Foaming of trans‐polyisoprene using N2 as the blowing agent

Foaming of trans‐1,4‐polyisoprene (TPI) polymer was carried out through a batch process using nitrogen (N₂) as the blowing agent. TPI vulcanizates having varying crosslink densities were prepared by varying crosslinking agent content and curing time. The vulcanizates were then saturated with N₂ inside a pressure vessel at a pressure of 14 MPa and varying temperatures for 5 hours before effecting the foaming by rapidly quenching the pressure. The effects of varying the crosslinking agent content, silica filler content, and precuring time of the vulcanizates and the effects of varying the gas saturation temperature of foaming on the cell characteristics and physical properties of the foam prepared were investigated. The cells of the TPI foams had a spherical, closed structure. The density, expansion ratio, cell size, cell density, and tensile properties of the foams varied with varying crosslink density of the TPI vulcanizates as well as the saturation temperature of foaming. The important effects of crosslink density and saturation temperature on the N₂ solubility in the TPI matrix and thus on the foam expansion were discussed. The silica filler was found to be acting as a cell nucleating agent and reinforcing filler for the TPI foams.     

热塑性聚氨酯微孔发泡材料的表观密度与其力学性能的关系

用高压CO2流体通过升温发泡法制备了一系列不同表观密度的热塑性聚氨酯(TPU)微孔发泡材料,探究了TPU发泡材料的表观密度与其力学性能的关系.微孔发泡材料的泡孔结构和表皮结构由扫描电子显微镜表征;不同表观密度材料的力学性能利用万能材料试验机和旋转流变仪表征.研究发现:TPU微孔发泡材料的表观密度主要是由材料皮层厚度占比和泡孔层密度决定的,皮层厚度占比越小和泡孔面积占有率越高,泡沫的表观密度越小;微孔发泡材料在线性应变区的压缩模量E与材料表观密度ρ的关系为:E∝ρ1.7,符合泡沫材料压缩模量与表观密度呈指数关系的基本结论;循环压缩实验中,随微孔发泡材料表观密度减小,损耗百分比增大,残余应变减小;流变实验中,微孔发泡材料的模量随表观密度变化没有明显的变化,阻尼因子tanδ随泡沫表观密度变化不呈单一的规律性.同时,阐明了微孔发泡材料的压缩模量E和损耗百分比随表观密度变化的机理.     

新型PES微孔材料的制备及性能研究

合成了新型双烯丙基聚醚砜(PES), 采用超临界CO2作为物理发泡试剂制备微孔材料, 研究了不同发泡温度、饱和压力、发泡时间和放气时间等因素对微孔形貌的影响. 结果表明, 发泡温度在110~170 ℃之间, 随着温度的升高, 泡孔直径增加, 泡孔密度在140 ℃达到一个最大值; 随着饱和压力的升高, 泡孔直径减小, 泡孔密度增大; 发泡时间和放气时间对微孔直径和密度影响不大; 研究了在不同辐照剂量下微孔材料的交联性能, 结果表明, 在600 kGy辐照剂量以下, 交联效果不明显, 在800 kGy以上, 随着辐照剂量的增大, 凝胶含量增加, 辐照后的样品在265 ℃热处理10 min, 仍能保持完好的微孔结构.     

应用超临界CO2制备微孔聚丙烯的微孔形貌

研究了应用超临界CO2技术制备微孔聚丙烯时发泡条件和聚丙烯(PP)的熔体强度对微孔形貌的影响。结果表明:在一定的饱和压力下,随着温度的升高,PP的变形能力改善,有利于泡孔的长大。随着饱和压力的增加,PP的熔点降低,升高压力和升高温度具有一定的等同作用。由于CO2在PP内分散的不同,高压低温时得到的泡孔比高温低压时得到的泡孔要规整。降压速率对泡孔形貌的影响因饱和压力的大小而异,饱和压力较高时随着降压速率的提高,孔密度增加,泡孔形貌经历了一个从球体到多面体转变的过程。由于PP熔体强度较低,在发泡温度和PP熔点之间非常接近时,CO2气体容易冲破孔壁而使泡孔呈开孔结构。     

