STRUCTURE-PROPERTY RELATIONSHIPS IN POLYOLEFIN FOAMS

Two theoretical models that can be used to predict the thermal conductivity and Young's modulus of low-density polyethylene (LDPE) foams produced by a high-pressure nitrogen solution process are presented. The main factors that influence the properties of these materials were studied in terms of these models. The results show that the two properties depend on different factors. Moreover, the matrix polymer morphology of the foams was studied and compared to that of the solid sheet from which the foams were manufactured.     

Synthesis and Mechanical Characterization of Nanoparticles Infused Polyurethane Foams; Statistical Analysis of Foam Morphology

Nanocomposite polyurethane foams filled with different loadings (0.1–0.7 wt.%) of nanosized silica (average grain size of about 7 or 12 nm) and organoclay were prepared by a prepolymer method, and their mechanical properties were investigated. Statistical analysis of the size distribution of the foam cells was successfully applied for the characterization of their morphology. It was shown that the developed approach provided detailed analysis of the morphology development in PU foams, including the primary cell formation and their break-up and coalescence. The degree of phase separation in nanocomposite polyurethane foams in its dependence on nanofiller type and content was calculated from the IR spectra. The presence of silica nanoparticles and organoclays gives rise to significant differences in the mechanical (stress–strain) properties of the nanocomposite polyurethane foams with respect to the pure polymer.     

In situ observations of compressive behaviour of aluminium foams by local tomography using high-resolution X-rays

We have investigated the compressive behaviour of closed-cell aluminium foams using a high-resolution X-ray CT. The microstructures of cell walls or Plateau borders in the foams were visualized in 3D using the local tomography technique which is a high-resolution CT method to reconstruct a region of interest within a large sample. The shapes and the 3D distribution of micropores, particles, and regions of solute segregation in the foams are evaluated, comparing the cell walls with the Plateau borders. Under compressive loads, the damage behaviour of such microstructures has been observed using an in situ test rig. It is found that the microcracks were mainly initiated from the cell walls and the micropores with large diameters were also damaged. The crack initiation sites are classified from the results. In addition, a method for non-destructive characterization of elastic and plastic deformation in the foams, which is called a 3D microstructure gauge (MG) method, is presented. Thousands of micropores as markers on each load were automatically matched by the information of those volumes and surface areas. The local strain mapping by the MG indicates that the edges of the micropores with large diameters have large strain under compression and this is consistent with the crack analyses.     

Fabrication and Physical Characterization of Biodegradable Poly(butylene succinate)/Carbon Nanofiber Nanocomposite Foams

Nanocomposites of biodegradable poly(butylene succinate) (PBS) and carbon nanofibers (CNFs) were prepared by three different methods, that is, solution blending, melt compounding, and solution and subsequent melt blending (SOAM) method, among which the SOAM method, where nano-scale fillers and polymer matrix are solution-blended and subsequently melt-mixed in a torque rheometer, is a two-step process for obtaining polymer nanocomposite. Dispersion of CNFs in the PBS matrix was characterized by FE-SEM, while thermal and mechanical properties were analyzed by thermogravimetric ananlysis (TGA) and universal test machine (UTM), respectively. The PBS/CNF nanocomposites were then converted to foams by employing a chemical blowing agent (CBA) in the melt. The presence of CNFs increased the melt viscosity of PBS so that the PBS/CNF nanocomposite foams were produced without modifying the chemical structure of the PBS. Nanocomposite foams prepared by the SOAM method showed higher physical properties compared with those prepared by the solution blending and the melt mixing. Cell size and blowing ratio increased with the increase in the CBA content, blowing temperature and time. Cell morphology of the nanocomposite foams was examined by optical microscopy, and the cell size distribution was also investigated.     

Impact of γ-rays on constructional,optical and thermal behavior of alkaline and non alkaline low density polyethylene

ABSTRACT

In this study, we investigated the graft copolymerization of methyl methacrylate (MMA) onto low-density polyethylene (LDPE) in the presence of aniline as an inhibitor by gamma radiation. An alkaline treatment was carried out for the prepared graft copolymer. The structural properties of the prepared samples were examined via X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD peaks were slightly shifted, indicating an interaction between MMA and the polyethylene matrix. The morphology of the samples confirmed the homogenous grafted phase scattered onto the LDPE surface. Analysis of the absorption spectra indicated an allowed indirect transition mechanism. The Urbach energy (E_U) results showed that the value of the E_U for grafted LDPE was found to be higher than that of pure LDPE—up to 15?kGy irradiation dose, although this value decreases upon grafting. However, the value of the E_U for alkaline-treated grafted films decreases systematically by increasing the degree of grafting. The thermogravimetric analysis (TGA) of the sample indicated that the thermal stability of LDPE samples is significantly changed by grafting MMA onto it. Horowitz and Metzger's models were utilized to measure the activation energy of the thermal decomposition of all samples.     

