adsorption capacity per gram of wet membrane strongly increases with the chitosan concentration in the acetic acid solution but remains constant per gram of dry chitosan. The optimum solution for membrane production consists of 7 mass % chitosan and 4 mass % acetic acid in de-ionised water. The sodium hydroxide concentration for phase inversion is at optimum at 5 mass %. The optimum cross-linking time was determined to be 6 hours (Percentage crosslinking of 18%). As the cross-linking time increases the adsorption of the zinc decreases (150-50 mg.g-1) in the time range of 0 to 12 hours. After a crosslinking time of 12 hours, the adsorption capacity remains constant. This trend is comparable to the effect on flux through the membrane. The flux decreases (10-3 L.m-2.hr-1) with an increase in crosslinking time range of 0 to 12 hours and reaches a constant minimum after 12 hours.

Keywords: chitosan, membrane, waste water, heavy metal ions, adsorption

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Authors: Shuo Huang, Huomiao Guo, Wenrui Huang

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In navigation channels located in coasts and estuaries as the waterways connecting coastal water to ports or harbors, density-induced flow often exist due to the density-gradient or gravity gradient as the results of mixing between fresh water from coastal rivers and saline water in the coasts. The density-induced flow often carries sediment transport into navigation channels and causes sediment depositions in the channels. As a result, expensive dredging may need to maintain the water depth required for navigation. In our study, we conduct a series of experiments to investigate the characteristics of density-induced flow in the estuarine navigation channels under different density gradients. Empirical equations between density flow and salinity gradient were derived. Effects of coastal structures for regulating navigation channel on density-induced flow have also been investigated. Results will be very helpful for improving the understanding of the characteristics of density-induced flow in estuarine navigation channels. The results will also provide technical support for cost-effective waterway regulation and management to maintain coastal and estuarine navigation channels.

Keywords: density flow, estuarine, navigation channel, structure

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Authors: Raymond Dominic Uzoh

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Starch fillers were extracted from three plant sources namely amora tuber (a wild variety of Irish potato), sweet potato and yam starch and their particle size, pH, amylose, and amylopectin percentage decomposition determined accordingly by high performance liquid chromatography (HPLC). The starch was introduced into natural rubber in liquid phase (through gelatinization) by the latex compounding method and compounded according to standard method. The prepared starch/natural rubber composites was characterized by Instron Universal testing machine (UTM) for tensile mechanical properties. The composites was further characterized by x-ray diffraction and crosslink density analysis. The particle size determination showed that amora starch granules have the highest particle size (156 × 47 μm) followed by yam starch (155× 40 μm) and then the sweet potato starch (153 × 46 μm). The pH test also revealed that amora starch has a near neutral pH of 6.9, yam 6.8, and sweet potato 5.2 respectively. Amylose and amylopectin determination showed that yam starch has a higher percentage of amylose (29.68), followed by potato (22.34) and then amora starch with the lowest value (14.86) respectively. The tensile mechanical properties testing revealed that yam starch produced the best tensile mechanical properties followed by amora starch and then sweet potato starch. The structure, crystallinity/amorphous nature of the product composite was confirmed by x-ray diffraction, while the nature of crosslinking was confirmed by swelling test in toluene solvent using the Flory-Rehner approach. This research study has rendered a workable strategy for enhancing interfacial interaction between a hydrophilic filler (starch) and hydrophobic polymeric matrix (natural rubber) yielding moderately good tensile mechanical properties for further exploitation development and application in the rubber processing industry.