Absorption and foaming of plastics using carbon dioxide

In this study, carbon dioxide was used as a foaming agent for common plastics, such as acrylonitrile–butadiene–styrene (ABS) polymer, polystyrene (PS), polypropylene (PP), high-density polyethylene (HDPE), and high impact polystyrene (HIPS). Carbon dioxide was first absorbed by the sample plastics placed within a pressure vessel at various pressure levels and absorption time intervals. The Henry’s constant of the absorbed carbon dioxide in the plastics was determined. The diffusion coefficient of carbon dioxide in polymer was also identified by curve-fitting with the relationship between the absorbed amount and time. The results showed that ABS, PS, and HIPS absorbed more gas than did PP and HDPE, because PP and HDPE exhibit higher crystallinity. Generally, a polymer can take up saturation absorption of gas under higher pressure. After absorption, the foaming process occurred at various temperatures and time intervals. The cell structure, density, and size of the plastic foams were then investigated using scanning electron microscopy. A longer foaming period and higher temperature increase the size of the cell and decrease the cell density (the number of bubbles per unit volume). A dense skin layer without bubbles appeared directly adjacent to the surface of the foamed plastics. Its thickness decreased if the foaming process took place at higher temperatures.     

A novel method to prepare microcellular poly(vinyl alcohol) foam based on thermal processing and supercritical fluid

Combining the thermal processing and supercritical fluid technology develops a novel preparation method of microcellular poly(vinyl alcohol) (PVA). Water, as the plasticizer in system, can form the hydrogen bonding with pendant hydroxyl of PVA and weaken its strong intermolecular and intramolecular forces to realize the thermal processing. Supercritical carbon dioxide (sc‐CO₂) can easily dissolve into water‐plasticized PVA (WPVA) because of the destruction of crystal region caused by water, and the enhanced sc‐CO₂ solubility can greatly improve the foamability of WPVA. The porous structure generates through the saturation of sc‐CO₂ in WPVA sample and followed by pressure drop‐induced phase separation. The foaming behavior of WPVA was studied as a function of saturation pressure, foaming temperature, and saturation time. The cell density, cell size, and distribution of the obtained foam can be controlled by tuning processing conditions. The results revealed that the cell size decreased, and its distribution narrowed with saturation pressure increasing, or decrease of foaming temperature. But excessively increasing the saturation time generated a negative effect on the foaming behavior owing to the deteriorated plasticization effect resulted from the loss of water. Copyright © 2016 John Wiley & Sons, Ltd.     

Poly(ε-caprolactone) (PCL)/cellulose nano-crystal (CNC) nanocomposites and foams

Poly(ε-caprolactone) (PCL)/cellulose nanocrystal (CNC) nanocomposites were produced via twin-screw extrusion. Microcellular nanocomposite samples were produced with microcellular injection molding using carbon dioxide (CO₂) as physical blowing agent. The foaming behavior, physical properties, thermal properties, crystallization behavior, and biocompatibility were investigated. It was found that the CNCs interacted with the PCL matrix which led to a strong interface. The CNCs effectively acted as nucleation agents in microcellular injection molding. Both solid and foamed samples with higher levels of CNC content showed higher tensile moduli, complex viscosities, and storage moduli due to the reinforcement effects of CNCs. Furthermore, improvement in the foamed samples was more significant due to their fine cell structure. The addition of CNCs caused a reduction of the decomposition temperature and an increase in the glass transition temperature, crystallization temperature, and crystallinity of PCL. Moreover, the biocompatibility of the foamed nanocomposites with low CNC content was verified by 3T3 fibroblast cell culture.     

Statistical and experimental investigation on low density microcellular foaming of PLA-TPU/cellulose nano-fiber bio-nanocomposites

This study dedicates to foaming of biocompatible blends of polylactic acid and thermoplastic polyurethane reinforced with bio-degradable cellulose nanofibers. This research primarily was associated with fabrication of PLA-TPU nanocomposites using a low weight fraction of cellulose nanofibers as a biodegradable reinforcement. Microstructural and mechanical properties of fabricated nanocomposites were examined and diffractometry was utilized to verify formation of percolated nanocomposites. Microcellular foaming was then performed with CO₂ as a blowing agent. Central composite design was applied in designing the experiments to evaluate the effects of main operating variables consisting of saturation pressure and time, heating time and foaming temperature. The results demonstrated that high saturation pressure and time promoted low cell diameters (below 5 μm) and high cell densities (above 10⁹ cell/cm³) due to the grown degree of crystallinity and higher PLA-TPU miscibility. Accordingly, adding TPU and CNF to the matrix create high crystalline foamed samples decorated with low bulk density.     

