Effect of non-Gaussian chains on fluctuations of junctions in bimodal networks

A simple tetrahedron model is used to study the effect of non-Gaussian chains on fluctuations of junctions in bimodal networks. The four chains are assumed to meet at a junction with their other ends being fixed at the vertices of the tetrahedron. It is assumed that the angles between mean end-to-end vectors of all four chains connected at the junction are tetrahedral, but the lengths of edges of the tetrahedron may differ due to the difference in the lengths of the chains. The central junction is free to fluctuate, subject to the constraints imposed by the pendant chains. The long chains are chosen to be Gaussian. The short chains are assumed to be non-Gaussian. Calculations show that the non-Gaussian nature of the short chains imposes severe restrictions on the fluctuations of the central junction. The strength of these restrictions directs attention to the importance of anharmonic modes in networks.     

Some dynamic mechanical properties of unimodal and bimodal networks of poly(dimethylsiloxane)

Summary Elastomeric networks of polydimethylsiloxane prepared by end-linking chains having molecular weights in the range 18,500 to 220 g mol^-1 were studied from -128 to 50°C using a Rheovibron DDV III Viscoelastometer. In the case of the unimodal networks, the glass transition temperature T_g was generally insensitive to degree of cross-linking. The intensity of the tan δ relaxation, however, increased by over an order of magnitude over the range of cross-link densities investigated. Bimodal networks prepared from mixtures of relatively long and very short PDMS chains also had values of T_g which were insensitive to degree of cross-linking. Finally, as expected, the intensities of the tan δ peak for the bimodal networks could not be explained on the basis of simple additivity of contributions from the relatively long and the very short network chains.     

A study of the sintering of diatomaceous earth to produce porous ceramic monoliths with bimodal porosity and high strength

Diatomite powder, a naturally occurring porous raw material, was used to fabricate ceramic materials with bimodal porosity and high strength. The effect of the sintering temperature on the density and porosity of dry pressed diatomite green bodies was evaluated using mercury porosimetry and water immersion measurements. It was found that the intrinsic porosity of the diatomite particles with a pore size around 0.2 µm was lost at sintering temperatures above 1200 °C. Maintaining the sintering temperature at around 1000 °C resulted in highly porous materials that also displayed a high compressive strength. Microstructural studies by scanning electron microscopy and energy-dispersive X-ray analysis suggested that the pore collapse was facilitated by the presence of low melting impurities like Na₂O and K₂O.     

Preparation of mesoporous NiO with a bimodal pore size distribution and application in electrochemical capacitors

Mesoporous nickel oxide with a porous structure exhibiting a bimodal pore size distribution (2.6 and 30.3 nm diameter pores) has been synthesized in this paper. Firstly, a mesoporous precursor of coordination complex Ni₃(btc)₂·12H₂O (btc = 1,3,5-benzenrtricarboxylic acid) is synthesized based on the metal-organic coordination mechanism by a hydrothermal method. Then mesoporous NiO with a bimodal size distribution is obtained by calcining the precursor in the air, and characterized by transmission electron microscopy and N₂ adsorption measurements. Such unique multiple porous structure indicates a promising application of the obtained NiO as electrode materials for supercapacitors. The electrochemical behavior has been investigated by cyclic voltammogram, electrochemical impedance spectra and chronopotentiometry in 3 wt.% KOH aqueous electrolyte. The results reveal that the prepared NiO has high-capacitance retention at high scan rate and exhibits excellent cycle-life stability due to its special mesoporous character with bimodal size distribution.     

Thermal properties and surface energy characteristics of interpenetrating polyacrylate and polybenzoxazine networks

We have prepared semi-interpenetrating polyacrylate networks (PA/BA-m s-IPNs) through rapid photopolymerization of a triacrylate monomer (TMPTA) in the presence of a photoinitiator (I184), a tetramercaptane transfer agent (4SH), and N-methyl-bisbenzoxazine (BA-m). Next, we prepared novel fully interpenetrating polyacrylate (PA) and polybenzoxazine (PBZ) networks (PA/PBZ f-IPNs) through thermal polymerization of the BA-m monomer at 180 °C for 4 h. For the PA/BA-m s-IPNs, the BA-m monomers can be frozen and dispersed in the UV-cured PA network within 5 min to inhibit macrophase separation. After thermal polymerization, the phenol units of the ring-opened PBZ segments can form a hydrogen-bonding interface with the carbonyl groups to improve the compatibility between the PBZ microdomains and the PA networks. From an analysis using Kissinger's method, the non-isothermal kinetics of the thermal polymerization for the PA/BA-m s-IPNs indicate that an increase in the PA content increased the steric hindrance of PBZ polymerization. We used DSC, TGA, and contact angle analyses to determine the glass transition temperature, thermal stability, and surface free energy, respectively, of the PA/PBZ f-IPNs. The thermal stability and surface free energy of these PA/PBZ f-IPNs display linear relationships with respect to the PBZ content.     