Keywords: natural rubber, fillers, starch, amylose, amylopectin, crosslink density

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Authors: K. Anas, M. Selvakumar, Samson David, R. R. Babu, S. Chattopadhyay

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The dynamic deformation of a visco elastic material can cause heat generation. This heat generation is aspect energy dissipation. The present work investigates the contribution of various factors like; elastomer structure, cross link type and density, filler networking, reinforcement potential and temperature at energy dissipation mechanism. The influences of these elements are investigated using very high frequency analyzer (VHF ) and dynamical mechanical analysis(DMA).VHF follows transmissibility and vibration isolation principle whereas DMA works on dynamical mechanical deformation principle. VHF analysis of different types of elastomers reveals that elastomer can act as a transmitter or damper of energy depending on the applied frequency ratio (ω/ωn). Dynamic modulus (G') of low damping rubbers like natural rubber does not varies rapidly with frequency but vice-versa for high damping rubber like butyl rubber (IIR). VHF analysis also depicts that polysulfidic linkages has high damping ratio (ζ) than mono sulfidic linkages due to its dissipative nature. At comparable cross link density, mono sulfidic linkages shows higher glass transition temperature (Tg) than poly sulfidic linkages. The intensity and location of loss modulus (G'') peak of different types of carbon black filled natural rubber compounds suggests that segmental relaxation at glass transition temperature (Tg) is seldom affected by filler particles, but the filler networks can influence the cross link density by absorbing the curatives. The filler network breaking and reformation during a dynamic strain is a thermally activated process. Thus, stronger aggregates are highly dissipative in nature. Measurements indicate that at lower temperature regimes polymeric chain friction is highly dissipative in nature.

Keywords: damping ratio, natural frequency, crosslinking density, segmental motion, surface activity, dissipative, polymeric chain friction

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Authors: S. Md. Shaarani, J. Md. Jahim, R. A. Rahman, R. Md. Illias

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Modern developments in biotechnology have paved the way for extensive use of biocatalysis in industries. Although it offers immense potential, industrial application is usually hampered by lack of operational stability, difficulty in recovery as well as limited re-use of the enzyme. These drawbacks, however, can be overcome by immobilization. Cross-linked enzyme aggregates (CLEAs), a versatile carrier-free immobilization technique is one that is currently capturing global interest. This approach involves precipitating soluble enzyme with an appropriate precipitant and subsequent crosslinking by a crosslinking reagent. Without ineffective carriers, CLEAs offer high enzymatic activity, stability and reduced production cost. This study demonstrated successful CLEA synthesis of recombinant xylanase from Trichoderma reesei using ethanol as aggregating agent and glutaraldehyde (2% (v/v); 100 mM) as crosslinker. Effects of additives including proteic feeder such as bovine serum albumin (BSA) and poly-L-Lysine were investigated to reveal its significance in enhancing the performance of enzyme. Addition of 0.1 mg BSA/U xylanase showed considerable increment in CLEA development with approximately 50% retained activity.

Keywords: cross-linked, immobilization, recombinant, xylanase

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Authors: K. Khouzami, J. Brassinne, C. Branca, E. Van Ruymbeke, B. Nysten, G. D’Angelo

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The development of hybrid organic-inorganic nanocomposites has recently attracted great interest. Typically, polymer silicates represent an emerging class of polymeric nanocomposites that offer superior material properties compared to each compound alone. Among these materials, complexes based on silicate clay and polysaccharides are one of the most promising nanocomposites. The strong electrostatic interaction between chitosan and montmorillonite can induce what is called physical hydrogel, where the coordination bonds or physical crosslinks may associate and dissociate reversibly and in a short time. These mechanisms could be the main origin of the uniqueness of their rheological behavior. However, owing to their structure intrinsically heterogeneous and/or the lack of dissipated energy, they are usually brittle, possess a poor toughness and may not have sufficient mechanical strength. Consequently, the properties of these nanocomposites cannot respond to some requirements of many applications in several fields. To address the issue of weak mechanical properties, covalent chemical crosslink bonds can be introduced to the physical hydrogel. In this way, quite homogeneous dually crosslinked microstructures with high dissipated energy and enhanced mechanical strength can be engineered. In this work, we have prepared a series of chitosan-montmorillonite nanocomposites chemically crosslinked by addition of poly (ethylene glycol) diglycidyl ether. This study aims to provide a better understanding of the mechanical behavior of dually crosslinked chitosan-based nanocomposites by relating it to their microstructures. In these systems, the variety of microstructures is obtained by modifying the number of cross-links. Subsequently, a superior uniqueness of the rheological properties of chemically crosslinked chitosan-montmorillonite nanocomposites is achieved, especially at the highest percentage of clay. Their rheological behaviors depend on the clay/chitosan ratio and the crosslinking. All specimens exhibit a viscous rheological behavior over the frequency range investigated. The flow curves of the nanocomposites show a Newtonian plateau at very low shear rates accompanied by a quite complicated nonlinear decrease with increasing the shear rate. Crosslinking induces a shear thinning behavior revealing the formation of network-like structures. Fitting shear viscosity curves via Ostward-De Waele equation disclosed that crosslinking and clay addition strongly affect the pseudoplasticity of the nanocomposites for shear rates γ ̇>20.

