Graft interpenetrating polymer networks of polyurethane and epoxy containing rigid rods in side chain

The rigid rod‐like 4,4′‐bis(6‐hydroxyhexyloxy)biphenyl (BHHBP) units were distributed in either the epoxy or polyurethane to become SR‐epoxy and PU (with or without BHHBP) polymer matrices. The interpenetrating polymer networks (IPNs) of PU (with or without BHHBP) and SR‐epoxy were synthesized through simultaneous polymerization, and connected each other via the grafting reaction between the ? NCO groups of the PU polymer network and the ? OH groups on the side chains of SR‐epoxy network. The thermal and mechanical characteristics, compatibilities, and morphologies of these PU (with or without BHHBP)/SR‐epoxy graft‐IPNs were investigated. The polyether‐type PU(PPG series)/SR‐ epoxy graft‐IPNs exhibited two‐phased morphologies (i.e., phase separation occurred), and higher fracture energies (G_IC). Whereas the polyester‐type PU(PBA series)/SR‐ epoxy graft‐IPNs were homogeneous (no phase separation), and exhibited higher tensile and Izod impact strengths. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Studies on the mechanical,thermal, and morphological properties of poly(ether ether ketone)/poly(ether sulfone)/barium titanate nanocomposites: Correlation of experimental results with theoretical predictive models

In this study, mechanical, thermal, and morphological properties of the nanocomposites fabricated with the optimized blend of poly(ether ether ketone) (PEEK) and poly(ether sulfone) (PES) incorporated with nanobarium titanate (BT) were investigated. The optimized blend was based on the mechanical and thermal properties of the PEEK and PES in the ratio of 75 : 25 wt %. Nanoparticles were incorporated into the optimized blend with the help of twin‐screw extruder. The concentration of nano‐BT was varied from 2 to 6 wt % (0.41–1.28 vol %). With the increase in the nanosized BT concentrations, the tensile strength, tensile modulus, and elongation at break increased, whereas the crystallinity of the nanocomposites calculated by using differential scanning calorimetry method was found to decrease marginally. Morphological studies were carried out using scanning electron microscopy. The nanocomposites were evaluated by using theoretical predictive models according to “Pukanszky model” applicable to tensile strength and “Takayanagi's model” and “Guth and Smallwood model” applicable to tensile modulus. Upper and lower boundary of Hashin–Shtrikman model as well as Paul's model, applicable to tensile modulus, were also used to compare the experimental data. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Interrelation of Scanning Electron Micrographs with Flexural Behavior of Ferrite and Nano-Barium Titanate Reinforced Poly-Ether-Ether-Ketone (PEEK) Composites

ABSTRACT

The flexural behavior of ferrite filled poly-ether-ether-ketone (PEEK) composites, with and without reinforcement of nano-barium titanate, was studied and was corroborated through scanning electron microscopy (SEM). In this study, ferrite filled PEEK, and ferrite and nano-barium titanate reinforced PEEK composites were prepared. Ferrite filled PEEK composites showed reduction in flexural strength and increase in flexural modulus with the increase in ferrite content, whereas, with the reinforcement of nano-barium titanate, flexural strength increased and flexural modulus decreased at similar ferrite content. The SEM micrographs corroborated well with flexural behavior, as ferrite particles and smooth topographic surfaces of brittle fracture were evident in the samples having higher ferrite content in ferrite filled PEEK composites, whereas, typical yield pattern of crust and trough on fractured topographic surfaces of ferrite and nano-barium titanate, reinforced PEEK composites, was visible.     

Polysiloxanes containing polyhedral oligomeric silsesquioxane groups in the side chains; synthesis and properties

Linear polysiloxanes having different amounts of polyhedral oligomeric silsequioxane (POSS) side groups were prepared from the hydrosilylation reaction of poly(ethylhydrosiloxane) with different amount of POSS and 1-octene using platinum(0)-divinyl tetramethyldisiloxane as a catayst. 1-Octene and platinum(0)-divinyl tetramethyldisiloxane were found to be very important for the preparation of the linear polymer without any cross-linked structures. The linear polysiloxanes with POSS side groups are soluble in various organic solvents. When the content of POSS-containing monomeric unit is larger than 10 mol%, free standing films can be prepared from a routine solution casting method, although this polysiloxane is not cross-linked.     

