Thermally resolved synchrotron FT-IR microscopy of structural changes in bloodmeal-based thermoplastics

Synchrotron FT-IR micro-spectroscopy was used to determine thermally induced structural changes in thermoplastic protein produced from bloodmeal after mixing with sodium sulphite, sodium dodecyl sulphate, urea, tri-ethylene glycol and water. Changes in protein secondary structure at elevated temperature were assessed using second derivative peak height ratios in the amide III region (1,200–1,330 cm^?1) and compared with DSC and DMA results over the same temperature range. The results show an increase in ordered β-sheet structures with temperature at the expense of random coils, and that these β-sheets do not melt in the temperature range up to extrusion temperature of 120 °C. The implication of this is that during melt processing, β-sheet clusters may remain intact, similar to dispersed particulate fillers.     

Characteristics and flow behavior of molten tin-polypropylene blend systems

An experimental study of tin-polypropylene compounds involving melt mixing and melt extrusion and molding over a range of temperatures is described. Problems of coalescence which make continuous mixing impossible above the melting temperature are described. Significant coalescence of the tin also results in extrusion and injection-molding problems. The influence of tin content and melt temperature on shear viscosity and extrusion character is discussed and interpreted. The electrical properties of the compounds are investigated.     

Rheological behavior of PET/HDPE in situ microfibrillar blends: Influence of microfibrils' flexibility

Poly(ethylene terephthalate) (PET)/high‐density polyethylene (HDPE) in situ microfibrillar reinforced blends were prepared via a slit die extrusion‐hot stretch‐quenching process. The in situ PET microfibrils contain various contents of a segmented thermoplastic elastomer, Hytrel 5526 (HT), hence having different flexibility as demonstrated by dynamic mechanical analysis. It is interesting that the simple mixing leads to nanoscale particles of the HT phase in PET phase, and the size of the HT particles is almost independent of the HT concentration, as observed from the scanning electron microscope micrographs which show that the microfibrils with different HT concentrations have almost the same diameter and smooth surfaces. The static rheological results by an advanced capillary rheometer show that the entrance pressure drop and the viscosity of the microfibrillar blends both reduced with increasing the microfibrils' flexibility. Furthermore, the data obtained by the temperature scan of the PET/HT/HDPE microfibrillar blends through a dynamic rheometer indicates that the more flexible microfibril leads to lower melt elasticity and slightly decreases the viscosities of blends, presenting a consistent conclusion about influences of the microfibrils' flexibility on the rheological behavior from the static rheometer measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1205–1216, 2007     

Orientation Effects in Hybrid-Polymer Mixtures

Composites based on melts of boron-oxide oligomer (BOO) and low-density polyethylene (LDPE) in the polyoxide-concentration range of 0–64 vol % were synthesized. The measurements of the thermomechanical and mechanical properties of the composites showed the incompatibility of the mixture components. The abnormal increase in the strength and the Young’s modulus of the LDPE/boron-oxide oligomer mixtures under the tension of molded composite specimens was registered in the range of 25–50 vol % polyoxide. The anomalies were explained as being due to polyoxide-fiber formation and confirmed by the electron-microscopy images. The abnormal changes in the differential pressure in a melt flow and the torque of an extrusion auger were observed in the same polyoxide-concentration range, which was explained by the polyoxide orientation in a melt flow and its planar structure. The chemical structure of boron-oxide oligomer exposed to extrusion mixing and its distribution within a molded specimen of the mixture were analyzed by IR spectroscopy. The opportunity to synthesize hydrolytically stable composites in a wide range of ratios owing to the polyoxide encapsulation in a polyethylene matrix was shown.     