Keywords: chitosan, crossliking, nanocomposites, rheological properties

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Authors: S. B. Provost, Susan Sheng

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An alternative bivariate density estimation methodology is introduced in this presentation. The proposed approach involves estimating the density function associated with the marginal distribution of each of the two variables by means of the saddlepoint approximation technique and applying a bivariate polynomial adjustment to the product of these density estimates. Since the saddlepoint approximation is utilized in the context of density estimation, such estimates are determined from empirical cumulant-generating functions. In the univariate case, the saddlepoint density estimate is itself adjusted by a polynomial. Given a set of observations, the coefficients of the polynomial adjustments are obtained from the sample moments. Several illustrative applications of the proposed methodology shall be presented. Since this approach relies essentially on a determinate number of sample moments, it is particularly well suited for modeling massive data sets.

Keywords: density estimation, empirical cumulant-generating function, moments, saddlepoint approximation

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Authors: Serge B. Provost

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Numerous statistical inference and modeling methodologies are based on sample moments rather than the actual observations. A result justifying the validity of this approach is introduced. More specifically, it will be established that given the first n moments of a sample of size n, one can recover the original n sample points. This implies that a sample of size n and its first associated n moments contain precisely the same amount of information. However, it is efficient to make use of a limited number of initial moments as most of the relevant distributional information is included in them. Two types of density estimation techniques that rely on such moments will be discussed. The first one expresses a density estimate as the product of a suitable base density and a polynomial adjustment whose coefficients are determined by equating the moments of the density estimate to the sample moments. The second one assumes that the derivative of the logarithm of a density function can be represented as a rational function. This gives rise to a system of linear equations involving sample moments, the density estimate is then obtained by solving a differential equation. Unlike kernel density estimation, these methodologies are ideally suited to model ‘big data’ as they only require a limited number of moments, irrespective of the sample size. What is more, they produce simple closed form expressions that are amenable to algebraic manipulations. They also turn out to be more accurate as will be shown in several illustrative examples.

Keywords: density estimation, log-density, polynomial adjustments, sample moments

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Authors: Meng-Yu Tsai, Jui-hun Chang, Wen-Feng Hung, Jing-Dong Chou

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The objective of this paper was to use gravitrap to survey the mosquito density in Kaohsiung. Gravitrap is one of the tools for surveillance the mosquito density. Gravitrap not only monitor the mosquito density but also decrease the mosquito density. Kaohsiung Environment Protection Bureau (KEPB) used gravitrap to monitor the mosquito density in 2016. KEPB put gravitrap in five districts which had the more confirmed dengue cases in 2015. The results indicated that (1)the highest positive rate (PR) of gravitrap was in Gushan district, the PR of gravitrap in Gushan district was 19.25%. (2) the lowest PR of gravitrap was in Sanmin district, the PR of gravitrap in Sanmin district was 8.55%. (3) compared these two districts, the most important factor to influence of PR of gravitrap was the knowledge of dengue prevention. Therefore, the PR of gravitrap was one of the references for making dengue prevention policy.