Microstructure and properties of high alumina castables containing calcium alumino‐titanate

Calcium alumino‐titanate (CAT)‐containing high alumina castables were prepared using bauxite, CAT, and α‐Al₂O₃ as starting materials, and subsequently heat treated at various temperatures ranging from 1400°C to 1600°C. The thermo‐mechanical properties of the specimens as a function of the temperature were characterized in terms of linear shrinkage, bulk density, apparent porosity, cold crushing strength (CCS), modulus of rupture (MOR), residual ratio of MOR, and coefficient of thermal expansion (CTE). X‐ray diffraction (XRD) and scanning electron microscopy (SEM) were used to determine the phase composition and microstructural evolution, respectively. Sintering at temperatures between 1450 and 1500°C promoted normal grain growth, with the formation of a granular surface contact, and abnormal grain growth occurred at higher temperatures (≥ 1550°C). The cold strength of the specimen initially increased and subsequently decreased with temperature, whereas the residual ratio of MOR initially decreased with increasing temperature to 1550°C, then increased above 1550°C. In addition, the CTE of the specimen was only minimally influenced by the firing temperature.     

Solution properties of poly(thiocarbonates) containing cyclic side chains

Poly(thiocarbonates) with cyclic side chains have been studied in the theta solvent 1,4-dioxane. The Mark-Houwink-Sakurada (MHS) relationships were established and the unperturbed dimensions determined. The conformational parameters were compared with those of other poly(thiocarbonates) and related polymers. It was found that the polymers containing cyclic groups present a more extended and rigid chain. A marked influence of the nature and structure of the side chain on the conformational parameters was found.     

High-resolution scanning electron microscopy for the characterization of supported metal catalysts

A scanning electron microscope with a short-focal-length immersion lens and subnanometer resolution has been used to characterize several oxide-supported metal particle catalysts. Nanometer-sized metal particles in the Pt/TiO₂ and Pd/SiO₂ systems could be imaged with best clarity at the upper end of the operating voltage range (20–30 kV). However, visibility depended upon an adequate yield of secondary electrons relative to the support: small Pt particles on CeO₂ could not be located by secondary electron imaging. Best visibility of the surface topography of the support was obtained at lower accelerating voltages.     

Confocal Scanning Laser Microscope Image of Gradient Structure Formed in an Acrylate Copolymer/Fluoro-copolymer Blend

Thin films of poly(2-ethylhexyl acrylate-co-acrylic acid-co-vinyl acetate)/poly(vinylidene fluoride-co-hexafluoro acetone) [P(2EHA-AA-VAc)/P(VDF-HFA)] of 30/70 (by weight) blends without and with addition of 2 wt% fine silica gel were prepared on poly(ethylene terephthalate) (PET) from 20 wt% THF solution. Gradient domain morphology formed in the 30/70 blend was observed with a confocal scanning laser microscope (CSLM). Separate domains composed of P(2EHA-AA-VAc) phase were found in P(VDF-HFA) matrix at various levels of increasing depth with increasing domain size. Thus, CSLM is quite effective in morphological observation of the gradient structure formed in polymer blends, provided the blends are transparent.     

基于环境评价的页岩气特性研究

页岩气被认定为:采用游离或者吸附方式赋在有生径特点的页岩等地层的天然气,其具备了吸附成藏、自我生储等显著特点。通过页岩气制作,页岩气实验室特性曲线和扫描电镜等实验方式,对页岩气特性完成了分析,采用环境因子模型实现了特性的定量分析,这一研究对于我国页岩气的发展具有一定的理论和实际意义。     

Synthesis and properties of novel biodegradable polyurethanes containing fluorinated aliphatic side chains

This study used 5H–octafluoropentanoylfluoride and 2-amino-2-methyl-1,3-propanediol to synthesize a novel fluoro chain extender 2,2,3,3,4,4,5,5-octafluoro-N-(1,3-dihydroxy-2-methylpropan-2-yl) pentanamide (ODMP). Furthermore, 4,4′-diphenylmethane diisocyanate served as the hard segment, polycaprolactone diol (PCL) served as the soft segment, and ODMP served as the chain extender in the novel synthesized polyurethanes (ODMP/PUs). Gel permeation chromatography revealed that the molecular weight of the ODMP/PUs increased when the ODMP content was increased. ¹H and ¹⁹F nuclear magnetic resonance and Fourier transform infrared spectroscopy verified that the ODMP chain extenders were successfully synthesized and that the ODMP chain extenders were successfully incorporated into the backbone of the PUs. The interaction between the -NH (hydrogen bond) and CF₂ groups in the ODMP/PUs became stronger when the ODMP content was increased. Thermal analysis revealed that the initial decomposition temperature of the ODMP/PUs decreased and the second decomposition temperature increased when the polymers’ ODMP content was increased. Higher ODMP content also resulted in the ODMP/PUs’ higher glass transition and dynamic glass transition temperatures and lower ODMP maximum stress and Young’s modulus, causing a lower elongation at break. ODMP/PUs with higher ODMP content exhibited more protrusions and more rugged surfaces. The chemical resistance of the ODMP/PUs increased when the fluorine content was increased. Scanning electron microscopy revealed that ODMP/PUs with higher PCL content exhibited higher levels of hydrolytic degradation. Finally, in vitro erythrocyte tests revealed that increasing the ODMP chain extender content reduced the average number of erythrocytes adhering to the surface of the PUs.     

