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.     

Foaming behavior,cellular structure and physical properties of polybenzoxazine foams

In this paper, polymer foams based on a benzoxazine resin have been successfully prepared using azodicarbonamide (ADC) as a chemical blowing agent and have been characterized regarding their foaming behavior, cellular structure, and physical properties. The effect of the ADC on the curing process of the resin was analyzed using differential scanning calorimetry and blowing agent decomposition was followed by thermogravitmetric analysis (TGA). The characterization of the cellular structure of the foamed samples was done using scanning electron microscopy. The mechanical properties of the foams were determined using compression tests and the thermal conductivity was assessed using the transient plane source method. The results indicated that the curing process and gas release took place in a similar time interval. The foams showed an isotropic cellular structure with relative densities in the range 0.35–0.60, and showed compressive strengths and compressive moduli in the range of 10–70 MPa and 400–1100 MPa, respectively. Thermal conductivities were in the range of 0.06–0.12 W m^?1K^?1. The findings in this paper demonstrate the possibility of producing polybenzoxazine foams using a simple process in which curing and foaming take place simultaneously. In addition, the mechanical characterization of these materials indicates that they are suitable for structural applications. Copyright © 2011 John Wiley & Sons, Ltd.     

A multi point conductivity measurement system for characterisation of protein foams

Protein foams play an important role in both food and biotechnological processes. A sound understanding of foaming properties of proteins relevant to such processes is useful e.g. to allow adequate control of unwanted foams and appropriate choice of protein-physical system when foams of certain characteristics are required. In general, measurements of changes in foam volume (volumetric method) are used for foam characterisation. However, recently there has been increased interest in the use of measurement methods based on conductivity and capacitance. Simple relative techniques based on electrical conductivity measurements provide information on both foamability and foam stability. A multi point conductivity measurement system has been designed and used for characterisation of model protein foams (0.1 and 1.0 mg ml⁻¹ Bovine serum albumin, BSA). The solution of BSA was sparged with nitrogen or carbon dioxide gas at constant flow rate (90 cm³ min⁻¹) via a stainless steel sinter (0.5 or 2.0 μm in pore size). A comparison of foaming properties determined by volumetric and conductimetric techniques is provided. Both methods show that more stable foams are obtained for solutions at higher BSA concentrations. At all BSA concentrations, higher foamability and stability are achieved with a smaller sinter pore size. When nitrogen rather than carbon dioxide is used as a dispersed phase, higher foamability and foam stability are obtained. The conductivity measurements indicate that foamability is dependent on gas type, whereas, volumetric measurements do not show such differences.     

Open-pore biodegradable foams prepared via gas foaming and microparticulate templating

Open-pore biodegradable foams with controlled porous architectures were prepared by combining gas foaming and microparticulate templating. Microparticulate composites of poly(epsilon-caprolactone) (PCL) and micrometric sodium chloride particles (NaCl), in concentrations ranging from 70/30 to 20/80 wt.-% of PCL/NaCl were melt-mixed and gas-foamed using carbon dioxide as physical blowing agent. The effects of microparticle concentration, foaming temperature, and pressure drop rate on foam microstructure were surveyed and related to the viscoelastic properties of the polymer/microparticle composite melt. Results showed that foams with open-pore networks can be obtained and that porosity, pore size, and interconnectivity may be finely modulated by optimizing the processing parameters. Furthermore, the ability to obtain a spatial gradient of porosity embossed within the three-dimensional polymer structure was exploited by using a heterogeneous microparticle filling. Results indicated that by foaming composites with microparticle concentration gradients, it was also possible to control the porosity and pore-size spatial distribution of the open-pore PCL foams.     

Crosslinked polyethylene foams, via EB radiation

Polyethylene foams, produced by radio-induced crosslinking, show a smooth and homogeneous surface, when compared to chemical crosslinking method using peroxide as crosslinking agent. This process fosters excellent adhesive and printability properties. Besides that, closed cells, intrinsic to theses foams, imparts opitmum mechanical, shocks and insulation resistance, indicating these foams to some markets segments as: automotive and transport; buoyancy, flotation and marine: building and insulation: packaging: domestic sports and leisure goods. We were in search of an ideal foam, by adding 5 to 15% of blowing agent in LDPE. A series of preliminary trials defined 203° C as the right blowing agent decomposition temperature. At a 22.7 kGy/dose ratio, the lowest dose for providing an efficient foam was 30 kGy, for a formulation comprising 10% of azodicarbonamide in LDPE, within a 10 minutes foaming time.     