The use of thermoplastic elastomers as polymer processing aids in processing of linear low density polyethylene

Commercially available thermoplastic elastomers based on block copolymers of diisocyanates and polyols and based on silicones have been reported by Kulikov et al. (2004 and 2006) to delay sharkskin in extrusion of Linear Low Density Polyethylene. In this work thermoplastic elastomers have been used as polymer processing additives in blown film extrusion of Linear Low Density Polyethylene. When a thermoplastic elastomer is added in small amounts to Linear Low Density Polyethylene it deposits at the die surface during extrusion and may postpone the onset of sharkskin enabling up to 20 times higher rate of extrusion. Many thermoplastic elastomers are certified for body and food contacts and could be a cost-effective substitution of fluorinated polymers in processing of Linear Low Density Polyethylene by extrusion. Oscillating and capillar rheometry have been used to reveal the mode of action of the additives. Results of capillar rheometry showed a decrease of apparent viscosity of the polymer melt when additive was added. Therefore Mooney method (Mooney, 1931) was applied to prove occurring slip inside of the die. Substantial delay of sharkskin was achieved also in conditions without slip of molten polyethylene inside the die by adding thermoplastic elastomer based on urethanes. Oscillating rheometry has been used to characterize elasticity of the materials. It could be shown that efficiency to delay sharkskin depends on elasticity of the specific thermoplastic elastomer at processing temperature. Surface tension of the solid materials was used to estimate the mutual affinity of the materials. Therefore a theoretical model of Rathod and Hatzikiriakos (2004) was used to evaluate the data. Finally a classification of polymer processing aids into “slip inducers” and “flow enhancers” by their mode of action was done. Ability of novel processing aids to postpone sharkskin was shown in blown film extrusion. Applicability of polymer processing aids in injection moulding could be proved by use of a mould with spiral cavity.     

Preparation of rechargeable biocidal polypropylene by reactive extrusion with diallylamino triazine

Biocidal polypropylene (PP) was prepared by using a reactive extrusion process, in which PP was grafted with an N-halamine precursor, 2, 4-diamino-6-diallylamino-1, 3, 5-triazine (NDAM). After chlorination the grated PP was converted to biocidal halamine structures. Effects of monomer and initiator concentration on grafting yield, thermal properties, and biocidal efficacy were studied. The Fourier transformed spectroscopy (FTIR) results and nitrogen analysis confirmed the graft polymerization on PP backbone during the reactive extrusion. The results also indicated that at low monomer concentration, increase in initiator concentration led to increase in PP chain scission and decrease in mixing torque, or polymer chain length. As the monomer concentration increases, grafted monomer content in the products showed a steady increase, indicating more grafting copolymerization in the system. The halogenated products exhibited potent antimicrobial properties against Escherichia coli, and the antimicrobial properties were durable and regenerable.     

原位复合材料的加工性能

使用ＨＢＩＲｈｅｏｍｉｘ６１０型混合机将四种全芳香族热致液晶聚合物与热塑性树脂熔融共混，研究了混合效果，混合过程的平衡转矩与时间，温度的关系，结果显示，用该混合机可以得到均匀分散的共混体系，这些液晶聚合物具有大大低于纯聚砜的熔体粘度，将其与聚砜熔混，可使其混体系的平衡转矩比纯聚砜减小２－３倍，说明液晶聚合物是一种加工助剂，能用来改善高性能工程塑料的加工性能。     

Fabrication of colloidal doublets by a salting out-quenching-fusing technique

It is well-known that high ionic strength promotes colloid aggregation. Here we show that, by controlling this aggregation process, we can produce high yields of homodoublet and heterodoublet polymer colloids. The aggregation process is started by increasing the ionic strength to roughly 250 mM KCl. After approximately the rapid flocculation time, we quench the "reaction" by mixing in a large quantity of deionized water, which dilutes the ionic strength and prevents further aggregation. At this point, the suspension consists primarily of singlet and doublet particles. Through heating above the glass transition temperature of the polymers, the doublets are fused together and remain intact even after sonication. It is also shown that heterodoublets can include a silica particle together with a polymer colloid. The salting out-quenching-fusing technique is a rapid, easy-to-perform, repeatable process for fabricating colloidal doublets from polymers and other materials.     

Plasticization of corn gluten meal and characterization of the blends

Corn gluten meal has thermoplastic properties enhanced by it's high zein content. The addition of an efficient plasticizer is necessary to lower the glass transition temperature. Homogeneous blends of plasticizer and corn gluten meal can be obtained either by a wet mixing technique or by compounding the two substances in an heated batch mixer. The resulting raw material is suitable for “thermoplastic forming” of low cost biomaterials.     