Epoxy networks toughened by core–Shell particles: Influence of the particle structure and size on the rheological and mechanical properties

The core–shell particles considered were poly(butyl acrylate) core/epoxy groups functionalizing the poly(methyl methacrylate) shell. Physical and thermomechanical properties of benzyl dimethylamine (BDMA)‐catalyzed diglycidyl ether of bisphenol A (DGEBA)/dicyandiamine epoxy networks toughened with core–shell particles were studied. The blends were prepared under well‐defined processing conditions. The resulting properties were found to depend on the state of the dispersion of the particles in the prepolymer matrix before crosslinking. These particles were dispersed at different volume fractions in order to vary the interparticle distance. The relationships between the size of the core–shell particles and the level of toughening are reported. Static mechanical tests were performed in tension and compression modes on these core–shell polyepoxy blends. A slight decrease in the Young's modulus and an increase in the ability to plastic deformation were observed. Using linear fracture mechanics (LEFM), an improvement of the fracture properties (K_IC) was measured. By varying the volume fraction of core–shell particles, an optimum toughness improvement was found for an interparticle distance equal to 400 nm (with an average particle size of 600 nm). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 849–858, 1999     

Dicyanate ester–polyetherimide semi‐interpenetrating polymer networks. II. Effects of morphology on the fracture toughness and mechanical properties

A high temperature thermosetting bisphenol‐A dicyanate (BADCy) was modified with polyetherimide (PEI) at various compositions. The effects of the morphology of the blends on the fracture toughness and mechanical properties were investigated. For this purpose, fracture, flexural, and compression tests were carried out. The fracture surfaces of the broken specimens were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The morphology was controlled by changing the curing conditions and PEI content. A good correlation between fracture properties and microstructural features of the mixtures has been observed. The phase‐inverted morphologies showed the highest fracture toughness, which was further increased by increasing the cure temperature. The mechanical properties of the matrix (modulus, yield strength) were not affected by the addition of the thermoplastic. Fracture energy values show similar trends for the different mechanical tests performed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2759–2767, 2001     

Gas permeability of model polyurethane networks and hybrid organic-inorganic materials: Relations with morphology

Various polyurethane (PU) and hybrid organic-inorganic networks based on isocyanate chemistry were synthesized using a two-stage method. All the networks were amorphous. For PU membranes the morphology and the permeability coefficients of different gases (H₂, N₂, O₂) were a function of the polarity and the chain length of the soft segment and a function of the composition of the networks. The membranes based on the same soft segment chain length and on the same molar composition were structurally nanoheterogeneous systems for the less polar soft segments (α, ω-hydroxy-terminated hydrogenated polybutadiene and a fatty acid oligoester). They were homogeneous for a polycaprolactone type soft segment. The gas diffusion was appreciably hindered in the case of better miscibility between the soft chains and the hard crosslinks. Decreasing the soft segment length decreased the gas permeability coefficient of the network. As the chemical compositions were changed by increasing the soft segment content, an increase in permeability coefficients was observed. The morphology and transport properties of PU networks and hybrid organic-inorganic networks with low inorganic content were compared for the same soft segment content. The similarities observed between the two types of networks led us to conclude that the organic or inorganic nature of the crosslinking agent has no influence on the gas transport properties of these networks. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2579–2587, 1997     

Experimental and theoretical investigations on petroleum-based elastomers with two cross-linking systems of different lengths viewed as bimodal networks