Statistical Analysis of Morphology of Low Density Polyethylene/Polyamide 6 Blends with Addition of Organoclay and Maleic Anhydride-Grafted Polystyrene-b-Poly(Ethylene-co-Butene-1)-b-Polystyrene Copolymer As Compatibilizers

Statistical analysis of the size distribution of a polymer minor phase droplets was successfully applied for the characterization of the morphology in a LDPE/PA6 blend (75/25 wt/wt) obtained after mixing with added SEBS-g-MA(S) compatibilizer and/or organoclay 20A. It was shown that the developed approach provided detailed analysis of the morphology development in the polymer blends, including the primary droplets formation of the minor polymer phase and their break-up and coalescence. The introduction of organoclay increased the break-up of primary droplets and completely suppressed their coalescence. The addition of compatibilizer S, in contrast to nanoclay, did not suppress coalescence but the mean size of the primary droplets as well as the droplets formed at coalescence was strongly reduced. The combined addition of compatibilizer S and nanoclay did not change the morphology development of the LDPE/PA6 blend. Both processes of the droplet transformation were accelerated, similar to the system with addition of compatibilizer S only. However, an increase of nanoclay amount disturbed the break-up of the primary droplets, and the mean size of these droplets increases. Thereafter, the mean size of droplets formed at coalescence also increased. The results of statistical analysis of the phase morphology were found to correlate with the mechanical properties of the polymer blends. The fine dispersion of the minor polymer phase improved the stiffness of the polymer blends. For enhanced impact properties, the presence of relatively broad distribution of the minor polymer phase was necessary.     

低密度微孔聚合物泡沫的制备

 介绍了一种利用聚合物和溶剂的相分离，经过冷冻干燥来制备聚合物泡沫（特别是聚苯乙烯类泡沫）的通用技术。采用该技术制备的具有开放状孔洞结构的聚苯乙烯泡沫的密度为0.02~0.1g/cm3，平均孔径为1～20μm，而且泡沫具有各向同性，孔径非常均匀。通过对聚合物泡沫的表征，对影响泡沫形貌和密度的因素，如聚合物/溶剂体系，冷却速率等进行了研究，结果表明：所用溶剂对于该聚合物的Θ温度（溶剂与聚合物作用力为零的温度）必须高于该溶剂的熔点；采用单轴冷却方式可以减小由于溶液中心处和外围处的温差而引起的热应力对泡沫形貌的影响，冷却速率为100℃/min。     

Formulation and mechanical properties of emulsion-based model polymer foams

We produce cellular material based on the formulation of model emulsions whose drop size and composition may be continuously tuned. The obtained solid foams are characterized by narrow cell and pore size distributions in direct relation with the emulsion structure. The mechanical properties are examined, by varying independently the cell size and the foam density, and compared to theoretical predictions. Surprisingly, at constant density, Young’s modulus depends on the cell size. We believe that this observation results from the heterogeneous nature of the solid material constituting the cell walls and propose a mean-field approach that allows describing the experimental data. We discuss the possible origin of the heterogeneity and suggest that the presence of an excess of surfactant close to the interface results in a softer polymer layer near the surface and a harder layer in the bulk.     

Radiative properties of extruded polystyrene foams: Predictive model and experimental results

The radiative properties of extruded polystyrene foams (XPS) were predicted using morphological data and optical properties of bulk medium. A particular attention was paid on the modelling of the radiative properties of struts, which are located at the junctions between cell walls. The radiative properties of XPS foams were determined by adding the contributions of each particle (walls and struts) using the independent scattering hypothesis. Hemispherical reflectance and transmittance measurements were made in addition to total thermal conductivity measurements. Comparisons were made between theoretical and experimental results and some improvements were suggested to better improve modelling of foam radiative properties.     

低密度聚亚胺酮泡沫的制备

确定了以1,4-二氧六环为溶剂体系,经热致相分离和冷冻干燥技术制备了低密度聚亚胺酮泡沫,分析了其质量浓度对泡沫密度的影响,结果显示:泡沫实验密度与聚合物浓度有较好的线性关系,可实现对泡沫密度的有效控制。差示扫描量热法、热重法等热性能测试结果表明:聚亚胺酮泡沫材料的热分解行为与本体材料一致,但玻璃化温度较本体材料玻璃化温度高。泡沫孔结构测试结果表明:随着密度的增加,平均孔径有降低的趋势,孔径分布趋于单一化。对其力学性能进行分析可知:所制备的泡沫硬而强,具有较高的模量和抗压强度,断裂压缩随密度增加而增加。随着泡沫密度的增加,其破坏形变随之增加。     