Keywords: continuous assessment, course integration, curricular reform, student feedback

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Authors: Z. Haddad, C. Abid, O. Rahli, O. Margeat, W. Dachraoui, A. Mataoui

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The present study aims to measure the volumetric mass density of NiPd-heptane nanofluids synthesized using a one-step method known as thermal decomposition of metal-surfactant complexes. The particle concentration is up to 7.55 g/l and the temperature range of the experiment is from 20°C to 50°C. The measured values were compared with the mixture theory and good agreement between the theoretical equation and measurement were obtained. Moreover, the available nanofluids volumetric mass density data in the literature is reviewed.

Keywords: NiPd nanoparticles, nanofluids, volumetric mass density, stability

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Authors: Nieves M. C. Talavera-Prieto, Abel G. M. Ferreira, António T. G. Portugal, Rui J. Moreira, Jaime B. Santos

Abstract:

The knowledge of biodiesel density over large ranges of temperature and pressure is important for predicting the behavior of fuel injection and combustion systems in diesel engines, and for the optimization of such systems. In this study, cottonseed oil was transesterified into biodiesel and its density was measured at temperatures between 288 K and 358 K and pressures between 0.1 MPa and 30 MPa, with expanded uncertainty estimated as ±1.6 kg.m^-3. Experimental pressure-volume-temperature (pVT) cottonseed data was used along with literature data relative to other 18 biodiesels, in order to build a database used to test the correlation of density with temperarure and pressure using the Goharshadi–Morsali–Abbaspour equation of state (GMA EoS). To our knowledge, this is the first that density measurements are presented for cottonseed biodiesel under such high pressures, and the GMA EoS used to model biodiesel density. The new tested EoS allowed correlations within 0.2 kg•m-3 corresponding to average relative deviations within 0.02%. The built database was used to develop and test a new full predictive model derived from the observed linear relation between density and degree of unsaturation (DU), which depended from biodiesel FAMEs profile. The average density deviation of this method was only about 3 kg.m-3 within the temperature and pressure limits of application. These results represent appreciable improvements in the context of density prediction at high pressure when compared with other equations of state.

Keywords: biodiesel density, correlation, equation of state, prediction

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Authors: Bachir Chemani, Rachid Halfaoui

Abstract:

The aim of work is to define the distribution density of winding yarn on cylindrical and conical bobbins. It is known that parallel winding gives greater density and more regular distribution, but the unwinding of yarn is much more difficult for following process. The conical spool has an enormous advantage during unwinding and may contain a large amount of yarns, but the density distribution is not regular because of difference in diameters. The variation of specific density over the reel height is explained generally by the sudden change of winding speed due to direction movement variation of yarn. We determined the conditions of uniform winding and developed a calculate model to the change of the specific density of winding wire over entire spool height.

Keywords: textile, cylindrical bobbins, conical bobbins, parallel winding, cross winding

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Authors: Nigus Maregu Demewoz, Shu-Kai Yeh

Abstract:

Low-density nanocellular foam is a fascinating new-generation advanced material due to its mechanical strength and thermal insulation properties. In nanocellular foam, reducing the density increases the insulation ability. However, producing a nanocellular foam of densities less than 0.3 with a cell size of less than 100 nm is very challenging. In this study, poly (methyl methacrylate) (PMMA) was blended with Polyether block amide (PEBAX) to study the effects of PEBAX on the nanocellular foam structure of the PMMA matrix. We added 2 wt% of PEBAX in the PMMA matrix, and the PEBAX nanostructured domain size of 45 nm was well dispersed in the PMMA matrix. The foaming result produced a new generation special bouquet-like nanocellular foam of cell size less than 50 nm with a relative density of 0.24. Also, we were able to produce a nanocellular foam of a relative density of about 0.17. In addition to thermal insulation applications, bouquet-like nanocellular foam may be expected for filtration applications.