A review with 36 references discussing the chemistry and the structure-property relationship of elastomers cured with two cross-linking systems of different chain lengths such as sulfur and the polymerization products of p-benzoquinone and viewed as bimodal networks. These exceptional networks have shown remarkable improvements in the overall mechanical properties which are anticipated to be due to the non-Gaussian effects known for bimodal networks and evident by the anomalous upturn in the modulus values in Mooney-Rivlin stress-strain data representations. Proton and ¹³C NMR as well as energy minimization calculations were used to study the chemical structures and single chain contributions of polyquinones. Nuclei bending of these oligomers have shown to be greatly influenced by the restricted torsional behavior due to the presence of the hydrogen bonds between the benzenoid nuclei. Intrinsic atomic-level forces for the networks were evaluated using molecular dynamics techniques and showed that while the forces acting on the junction points of the cross-linking segments and the elastomeric chains had no apparent change as a consequence of the networks' bimodal formation, forces acting on the short chains of the bimodal networks are of much higher values as compared to those of unimodal networks. The presence of the relatively long polyquinone chains in the bimodal networks has caused the short sulfur chains to stretch to its maximum extensibility and no longer can increase its end-to-end distance separation by simple rotations about its skeletal bonds. Limited chain extensibility of the short chains resulting from the deformation of the bond angles and bond lengths has lead to higher potential energies. Studies on the swollen bimodal networks have validated the above conclusions since swelling of the networks will prevent the elastomeric chains from undergoing possible strain-induced crystallization during the stress-strain experiments and any abnormalities in the mechanical behavior of these networks must be therefore the result of the limited extensibility of the short chains of the networks.     

Synthesis and Properties of Interpenetrating Polymer Networks Composed of Epoxy Resins and Polysulphones with Cross-linkable Pendant Vinylbenzyl Groups

Polysulphones with cross-linkable pendant vinylbenzyl groups (PSF-VB) were prepared via chloromethylation of commercial polysulphones. The curing reactivity of PSF-VB was investigated by differential scanning calori-metry. Interpenetrating polymer networks (IPNs) were prepared based on bisphenol A diglycidyl ether (DGEBA) and PSF-VB, where DGEBA was cured by 4,4′-diaminodiphenyl sulphone and VB groups of PSF-VB were radically polymerized using dicumyl peroxide (DCP). Polysulphones having pendant benzyl groups (PSF-Bz) were also prepared and used as non-reactive modifiers. The fracture toughness (K_IC) for the resulting epoxy/PSF-VB IPN increased by 65% with no loss of mechanical properties on 10wt% addition of PSF-VB (7·9mol% VB unit, MW 74000). Non-reactive PSF-Bz was less effective than PSF-VB. Although the PSF-Bz modified resin had a particulate structure, the morphologies of the PSF-VB/epoxy IPNs were not clear from scanning electron micrographs. Furthermore, the epoxy/PSF-VB IPNs had higher solvent resistance than the epoxy/PSF-Bz blends. Morphological behaviour, modification results and high solvent resistance of the cured epoxy/PSF-VB resins indicate that cross-linked PSF-VB and the epoxy network entangled fully in the presence of DCP. © of SCI.     

利用夹点技术分析优化甲基叔戊基醚装置换热网络

利用Aspen Plus软件计算出冷流股和热流股的焓变,冷热流股的焓变分别为1.4W和-1.2W,然后运用夹点技术对甲基叔戊基醚固定床装置换热网络进行优化分析.计算结果表明,优化后的换热网络节能效果较好.通过小试数据,可以推断中试乃至工业化装置的换热网络节能情况.     

Elaboration of a new anion-exchange membrane with semi-interpenetrating polymer networks and characterisation

A new anion-exchange membrane was prepared using the semi-interpenetrating networks (SIPN) technique. Poly(vinyl alcohol) (PVA) was chosen as the polymer matrix. Poly(1,3-diethyl-1-vinylimidazolium bromide) (PDVIBr) was first synthesised and characterised in order to use it as the cationic polyelectrolyte (Pe). The membrane was obtained by mixing aqueous PVA and Pe solutions (ratio 60/40), followed by evaporation and crosslinking with gaseous 1,2-dibromoethane. The influence of the crosslinking conditions on the sample properties was studied by infrared spectroscopy. The efficiency of the entrapment was monitored by swelling ratio and ion-exchange measurements. Ion-diffusion experiments, membrane conductivity measurements and ion-transport numbers calculations were performed on the membrane to highlight its ion-exchange properties.     