Synthesis of siloxanes containing reactive side chains

The synthesis and characterization of siloxanes containing methacrylate, epoxy, and amino side chains are described. Direct hydrosilylation of unsaturated methacrylate or epoxy compounds with methyl hydrogen siloxanes resulted in the attachment of methacrylate or epoxy groups as side chains on the siloxane in good yields. Amino side chains on siloxanes were formed by acidic hydrolysis of the ketenimine side chains, obtained by hydrosilylation of unsaturated ketenimines with methyl hydrogen siloxanes. Details of the preparation and characterization of such unsaturated ketenimines are reported.This paper is from the Second International Topical Workshop, Advances in Silicon-Based Polymer Science.     

Fabrication of honeycomb polyvinyl butyral film under humidity provided by super saturated salt solutions

We introduce a novel method for making breath figure arrays (BFAs) on polyvinyl butyral (PVB) films under humidity by putting the dip coated samples inside a chamber filled with supersaturated salt solutions. With the increase in humidity or retention time, multiple porous films with bigger pore sizes and wider size distributions are generally obtained, resulting from the coalescence of the following‐up water drops. The presence of nitrogen flow accelerates the evaporation of solvents and vapor, thus increases the elastic interaction among water droplets such that films with smaller pores can be obtained. Compared to PVB/ethyl acetate solution, it is easier to obtain a film with regular honeycomb pattern by using PVB/chloroform solution. Its lower boiling point makes it evaporate faster to increase temperature gradient between film surface and the atmosphere; while its higher density makes it provide stronger support to maintain the shape of water droplets. In this study, the solubility of polymer in solvents is initially proposed to explain the BFAs formation. Higher mobility of polymer chains in a good solvent increases chances of its polar groups to interact with water droplets, thus increases the possibility of regular arrangements of water droplets on the film. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Film‐forming process from globular polytetrafluoroethylene latex particles

Film formation from an aqueous polytetrafluoroethylene (p‐TFE) latex dispersion on glass tissues was studied. The p‐TFE particles were of globular shape, had a diameter of 220 ± 20 nm, and were of high crystallinity (～ 100%). The melting point of the material was 332°C. For the study of the film formation, stripes of glass tissues were dipped in a concentrated p‐TFE latex dispersion and then removed. The samples were then dried in an oven at well‐defined temperatures below and above the melting temperature T_m of the p‐TFE latex. The film formation from the particles was then studied by taking SEM micrographs of the surface of the samples at various times and conditions. It was observed that the globular particles kept their globular shape and did not coalesce to a film as long as the temperature of the sample was kept below T_m. When the samples were tempered with T > T_m the film formation started. The neighboring globular particles coalesced into wormlike particles that grew in length with time. During the growth of the particles the thickness of the particles remained constant. In the first stages the film can be imagined as a porous network from short wormlike objects. It is concluded that the coalescence begins above T_m when the polymer chains become mobile along their axis. The chains of neighboring particles can therefore interdigitate into each other along their main axis and crosslink the particles. The proposed mechanism of film formation is confirmed by AFM micrographs on which the individual particles from the dispersion are still visible in the wormlike objects. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 733–742, 2004     

Synthesis of block copolymers having perfluoroalkyl and silicone‐containing side chains using diazo macroinitiator and their surface properties

The fluorosilicone block copolymers of poly(perfluoroalkylethyl acrylate)‐b‐poly(3‐[tris(trimethylsilyloxy)silyl] propyl methacrylates) (PFA‐b‐PSiMAs) having perfluoroalkyl and silicone‐containing side chains were obtained by three‐step synthetic approaches. In the first step, hydroxyl‐terminated poly(perfluoroalkylethyl acrylate) macromonomer (PFAM) was prepared by the free‐radical polymerization of perfluoroalkylethyl acrylate and 2‐mercaptoethanol. In the second step, PFAM initiator (PFAMI) was prepared from the condensation reaction of the hydroxyl‐terminated PFAM and 4,4′‐azobis‐4‐cyanopentanoic acid chloride (ACPC). ACPC was obtained from the reaction of 4,4′‐azobis‐4‐cyanopentanoic acid and phosphorus pentachloride. In the third step, PFA‐b‐PSiMAs (BPFSs) were synthesized from the reaction of PFAMI macroinimer and SiMA. Fourier transform infrared spectroscopy and ¹H‐NMR analyses verified that the syntheses of ACPC, hydroxyl‐terminated PFAM, PFAMI, and BPFS were completed successfully. The intrinsic surface energies of BPFSs and their surface modification effects on poly(vinyl chloride) film were investigated by analyzing the surface free energies and atomic compositions of the outermost layer of the surfaces. BPFSs exhibit extremely low surface free energies of about 9.7–13.0 dynes/cm. It was confirmed that BPFS, having extremely low surface free energy, is preferentially enriched at the outermost layer of the surface of BPFS/poly(vinyl chloride) blend. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1917–1926, 1999     