Microcellular structure of a thin polycarbonate sheet prepared by compression molding

Microcellular thin polycarbonate sheets have been prepared by compression molding with the cell size in the range of 2∼20 microns, and cell density larger than 10⁸ cells/cm³. The effect of processing parameters on the microcellular polycarbonate structure has been investigated. The cell size decreases with increasing foaming time till 8 minute and then increases. Besides this parameter slightly decreases with increasing foaming pressure, but increases with increasing temperature. The variation of cell density is contrary to that of cell size, and the foam density decreases with increasing foaming pressure and foaming temperature and displays a variable trend with increasing foaming time under different foaming pressures.     

Preparation,characterization, and mechanical properties of microcellular poly(aryl ether ketone) foams

High‐performance microcellular closed‐cell foams were prepared by a two‐stage batch foaming process from fluorinated poly(ether ether ketone) and characterized by scanning electronic microscopy, tensile, and dynamic mechanical analysis (DMA). The effects of saturation pressure and temperature on the cell size, cell density, and bulk density of porous materials had been discussed. The resulting materials had average cell diameters in the range 3–17 μm, and cell densities (N_f) in the order of 0.6 × 10⁹–1.39 × 10¹⁰ cells/cm³. The porosity (V_f) was in the range of 0.2–0.85. In contrast, experimental values of Young's moduli were in good agreement with theoretically predicted values, but the relative strengths were somewhat lower than that predicted. The relaxation mechanism of microcellular was systematically investigated by DMA. The dynamic mechanical spectrometry showed that the storage modulus curve at high temperature region appeared a peak and the loss modulus was lower as compared to their solid counterparts. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 173–183, 2007     

Preparation and characterization of microcellular polystyrene/polystyrene ionomer blends with supercritical carbon dioxide

The preparation of microcellular polystyrene (PS), lightly sulfonated polystyrene (SPS), zinc‐neutralized lightly sulfonated polystyrene (ZnSPS), and blends of PS/SPS and PS/ZnSPS via supercritical CO₂ was carried out with the pressure‐quench process. Both higher foaming temperature and lower pressure result in larger cell sizes, lower cell densities, and lower relative density for microcellular ionomers and blends as for microcellular PS. The difference among various microcellular samples is the change of cell size with the sample composition. The cell size decreases in the sequence from SPS, through PS/SPS blends, PS and PS/ZnSPS blends, to ZnSPS. The diffusivity of CO₂ in samples also decreases in the sequence from SPS, through PS/SPS blends, PS and PS/ZnSPS blends, to ZnSPS. For this series of samples with similar structure and identical solubility of CO₂, the varying diffusivity is responsible for the difference of cell sizes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 368–377, 2003     

A steady‐state mass balance model of the polycarbonate–CO2 system reveals a self‐regulating cell growth mechanism in the solid‐state microcellular process

A simple mechanism regulating polymer mobility is demonstrated to determine initial and final growth states of solid‐state microcellular foams. This mechanism, governed by the extent of plasticization of the polymer by the dissolved gases, is examined with a mass balance model and results from foam growth experiments. Polycarbonate was exposed to CO₂, which acted as both a plasticizing gas and a physical blowing agent driving foam growth. The polycarbonate specimens were saturated to the equilibrium gas concentration at 25 °C for CO₂ pressures of 1–6 MPa in 1‐MPa increments. Equilibrated specimens were heated in a glycerin bath until thermal equilibrium was reached, and a steady foam structure was attained. Glycerin bath temperatures of 30–150 °C in 10 °C increments were examined. Using knowledge of gas solubility, the equation of state for CO₂, the effective glass‐transition temperature as a function of gas concentration, and a model for mass balance within a solid‐state foam, we demonstrate that foam growth terminates when sufficient gas is driven from the polycarbonate matrix into the foam cells. The foam cell walls freeze at the elevated bath temperature because of gas transport from the polycarbonate matrix and the associated rise in the polymer glass‐transition temperature to that of the heated bath. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 868–880, 2001     

Dynamic mechanical and dielectric relaxation characteristics of microcellular rubber composites

An in‐depth study of the surface characteristics of novel conductive carbon black Ensaco 350G has been carried out using XPS and high‐resolution vacuum FTIR. Both methods showed the existence of oxygen containing surface groups like carboxyls, carbonyls, etc. Dynamic mechanical analysis and dielectric relaxation spectra of conductive carbon black (Ensaco 350G) reinforced microcellular EPDM composites were used to study the relaxation behavior as a function of temperature (?90 to +100°C) and frequency (100–10⁶ Hz). The effect of filler and blowing agent loadings on dynamic mechanical and dielectric relaxation characteristics has been investigated. The effect of filler and blowing agent loadings on glass transition temperature was marginal for all the composites (T_g value was in the range of ?37 to ?32°C), which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. The variation in the real and imaginary parts of the complex impedance with frequency has been studied as a function of filler and blowing agent loading. Additionally, an in‐depth study of the surface characteristics of the filler using XPS, high‐resolution vacuum FTIR and Raman spectra is also reported. Copyright © 2008 John Wiley & Sons, Ltd.     