Keywords: nanocellular foam, low-density, cell size, relative density, PMMA/PEBAX

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Authors: Nigus Maregu Demewoz, Shu-Kai Yeh

Abstract:

Low-density nanocellular foam is a fascinating new-generation advanced material due to its mechanical strength and thermal insulation properties. In nanocellular foam, reducing the density increases the insulation ability. However, producing a nanocellular foam of densities less than 0.3 with a cell size of less than 100 nm is very challenging. In this study, poly (methyl methacrylate) (PMMA) was blended with Polyether block amide (PEBAX) to study the effects of PEBAX on the nanocellular foam structure of the PMMA matrix. We added 2 wt% of PEBAX in the PMMA matrix, and the PEBAX nanostructured domain size of 45 nm was well dispersed in the PMMA matrix. The foaming result produced a new generation special bouquet-like nanocellular foam of cell size less than 50 nm with a relative density of 0.24. Also, we were able to produce a nanocellular foam of a relative density of about 0.17. In addition to thermal insulation applications, bouquet-like nanocellular foam may be expected for filtration applications.

Keywords: nanocellular foam, low-density, cell size, relative density, PMMA/PEBAX blend

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Authors: Zeyu Zhou, Ziyu Zhao, Xiaochen Yang, Ling AI, Heng Zhai, Stuart Holmes

Abstract:

As a promising sustainable alternative to traditional fossil fuels, fuel cell technology is highly favoured due to its enhanced working efficiency and reduced emissions. In the context of high-temperature fuel cells (operating above 100 °C), the most commonly used proton exchange membrane (PEM) is the Polybenzimidazole (PBI) doped phosphoric acid (PA) membrane. Grafting is a promising strategy to advance PA-doped PBI PEM technology. The existing grafting modification on PBI PEMs mainly focuses on grafting phosphate-containing or alkaline groups onto the PBI molecular chains. However, quaternary ammonium-based grafting approaches face a common challenge. To initiate the N-alkylation reaction, deacidifying agents such as NaH, NaOH, KOH, K2CO3, etc., can lead to ionic crosslinking between the quaternary ammonium group and PBI. Polyvinylpyrrolidone (PVP) is another widely used polymer, the N-heterocycle groups within PVP endow it with a significant ability to absorb PA. Recently, PVP has attracted substantial attention in the field of fuel cells due to its reduced environmental impact and impressive fuel cell performance. However, due to the the poor compatibility of PVP in PBI, few research apply PVP in PA-doped PBI PEMs. This work introduces an innovative strategy to graft PVP onto PBI to form a network-like polymer. Due to the absence of quaternary ammonium groups, PVP does not pose issues related to crosslinking with PBI. Moreover, the nitrogen-containing functional groups on PVP provide PBI with a robust phosphoric acid retention ability. The nuclear magnetic resonance (NMR) hydrogen spectrum analysis results indicate the successful completion of the grafting reaction where N-alkylation reactions happen on both sides of the grafting agent 1,4-bis(chloromethyl)benzene. On one side, the reaction takes place with the hydrogen atoms on the imidazole groups of PBI, while on the other side, it reacts with the terminal amino group of PVP. The XPS results provide additional evidence from the perspective of the element. On synthesized PBI-g-PVP surfaces, there is an absence of chlorine (chlorine in grafting agent 1,4-bis(chloromethyl)benzene is substituted) element but a presence of sulfur element (sulfur element in terminal amino PVP appears in PBI), which demonstrates the occurrence of the grafting reaction and PVP is successfully grafted onto PBI. Prepare these modified membranes into MEA. It was found that during the fuel cell operation, all the grafted membranes showed substantial improvement in maximum current density and peak power density compared to unmodified one. For PBI-g-PVP 30, with a grafting degree of 22.4%, the peak power density reaches 1312 mW cm⁻², marking a 59.6% enhancement compared to the pristine PBI membrane. The improvement is caused by the improved PA binding ability of the membrane after grafting. The AST test result shows that the grafting membranes have better long-term durability and performance than unmodified membranes attributed to the presence of added PA binding sites, which can effectively prevent the PA leaching caused by proton migration. In conclusion, the test results indicate that grafting PVP onto PBI is a promising strategy which can effectively improve the fuel cell performance.

Keywords: fuel cell, grafting modification, PA doping ability, PVP

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