Unsaturated polyesters: influence of the molar mass on the cure with styrene and the properties of the resulting networks

Fractions of an unsaturated polyester resin (UP), based on 1 mol maleic anhydride, 1 mol isophthalic acid, 1 mol propylene glycol, and 1 mol diethylene glycol, were obtained from an industrial reactor at various times during polyesterification. They were characterized by ¹H-NMR and chemical titration. Increasing the reaction time from 1 to 9 h led to an increase in (a) the number-average molar mass (M_n) in the range 484–1712 g/mol, (b) the maleic acid–fumaric acid isomerization from 85 to 95%, (c) the glass transition temperature (T_g) from 251 to 267 K, and (d) the compatibility with styrene. Several of these fractions were cured with styrene, in amounts ranging from S/E = 2–5 (molar ratio of CC double bonds in styrene, S, and unsaturated polyester, E), using benzoyl peroxide as an initiator. Increasing M_n led to an increase in the T_g value and a decrease in the amount of moisture absorption. Both effects were explained by the decrease in the concentration of the polar end groups present in the UP chains. However, using a relatively high styrene fraction in the formulation (i.e., S/E = 5) led to cured products exhibiting reasonably high T_g values (approaching the pure polystyrene value) combined with a low moisture absorption. This constitutes a practical way to revalorize batches of UP resins with molar masses out of specification. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 755–760, 1997     

Solid polymer electrolytes V: microstructure and ionic conductivity of epoxide-crosslinked polyether networks doped with LiClO4

A crosslinked polyether network was prepared from poly(ethylene glycol) diglycidyl ether (PEGDE) cured with poly(propylene oxide) polyamine. Significant interactions between ions and polymer host have been observed for the crosslinked polyether network in the presence of LiClO₄ by means of FT-IR, DSC, TGA, and ⁷Li MAS solid-state NMR. Thermal stability and ionic conductivity of these complexes were also investigated by TGA and AC impedance measurements. The results of FT-IR, DSC, TGA and ⁷Li MAS solid-state NMR measurements indicate the formation of different types of complexes through the interaction of ions with different coordination sites of polymer electrolyte networks. The dependence of ionic conductivity was investigated as a function of temperature, LiClO₄ concentration and the molecular weight of polyether curing agents. It is observed that the behavior of ion transport follows the empirical Vogel-Tamman-Fulcher (VTF) type relationship for all the samples, implying the diffusion of charge carrier is assisted by the segmental motions of polymer chains. Moreover, the conductivity is also correlated with the interactions between ions and polymer host, and the maximum ionic conductivity occurs at the LiClO₄ concentration of [O]/[Li⁺]=15.     

Semi-interpenetrating polymer networks of Nafion and fluorine-containing polyimide with crosslinkable vinyl group

Fluorine-containing polyimide with crosslinkable vinyl group (FPI) was synthesized from 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB), and 4-amino styrene (AS). The reinforced composite membranes based on semi-interpenetrating polymer networks (semi-IPN) were prepared via solution casting of FPI and Nafion^®212, and crosslinking thereafter. The water uptake, swelling ratio, mechanical properties, thermal behavior, proton conductivity, and oxidative stability of the composite membranes were investigated. Compared with the recast Nafion^® 212, the composite membrane shows better mechanical properties and improved dimensional stability. The tensile strength of the composite membranes ranges from 39.0 MPa to 80.0 MPa, which is higher than that of the recast Nafion^® 212 membrane (26.6 MPa). The dimensional stability of the composite membranes increases with increasing FPI content in the membranes, whereas the proton conductivity decreases. The composite membranes show considerable proton conductivity from 2.0 × 10⁻² S cm⁻¹ to 8.9 × 10⁻² S cm⁻¹ at a temperature from 30 °C to 100 °C, depending on the FPI contents. The composite membranes with semi-IPN from FPI and Nafion^®212 have considerable high proton conductivity, excellent mechanical properties, thermal and dimensional stabilities.     

宽温域高阻尼互穿聚合物网络材料的结构与性能

以环氧丙烯酸酯和甲基丙烯酸丁酯(二者质量比为2/1)混合物为乙烯基酯树脂(VER)。1,4-丁二醇为扩链荆,采用“同步互穿”工艺,室温下与聚氨酯(PU)预聚物固化制备了低温至室温区阻尼温域近70℃、损耗因子(tanδ)大于0．4的PU/VER互穿聚合物网络(IPN)。结果表明,当PU/VER(质量比,下同)为70/30时,IPN的tanδ大于0.7的阻尼温域近40℃。采用傅里叶变换红外光谱仪及原子力显微镜考察了试样的连续相构成及微观结构表明,形成的双相连续“同步互穿”体系的相畴尺寸在纳米级范围,组成比为70/30的IPN较50/50者相容性好。力学性能测试结果表明,随VER用量的增加．试样具有由弹性到脆性的形变规律。     