Association Equilibrium of Methylene Blue by Spectral Titration and Chemometrics Analysis: A Thermodynamic Study

The monomer‐dimer equilibrium of methylene blue (MB, Scheme I) has been investigated by means of UV‐Visible spectroscopy in aqueous solutions. The self aggregation of MB in water has been investigated by recording absorption spectra in the wavelength range of 450–750 nm, and in different ionic strengths using concentrated KCl solutions in the temperature range of 20–90°C. Chemometrics analysis of the spectral data gave a dimerization constant, individual spectra of the monomer and dimer forms of the dye molecule. The quantitative analysis of the data of the undefined mixture was carried out by simultaneous resolution of the overlapping spectral bands in the whole set of absorption spectra. The dimerization constants of MB determined by mathematical deconvolution of the thermometric spectral titration data show dependency on temperature variations. The concentration range of MB was 6.00 × 10^?5‐3.00 × 10^?4 M. Utilizing the van't Hoff relation, which describes the dependence of the equilibrium constant on temperature, the thermodynamics parameters ΔH° and ΔS° of the aggregation process were determined. The compensation effect was verified by the thermodynamics results of the dimerization process of the dye.     

Stimuli-responsive controlled growth of mono- and bidimensional particles from basic zirconium sulfate hydrosols

A thermostimulated sol-gel transition in a system prepared by mixing a ZrOCl(2) acidified solution to a hot H(2)SO(4) aqueous solution was studied by dynamic rheological measurements and quasi-elastic light scattering. The effect of temperature and of molar ratio R(S) = [Zr]/[SO(4)] on the gelation kinetics was analyzed using the mass fractal aggregate growth model. This study shows that the linear growth of aggregates occurs at the early period of transformation, while bidimensional growth occurs at the advanced stage. The bidimensional growth can be shifted toward monodimensional growth by decreasing the aggregation rate by controlling the temperature and/or molar ratio R(S). EXAFS and Raman results gave evidence that the linear chain growth is supported by covalent sulfate bonding between primary building blocks. At the advanced stage of aggregation, the assembly of linear chains through hydrogen bonding gave rise to the growth of bidimensional particles.     

Dielectric properties under corona charging of thermoplastics for holographic optical switching

Photothermoplastics are materials which have been proposed for optical switching devices: a grating is recorded by surface deformation of the thermoplastic layer, coated on an organic photoconductive layer used, like in xerography, for an electrostatic image recording material. But first of all an electrical field is applied through a corona charging sequence and obviously dielectric properties of the abietic ester thermoplastic material are of importance. This paper discusses the behaviour of such a layered thermoplastic material in a corona set-up, by measuring the corona current and the surface voltage following thickness and temperature of the sample and charging or discharging times.     

Poly(butylene succinate) and graphene nanoplatelet–based sustainable functional nanocomposite materials: structure-properties relationship

Sustainable functional polymer nanocomposites from renewable resources are extremely promising materials that can provide the next-generation of lightweight, multifunctional materials for several applications including energy storage, automotive, construction, defense, aerospace, consumer products, biomedical and functional coatings to name few. There is limited information on the use of sustainable polymers and graphene nanoplatelets (GNs), as well as the combinations of these two can provide reduced water permeability or enhanced electrical conductivity and improved thermal properties, and so on. Building upon this hypothesis, biobased poly(butylene succinate)/few-layer GN nanocomposites were prepared via a solventless melt-blending technique. Different characterization techniques such as differential scanning calorimetery, thermogravimetric analysis, dynamic mechanical analysis, dielectric spectroscopy, X-ray diffraction (XRD) and hot stage optical microscopy were used to study the thermal and structural characteristics. The melt blending was characterized by torque and temperature curves which showed that torque was reduced by up to 15 Nm, and melt temperature was improved by up to 5 °C. The improved crystallization of the composites in low concentrations of GN was observed. Graphene has been found to increase the crystallization temperature up to 10 °C and yielded pronounced spherulite structure, whereas peak shift was observed in XRD. High filler loading from 0.5 to 6.0 wt% was used to obtain more insights for few-layer graphene applications for thermoplastic polymer processing applications.     