Anisotropic cellular structures from semi-crystalline polymer templates

We report an investigation to determine the effect of an anisotropic semi-crystalline template on the resulting cell morphology of microcellular polymeric foams generated in these materials. Poly(ethylene terephthalate) (PET)-polystyrene (PS) composite foams are prepared by using supercritical carbon dioxide (scCO₂) not only as a foaming agent but also as a transport medium of styrene and initiator into a biaxially-oriented PET templating film. The composite foam so obtained demonstrates a highly interpenetrating network verified by a single Tg of 98°C. Substrate orientation is observed not to dictate the cell formation; however highly anisotropic swelling and a shape-templating phenomenon is observed, with the most significant dimension change in the thickness of the film. Introducing confinement in the direction of maximum dimension change is found to introduce a highly anisotropic lamellar cell architecture.     

Supercritical CO<Subscript>2</Subscript> assisted preparation of open-cell foams of linear low-density polyethylene and linear low-density polyethylene/carbon nanotube composites

The open-cell structure foams of linear low-density polyethylene (LLDPE) and linear low-density polyethylene (LLDPE)/multi-wall carbon nanotubes (MWCNTs) composites are prepared by using supercritical carbon dioxide (sc-CO₂) as a foaming agent. The effects of processing parameters (foaming temperature, saturation pressure, and depressurization rate) and the addition of MWCNTs on the evolution of cell opening are studied systematically. For LLDPE foaming, the foaming temperature and saturation pressure are two key factors for preparing open-cell foams. An increase in temperature and pressure promotes both the cell wall thinning and cell rupture, because a high temperature results in a decrease in the viscosity of the polymer, and a high pressure leads to a larger amount of cell nucleation. Moreover, for the given temperature and pressure, the high pressurization rate results in a high pressure gradient, favoring cell rupture. For LLDPE/MWCNTs foaming, the addition of MWCNTs not only promotes the cell heterogeneous nucleation, but also prevents the cell collapse during cell opening, which is critical to achieve the open-cell structures with small cell size and high cell density.     

Au nanolayers deposited on polyethyleneterephtalate and polytetrafluorethylene degraded by plasma discharge

Polyethyleneterephtalate (PET) and polytetrafluorethylene (PTFE) foils were modified by plasma discharge. The effect of plasma modification on polymer surface wettability and on properties of gold coatings were studied as a function of time from plasma exposure (aging time) and polymer substrate temperature. Thickness, sheet resistance, and surface topology of gold layers were studied. Aging of the plasma‐exposed samples is accompanied by increase in contact angle, which is explained by rearrangement of the polymer segments in the polymer surface monolayer, and a decrease in the concentration of polar groups. The aging also leads to a decline in surface roughness R_a measured by atomic force microscopy (AFM). Under deposition conditions, comparable thicknesses of deposited Au layers were prepared on pristine PET and plasma‐treated PET and PTFE samples. The thinnest Au layers were evaporated onto pristine PTFE. The sheet resistance decreases with increasing thickness of Au layer. Plasma treatment leads to an increase of PTFE surface roughness, which becomes even more pronounced after Au deposition. A higher roughness shows that the PET samples are deposited with the Au layer at temperatures above the glassy transition temperature T_g. Copyright © 2006 John Wiley & Sons, Ltd.     

Effect of Supercritical Carbon Dioxide Conditions on PVDF/PVP Microcellular Foams

Supercritical carbon dioxide (ScCO₂) was used as a physical foaming agent to prepare poly(vinylidene f luoride)/poly(N-vinyl pyrrolidone) (PVDF/PVP) microstructure material. The effects of foaming conditions including saturation pressure, foaming temperature and foaming time on PVDF/PVP foams morphology, thermal and electrical behavior were systematically investigated by scanning electron microscope, differential scanning calorimeter and broadband dielectric spectrometer. Small cell and low cell density were achieved at low pressure of 12 MPa, as increasing saturation pressure, the average cell size increased first, and then decreased. The competition between the cell growth and cell nucleation played an important role in average cell size, which was directly related to ScCO₂ processing conditions. With increasing foaming temperature, cell size was increased and cell density was decreased, in a nearly linear manner. The variation of foaming time was considered to be closely related to the time for cells to grow. Thus, the results revealed that the average cell size enhanced with extending foaming time. The thermal properties of PVDF/PVP composites are slightly inf luenced by foaming parameters, and the dielectric constant of PVDF/PVP composite foams decreased with increasing volume expansion ratio.     