Electrical and dynamic mechanical behavior of BaTiO3/VGCF/LDPE composite

The electrical and dynamic mechanical behavior of barium titanate (BaTiO₃)/vapor-grown carbon fiber (VGCF)/Low Density Polyethylene (LDPE) composites has been studied. The measurement of electrical conductivity exhibits a lower percolation threshold and a more distinct two-stage percolation region, especially with a wide plateau between the two stages, for BaTiO₃/VGCF/LDPE composites compared to the two-component system of VGCF/LDPE. This can be attributed to increase of the effective concentration of VGCF and the obstruction of BaTiO₃ particles on VGCF networks. The dynamic mechanical spectra of BaTiO₃/VGCF/LDPE composites present a distinctive α relaxation region with its peak value nearly remaining constant at its high temperature side in contrast to the abrupt decrease of LDPE. Moreover, the loss factor in the α relaxation region reaches its largest value for the composite of 8 vol% VGCF content. This means that the piezo-damping effect really functions in BaTiO₃/VGCF/LDPE composites and only in certain conditions can this effect have practical significance. Further examination of the damping behavior in a different relaxation region demonstrates that the piezo-damping effect is directly related to the relaxation behavior of the polymeric matrix. Also, the piezo-damping effect is highly temperature and frequency dependent. The dielectric measurements suggest that, before the formation of a certain critical conducting state, the energy dissipation approach of the piezo-damping effect may be mainly determined by the interfacial polarization effect in the composite. Thus, it may be inferred that the piezo-damping effect also contributes to the dramatic increase of the loss factor at the high temperature side of the α relaxation peak for the BaTiO₃/LDPE composite and functions practically even if there is no presence of VGCF.     

Controlling the micro/nanostructure of self-cleaning polymer coating

Polypropylene bio-mimic self-cleaning surfaces with porous micro-nano-binary morphology structures were prepared by a simple casting method. The influence of the cooling process and solvent composition on water contact angle, sliding angles and self-cleaning properties has been investigated. Detailed SEM morphology studies revealed that the polymer used in this work is commercial-grade granular low-density polyethylene (LDPE) forms petal-like crystalline, which are of micrometer scale in length and nanometer scale in thickness. The nano-crystallines on the surface represent a porous three-dimensional micro-nano-binary structure. It was found that a compromise to the film porosity and crystal nano structure is essential for achieving a satisfied self-cleaning surface. Under optimum condition, a water contact angle of 152.2°, and a sliding angle of 1.7° can be obtained using this simple method.     

Morphology and Pore Size Distribution of Biocompatible Interconnected Porous Poly(L-lactic acid) Foams with Nanofibrous Structure Prepared by Thermally Induced Liquid–Liquid Phase Separation

Biocompatible, highly interconnected microporous poly(L-lactic acid) (PLLA) foams with nanofibrous structure, containing pores with average diameter below 1 μm and fibers with diameters of 10² nm scale, were prepared through the thermally induced liquid–liquid phase separation (TIPS) method consisting of quenching of the PLLA solution, freeze extraction with ethanol, and vacuum drying. Diverse foam morphologies were obtained by systematically changing parameters involved in the TIPS process, such as polymer concentration, solvent composition, and quenching temperatures. The morphology of different foams was examined by scanning electron microscopy to characterize the pore size and the pore size distribution. The results showed that most porous foams had a nanofibrous structure with interconnected open pores. In the case of using tetrahydrofuran (THF) as solvent, the higher the PLLA concentration, the smaller the average pore diameter and the narrower the pore size distribution. In the case of using the mixed solvents of THF/DOX (1,4-dioxane) with higher than 6/4 volume ratio, there appeared a maximum value of average pore diameter and a widest pore size distribution at 0.09 g/mL PLLA concentration. The average pore diameter of the foams increased with increasing DOX content in the mixed solvent and ranged from 0.2 to 0.9 μm depending on the process parameters. When the DOX content reached 60% by volume, the morphology of the foams contained some large closed pores with diameter ranging from 1 to 10 μm. By decreasing the quenching temperature, the average pore diameter of foams decreased and the pore size distribution became narrower. All the pore size distribution fit F-distribution equations.     

Structure formation of supercooled polymers in confined geometries -- A molecular-dynamics simulation study

Molecular-dynamics simulations of thin polymer films are performed with a recently introduced coarse-grained model. This model reproduces many features of polymer crystallization from the melt. In this work, we show how confining walls influence the structure formation depending on the degree of supercooling. Already in the melt at high temperature a preorder is induced near the walls. On lowering the temperature, crystalline order nucleates at the walls, from which it propagates into the film. We show how this growth can be influenced by prestructuring the wall.Received: 1 January 2003, Published online: 21 October 2003PACS: 61.20.Ja Computer simulation of liquid structure - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 68.55.-a Thin film structure and morphology     

Experimental Cosserat elasticity in open-cell polymer foam

Reticulated open-cell polymer foams exhibit substantial size effects in torsion and bending: slender specimens are more rigid than anticipated via classical elasticity. Such size effects are predicted by Cosserat (micropolar) elasticity, which allows points to rotate as well as translate and incorporates distributed moments (couple stresses). The Cosserat characteristic length is larger than the cell size. The Cosserat coupling coefficient is larger than in dense closed-cell foams and approaches 1 for foam with 0.4 mm cells.     