Thermal,combustion and optical properties of new polyimide/ODA-functionalized Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocomposites containing xanthene and amide groups

Polypropylene (PP), due to its chemical stability, is considered one of the main responsible of the increasing amount of plastic wastes on earth. To overcome this problem and to reduce the dependence of oil feedstocks, the use of lignocellulosics as fillers or reinforcements in thermoplastic materials has been increasing enormously in the last decades. In the present work, Liquid Wood (a mixture of cellulose, hemp, fax and lignin) was used to prepare, by mechanical mixing followed by thermal extrusion, blends of various PP/Liquid Wood ratios. Differential scanning calorimetry and thermogravimetric analysis experiments were performed in order to verify whether and how much the composition of the blends affects the thermal properties of the obtained compounds. Both calorimetric and thermogravimetric results indicate that the application of PP as a matrix does not limit the processing temperature of Liquid Wood, which may lead to a perfect marketable composite from these components. The addition of Liquid Wood also resulted in enhanced mechanical properties for the PP/Liquid Wood blends.     

Continuous hydrothermal synthesis of CoFe2O4 nanoparticles

We have investigated the continuous hydrothermal synthesis and crystallization of spinel CoFe₂O₄ via the reaction of ferric nitrate and cobalt nitrate with sodium hydroxide. The reaction was carried out in water at temperatures ranging from 475 to 675 K and pressures of 25 MPa. The relative solubility of the precipitating cations was found to play a critical role in attaining the correct product. It was found necessary to control pH and temperature in order to prevent premature precipitation of iron in the reactor. Two variations of the continuous hydrothermal technique were examined—cold mixing and hot mixing. The cold mixing experiments produced a product with less impurity than the hot mixing experiments. Furthermore, the cold mixing configuration was successful in producing uniform nanoparticles of CoFe₂O₄. A mechanism of particle formation was postulated involving the precipitation of metal hydroxides at ambient conditions, dissolution of the hydroxides as temperature is increased followed by rapid precipitation of metal oxides at elevated temperatures. The hot mixing experiments, on the other hand, simply involve the precipitation of metal oxides due to the addition of the hot hydroxide solution. In both cases, very fine particles of CoFe₂O₄ are produced in the range of the processing conditions investigated.     

Structure and Dehydrochlorination of Poly(vinyl Chloride)

The wide applicability of poly(vinyl chloride) (PVC), a tough thermoplastic resin, is due to a combination of moderate cost with the following characteristics [1]: (i) good general properties as a plastic material: (ii) great variation in properties, e.g., increase in heat distortion temperature, resistance to hot melt flow, improvement in mechanical, electrical properties, and processability of unplasticized PVC through external plasticization, block and graft copolymerization (internal plasticization), and chemical modification, e.g., chlorination, Friedel-Crafts, and cross-linking reactions: and (iii) processing versatility including injection molding, extrusion, blow molding, calendering, and lamination to produce many products of potential uses.     

Rapid mixing studies in an entrained flow process

This paper describes the experimental results of rapid mixing studies for a high temperature, entrained flow process (with flow time scales of a few milliseconds) where very rapid mixing and particle heating is required. To study the effect of mixing, experiments were conducted in a hot (about 2600 K) reacting entrained flow coal pyrolysis system using several coal and steam injector geometries designed to achieve uniform dispersion of coal particles in the hot background gases. These tests were conducted in the Avco Research Laboratory's high-throughput, two-stage, entrained flow reactor facility. To visually observe the mixing and solids dispersion patterns, a cold flow (room temperature) analog was developed by matching several dimensionless hydrodynamic groups with the hot reacting gasifier system. Experiments in the cold flow analog were carried out in a glass apparatus using air to simulate the main flow and using spherical glass beads carried by nitrogen to simulate the coal feed. Photographic techniques were used to study the mixing and spatial distribution of the particles. The results from the cold flow tests and the coal carbon conversions from hot flow runs indicate that the improvement in mixing results in higher pyrolysis yields that are no longer limited by gross, time-averaged mixing behavior but rather by chemical kinetics.     