侧链结晶PVC的结构和热性能

通过亲核取代反应制备了可侧链结晶的梳型接枝聚氯乙烯(PVC),利用傅里叶变换红外光谱、核磁共振氢谱和凝胶渗透色谱表征了梳型接枝PVC的结构,采用差示扫描量热法研究了接枝率与侧链长度对侧链结晶行为、熔融行为及玻璃化转变温度(tg)的影响。本研究方法可有效地将长链烷基接枝到PVC骨架上,并形成侧链结晶。侧链结晶的熔融焓和熔融温度随接枝率的增大而增大,随侧链的增长而减小。tg随接枝率的增大先降后增,连接含有较长侧链的PVC的tg明显高于不含侧链的PVC。     

Real Space and Wave‐Number Space Studies of the Phase Structure and Morphology of iPP/PEOc Blends Using Scanning Electron Microscopy

The influence of blend composition on the phase structure and morphology of poly(propylene)/poly(ethylene‐co‐octene) blends was studied using SEM. A diameter d_g was defined and calculated in real space to discuss the phase structure and morphology of iPP/PEOc blends. The figure‐estimation method was introduced to determine the distribution width of d_g. It was shown that the distribution of d_g obeys a log‐normal distribution and the distribution width σ of d_g was calculated. In wave‐number (h) space, the correlation distance, a_c, was defined by applying light scattering theory to power spectrum images obtained by 2D Fourier transformation. Moreover, a fractal dimension, D_c, was introduced to describe the uniformity of the spatial distribution.

     

Differential scanning calorimetric examination of melamine–formaldehyde microcapsules containing decane

The main objective of this study was to investigate the composition of microcapsules and the degree of curing of melamine–formaldehyde (MF) resin, which formed a shell of microcapsules, by the use of differential dynamic calorimetry (DSC). For this purpose, decane was chosen as core material. The microencapsulation of decane with MF resin was carried out at different temperatures and pH values. The temperature and pH value were kept constant during the process. The composition of the microcapsules and the degree of curing of the shell material were studied during and after the microencapsulation process. DSC analysis, in combination with scanning electron microscopy analysis, was revealed as an effective tool for the investigation of the microencapsulation process with MF resin. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and antibiofouling properties of novel crosslinkable terpolymers containing semifluoroalkyl substituted aromatic side chains

Synthesis, contact angle analysis, surface properties and biofouling characteristics of novel crosslinkable terpolymers with semifluoroalkyl substituted aromatic side chains have been described. These polymers are targeted for use as coatings to prevent marine biofouling. The marine antifouling properties of these materials were evaluated by laboratory assays employing the fouling diatom Nitzschia and ubiquitous Staphylococcus aureusi. Results indicated that the experimental coatings exhibited better antibiofouling performance than that of a standard Poly(dimethyl siloxane) (PDMS) coating. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Synthesis and properties of polymer brush consisting of poly(phenylacetylene) main chain and poly(dimethylsiloxane) side chains

A novel polymer brush consisting of poly(phenylacetylene) (PPA) main chain and poly(dimethylsiloxane) (PDMS) side chains was synthesized by the polymerization of phenylacetylene-terminated PDMS macromonomer (M-PDMS). The macromonomer was prepared by the esterfication of monohydroxy-ended PDMS (PDMS-OH, degree of polymerization (DP) = 42) with p-ethynylbenzoic acid. The polymerization of M-PDMS using [(nbd)RhCl]₂/Et₃N catalyst led to polymer brush, poly(M-PDMS), with M_n up to 349?000 (DP of main chain 104). Poly(M-PDMS) with narrow molecular weight distribution (M_n = 39?900, M_w/M_n = 1.11) was obtained with a vinyl-Rh catalyst, [Rh{C(Ph)CPh₂}(nbd){P(4-FC₆H₄)₃}]/(4-FC₆H₄)₃P. Poly(M-PDMS)s were brown to orange viscous liquids and soluble in organic solvents such as toluene and CHCl₃. The UV-vis absorptions of poly(M-PDMS) were observed in the range of 350-525 nm, which are attributable to the PPA main chain.