聚丙烯酸酯泡沫密度均匀性的射线检测技术

 低密度泡沫材料大多存在一定程度的密度不均匀性，这对其后续使用性能将带来不良影响。文中简述了ICF靶用聚丙烯酸酯泡沫的制备方法，并利用β射线和X射线检测技术，对直径为mm量级的低密度聚丙烯酸酯泡沫柱进行密度分布表征。研究结果表明：泡沫柱沿轴向的密度分布比较均匀，而沿径向呈内低外高分布，形成了明显的密度梯度。实验表明：射线检测技术测量靶用低密度泡沫的方法可基本满足目前的实验要求，但密度分辨率和空间分辨率还有待进一步提高。     

Phase Diagrams of Semicrystalline Polymer–Crystalline Substances: Polyolefins–1,2,4,5-Tetrachlorobenzene

The full phase diagrams of low-density polyethylene (LDPE), high-density polyethylene (HDPE), and isotactic polypropylene (i-PP) mixtures with 1,2,4,5-tetrachlorobenzene (TeCB), including the solubility curve of TeCB in a solid polymer, were constructed by an optical method. The diagrams contain a eutectic point that corresponds to the situation when the crystallization of TeCB out of its solution in a polyolefin is accompanied by the crystallization of monomer units of the macromolecules. As a result, the polymer acquires a gel structure with crystallites as crosslinks and amorphous regions saturated with TeCB. It is demonstrated that the eutectic point position on the phase diagram can be used for ranking polymers with respect to their thermodynamic affinity to a solvent. For the studied systems, the affinity to TeCB was decreased in the order i-PP, HDPE, and LDPE. Direct experimental evidence was obtained that TeCB crystals can be dissolved in a solid polymer via a vapor phase mechanism, which leads to the polymer amorphization.     

低密度聚环己基乙烯泡沫的制备

低密度CH聚合物多孔材料是惯性约束聚变(ICF)的重要靶材料,利用热致相分离原理对低密度聚环己基乙烯泡沫的制备进行了研究。首先通过聚苯乙烯(PS)氢化反应制备了聚环己基乙烯(PVCH),经过溶剂选择,确定以环己烷/1,4-二氧六环为溶剂体系,经热致相分离和冷冻干燥技术制备出低密度PVCH泡沫。通过分析溶液浓度对泡沫密度的影响,确定了泡沫密度与聚合物溶液质量浓度之间的关系,在0.04~0.15 g/cm3范围之内可实现对泡沫密度的有效控制。泡沫孔结构测试结果表明随着密度的增加,平均孔径有升高的趋势,孔径分布趋于单一化,孔径范围为23.63~0.83μm。     

低密度PMP聚合物泡沫成型控制

为了进一步提高低密度聚-4-甲基-1-戊烯（PMP）聚合物泡沫的成型性能,满足惯性约束聚变物理实验的需求,采用热诱导倒相法结合原位成型和机械加工来进行低密度PMP聚合物泡沫的成型控制研究。 研究结果表明:在热诱导倒相法制备过程中,聚合物溶液形成凝胶后施加气压,再将其在加压状态下在液氮中淬火,可以大大减少得到的PMP/溶剂混合体中大的孔洞,提高其强度,并且在溶剂脱除后PMP泡沫收缩变小,微观结构更加均匀, 孔径更加细小。采用原位成型和机械加工的方法,可以实现低密度PMP聚合物泡沫的精密成型控制。     

低密度聚乙烯光引发交联机理——Ⅱ.BNB自旋捕捉ESR研究(英文)

在光引发剂二苯甲酮(BP)存在下,紫外光辐照低密度聚乙烯(LDPE)所形成的自由基中间体已被自旋捕捉剂2,4,6-三特丁基亚硝基苯(BNB)所捕捉,其自旋加合物自由基已为电子自旋共振(ESR)所特征。现已检测和鉴定到二种自旋加合物:一种是叔碳自由基;另一种是仲碳自由基。它们分别是由BP的激发三重态从LDPE链的支化点和亚甲基团上夺氢所形成的自由基中间体同自旋捕捉剂BNB反应生成的。上述的证据表明:LDPE的光引发交联点主要发生在叔碳和仲碳原子上,且H-型交联点占主导地位。