Supercritical CO_2 Assisted Preparation of Open-cell Foams of Linear Low-density Polyethylene and Linear Low-density Polyethylene/Carbon Nanotube Composites

The open-cell structure foams of linear low-density polyethylene(LLDPE) and linear low-density polyethylene(LLDPE)/multi-wall carbon nanotubes(MWCNTs) composites are prepared by using supercritical carbon dioxide(sc-CO_2)as a foaming agent. The effects of processing parameters(foaming temperature, saturation pressure, and depressurization rate) and the addition of MWCNTs on the evolution of cell opening are studied systematically. For LLDPE foaming, the foaming temperature and saturation pressure are two key factors for preparing open-cell foams. An increase in temperature and pressure promotes both the cell wall thinning and cell rupture, because a high temperature results in a decrease in the viscosity of the polymer, and a high pressure leads to a larger amount of cell nucleation. Moreover, for the given temperature and pressure, the high pressurization rate results in a high pressure gradient, favoring cell rupture. For LLDPE/MWCNTs foaming, the addition of MWCNTs not only promotes the cell heterogeneous nucleation, but also prevents the cell collapse during cell opening, which is critical to achieve the open-cell structures with small cell size and high cell density.     

Generation of Microcellular Biodegradable Polycaprolactone Foams in Supercritical Carbon Dioxide

Present now the application of microcellular polymeric materials in biomedical field is growing rapidly, as that of guided tissue regeneration and cell transplantation. As far as guided tissue regeneration is concerned, porous implants are used as size selective membrane to promote the growth of a special tissue in a healing site. Ideally, the implant should be inherently biocompatible,have well-defined cell size and be resorbable with appropriate biodegradation rates.Poly(a-caprolactone) (PCL) is a kind of materials suit for the demands above. PCL is biocompatible and biodegradable aliphatic polyester which is nontoxic for living organisms and bioresorbable after a period of implantation. Because of its unique combination of biocompatibility, permeability and biodegradability, PCL and some of its copolymer with lactides and glycolide have been widely applied in medicine as artificial skin, artificial bone and containers for sustained drug release.Goel and Beckman have reported a new method to generate microcellular poly(methy l methacrylate) foams in which the samples are saturated with CO2 under a series of supercritical (SC)conditions, and then the system is rapidly depressurized to atmospheric pressure at constant temperature. Unlike traditional methods, it reduces glass-transition temperature (Tg) of the mixture to below the experimental temperature rather than directly heat the system above Tg. In this process of nucleation, no phase separation occurs as well as no phase boundary meets, so the cellular structure of the foam can be retained better.In this work, we have generated PCL foams by using supercritical CO2. Because of the low glass transition temperature (Tg = -60 ℃) of PCL far below the ice point, the experimental temperature in our study is much higher than Tg, which is different from the studies by others before. A series of variable factors on the foam structure as saturation temperature, saturation pressure, saturation time and depressurization time were studied. The experimental results indicate higher saturation temperature produce reduced bulk densities while holding other variable experimental conditions,and different saturation pressure produce different nucleation process. In addition, saturation time has profound effect on the structure of the product. XRD result shows that the foamed PCL is more inclined to degrade than the original PCL for the reason of its lower crystallinity.     

超临界流体制备微发泡聚合物材料的研究进展

以超临界流体为物理发泡剂制备的微发泡聚合物材料具有小的泡孔尺寸和高的泡孔密度,从而赋予材料优异的性能.本文首先阐述了微发泡聚合物材料的制备原理,以及聚合物微发泡过程中泡孔形成的四个阶段;基于这些认识,针对微发泡聚合物材料泡孔形态的改善,即增加泡孔密度、减小泡孔尺寸以及均化泡孔尺寸分布,从加强泡孔成核、控制泡孔增长的角度综述了近年来的研究进展;最后对如何有效控制泡孔形态提出了建议,并对微发泡聚合物材料的应用前景进行了展望.