Determination of cluster composition in heteroaggregation of binary particle systems by flow cytometry

Cluster composition in aggregation processes of multiple particle species can be dynamically determined by flow cytometry if particle populations are fluorescently labeled. By flow cytometric single particle analysis, aggregates can be characterized according to the exact amount of constituent particles, allowing the detailed and separate quantification of homo- and heteroaggregation. This contribution demonstrates the application of flow cytometry for the experimental detection of heteroaggregation in a binary particle mixture of oppositely charged polystyrene (PS) particles and Rhodamine-B labeled melamine-formaldehyde (MF-RhB) particles. Experiments with different particle concentration, temperature, mixing mode, ionic strength and particle mixing ratio are presented. Aggregation kinetics are enhanced with increasing particle concentration and temperature as well as by increased shear of mixing. These results represent well-known behavior published in previous investigations and validate the performance of flow cytometry for probing heteroaggregation processes. Physical insight with a novel level of detail is gained by the quantification of de- and restabilization phenomena. At low ionic strength, "raspberry"-type aggregates with PS cores are formed by primary heteroaggregation. At moderate particle number ratios, these aggregates are electrostatically destabilized and form more complex aggregates in a secondary heteroaggregation process. At high particle number ratios (> or =50:1), the raspberry-type aggregates are electrostatically restabilized and secondary heteroaggregation is prevented. The dynamic change of aggregate charge was verified by zeta-potential measurements. The elevation of salt concentration over several orders of magnitude retards aggregation dynamics, since attractive interparticle forces are diminished by an electrostatic double layer. This indicates that heteroaggregation induced by attractive interparticle forces is faster than aggregation due to random Brownian motion. Destabilization at high ionic strength is facilitated by charged ions and no longer by MF-RhB coverage. This results in a species independent one step aggregation process.     

Evaluation of groundwater tritium content and mixing behavior of Tatapani geothermal systems,Chhattisgarh, India

Isotopic investigations were carried out on hot springs, groundwater and surface water to evaluate the mixing processes within the geothermal system. Physico-chemical parameter (EC, pH, Temp.) and tritium content of groundwater, hot springs and surface water were measured. The temperature of the hot springs were varied from 60 to 98.8 °C and EC from 674 to 728 μS/cm. The tritium content of groundwater varies from 1.5 to 5 TU whereas, geothermal water have slightly less tritium and their values ranges from 1.4 to 4.4 TU. Low tritium, higher EC and high temperature of a few hot springs indicate insignificant mixing whereas high tritium, lower EC and low temperature indicates significant mixing of thermal and non-thermal water. The degree of mixing for geothermal springs is estimated. It is found that the groundwater components present in the diluted thermal waters are about 25–80%. It is also observed that mixing process is prominent along the fault and in the area where groundwater exploitation is more. Extensive pumping of groundwater causes an increase in the rate of mixing of thermal and non-thermal water. The tritium content of groundwater, surface water and hot springs are indicating, it is of modern recharge.     

Impingement mixing and its effect on the microstructure of RIM polyurethanes

The effect of impingement mixing on the microstructures developed during a reaction injection molding process in a thermoplastic urethane system was investigated. The polyurethane studied was a 4,4′-diphenylmethane diisocyanate/l,4-butane diol/poly(propyleneoxide) end-capped with poly(ethy1eneoxide) polyol system with a 5/4/1 molar ratio. Three different impingement mixing levels ranging from Re = 80 to Re = 210 were implemented by a laboratory RIM machine. The samples were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), optical microscopy, and transmission electron microscopy (TEM). Morphologies of hard-segment globules, hard-segment spherulites, and soft-segment rich matrix were observed. The multiple DSC endotherms were related to different crystalline structures. A higher level of mixing was found to increase the molecular weight and produce more paracrystalline structures. A lower mixing level produced better phase separation and spherulitic structures. High temperature annealing caused transurethanization, which may allow molecular rearrangement and change the crystalline structures.