A property‐based approach to the synthesis of material conservation networks with economic and environmental objectives

This article presents a multiobjective optimization model for the recycle and reuse networks based on properties while accounting for the environmental implications of the discharged wastes using life‐cycle assessment. The economic objective function considers fresh sources and treatment costs, whereas the environmental objective function is measured through the eco‐indicator 99. The model considers constraints in the process sinks as well as in the environment based on stream properties such as pH, chemical oxygen demand, toxicity, density, and color, in addition to the composition of the waste streams. A global optimization procedure is developed by indirectly tackling properties through property operators and by segregating the process streams before treatment. Three examples are included, and the results show that it is possible to consider simultaneously the trade‐offs between the total annual costs and the overall environmental impact using the proposed methodology. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Stochastic molecular descriptors for polymers. 4. Study of complex mixtures with topological indices of mass spectra spiral and star networks: The blood proteome case

The Quantitative Structure-Property Relationships (QSPRs) based on Graph or Network Theory are important for predicting the properties of polymeric systems. In the three previous papers of this series (Polymer 45 (2004) 3845-3853; Polymer 46 (2005) 2791-2798; and Polymer 46 (2005) 6461-6473) we focused on the uses of molecular graph parameters called topological indices (TIs) to link the structure of polymers with their biological properties. However, there has been little effort to extend these TIs to the study of complex mixtures of artificial polymers or biopolymers such as nucleic acids and proteins. In this sense, Blood Proteome (BP) is one of the most important and complex mixtures containing protein polymers. For instance, outcomes obtained by Mass Spectrometry (MS) analysis of BP are very useful for the early detection of diseases and drug-induced toxicities. Here, we use two Spiral and Star Network representations of the MS outcomes and defined a new type of TIs. The new TIs introduced here are the spectral moments (π_k) of the stochastic matrix associated to the Spiral graph and describe non-linear relationships between the different regions of the MS characteristic of BP. We used the MARCH-INSIDE approach to calculate the π_k(SN) of different BP samples and S2SNet to determine several Star graph TIs. In the second step, we develop the corresponding Quantitative Proteome-Property Relationship (QPPR) models using the Linear Discriminant Analysis (LDA). QPPRs are the analogues of QSPRs in the case of complex biopolymer mixtures. Specifically, the new QPPRs derived here may be used to detect drug-induced cardiac toxicities from BP samples. Different Machine Learning classification algorithms were used to fit the QPPRs based on π_k(SN), showing J48 decision tree classifier to have the best performance. These results suggest that the present approach captures important features of the complex biopolymers mixtures and opens new opportunities to the application of the idea supporting classic QSPRs in polymer sciences.     

含有互穿网络结构的丁腈橡胶改性环氧/酚醛胶粘剂的合成及其应用

合成了一种含有互穿网络结构的丁腈橡胶(BN)改性环氧/酚醛胶粘剂。通过扫描电镜(SEM)分析, 证明了此胶片具有互穿网络结构。同时对胶粘剂进行了差热分析(DTA),并考察了其粘结性能以及贮存性能。最后将其成功地应用到一种厚铜箔(0.4～0.5mm)环氧玻璃布层压板上,得到的覆铜板样品具有剥离强度高、平整度好、电性能优良等特点。     

Microstructural relationship with fracture toughness of undoped and rare earths (Y, La) doped Al2O3–ZrO2 ceramic composites

Ceramic composites in undoped Al₂O₃–5 wt% ZrO₂ (AZ) and doped with rare earth elements Y, La separately and simultaneously were prepared by solid state sintering process. These composites were characterized for microstructural investigation and determination of phase formation to draw a possible relationship between these characterization results with the fracture toughness measured by single-edge precracked beam (SEPB) test method using three-point bend test. The fracture toughnesses of Y and Y + La doped AZ are found to be higher for samples sintered at 1700 °C for long soaking times, than that of La doped and undoped AZ composites. It is predicted from the XRD and EDS analyses that the phases of Zr_0.88Y_0.12O_1.94 and Zr_0.935Y_0.065O_1.968 are formed at or near the intergranular region and therefore the higher fracture toughness of Y and Y + La doped AZ composites compared to undoped AZ and La doped AZ composite for samples sintered at 1700 °C for long soaking times, is attributed to these intergranular phases.