Improved cell morphology and reduced shrinkage ratio of ETPU beads by reactive blending

Thermoplastic polyurethane foam beads (ETPU) have attracted attention of researchers in recent years due to their wide use in industrial applications. In this study, a small amount of acrylonitrile-butadiene-styrene copolymer (ABS) was blended with TPU under the assistance of dicumyl peroxide (DCP) and maleic anhydride (MAH) to improve the cell morphology and reduce shrinkage ratio of the resulting blends. These blends were then foamed to prepare TPU/ABS blends foam beads in an autoclave using supercritical CO₂ as the blowing agent at different temperatures and FTIR spectra, and rheological and foaming properties of the samples were evaluated. The melt viscosity, melt strength and elasticity of TPU/ABS were improved with the increase of the ABS content. These results were attributed to the grafting and heterogeneous nucleation points provided by the ABS. These enhanced properties were used to produce foams with better cell morphology and increased expansion ratio. Furthermore, the TPU/ABS blends foam beads showed lower shrinkage ratios with increasing ABS content. Thus, the addition of ABS is a facile method for improving the cell morphology and anti-shrinkage properties of ETPU.     

Exploiting the Use of the Decarboxylative S-Alkylation Reaction to Produce Self-Blowing,Recyclable Polycarbonate Foams

Polymeric foams are widely used in many industrial applications due to their light weight and superior thermal, mechanical, and optical properties. Currently, increasing research efforts is being directed towards the development of greener foam formulations that circumvent the use of isocyanates/blowing agents that are commonly used in the production of foam materials. Here, a straightforward, one-pot method is presented to prepare self-blown polycarbonate (PC) foams by exploiting the (decarboxylative) S-alkylation reaction for in situ generation of the blowing agent (CO₂). The concomitant formation of a reactive alcohol intermediate promotes a cascade ring-opening polymerization of the cyclic carbonates to yield a cross-linked polymer network. It is shown that these hydroxyl-functionalized polycarbonate-based foams can be easily recycled into films through thermal compression molding. Furthermore, it is demonstrated that complete hydrolytic degradation of the foams is possible, thus offering the potential for zero-waste materials. This straightforward and versatile process broadens the scope of isocyanate-free, self-foaming materials, opening a new pathway for next-generation environmentally friendly foams.     

Chain Extension and Foaming of Recycled PET in Extrusion Equipment

In this work industrial scraps of poly(ethylene terephthalate) (PET) were used for the production of foamed sheets. The process was performed by making use of a chemical blowing agent (CBA) in the extrusion process. Due to the low intrinsic viscosity of the recycled PET (IV=0.48dl/g), a chain extender was also used in order to increase the molecular weight of the polymer matrix. Pyromellitic dianhydride (PMDA) and Hydrocerol CT 534 were chosen as chain extender and CBA, respectively. The reactive extrusion and foaming were performed in a two step process, analyzing the feasibility regarding an eventual use in an industrial context. Rheological characterization was carried out on PET samples previously treated with PMDA, as well as the morphological study was performed to define the cellular structure of the foams produced. Moreover, in order to correlate the working conditions in the reactive and the foaming processes with the final morphology of the foams, a mathematical modelling of the foaming process was applied.     

Unloaded polyether type polyurethane foams as solid extractants for trace elements

Polyether type polyurethane foams (PU) are regular stacks of solid quasi-spherical membranes produced by the reaction of polyisocyanates with polyols of polyether nature in the presence of a catalyst and a blowing agent. Contrary to conventional membrane separations, where a solid membrane is merely a differentially separating agent, or a transport medium, PU foams, apart from separation and preconcentration, also retain, i.e., sorb the species on, or in the membranes. Therefore, PU foam membranes can be considered to act as true sorbents. The membrane properties of PU foam sorbents offer unique advantages over conventional bulk type granular sorbents in rapid, versatile and effective separations and preconcentrations of different compounds from fluid samples. Unloaded PU foam sorbents have received considerable attention in the separation of different trace inorganic species.     

Physical properties of silicone foams filled with carbon nanotubes and functionalized graphene sheets

Free-rising silicone foams were made with loading fractions of up to 0.25 wt.-% functionalized graphene sheets (FGS) and up to 1.0 wt.-% carbon nanotubes (CNTs) using hydrogen as blowing agent. Scanning electron microscopy of the samples revealed an open cellular structure and a homogeneous dispersion of both types of nanofillers. The incorporation of nanofiller affected the foaming process and thus the final foam density and cellular structure. Transmission electron microscopy revealed the formation of a CNT network throughout the sample, while FGS presented an exfoliated and intercalated dispersion. The thermal stability of the samples was drastically affected by the presence of both nanofillers. Both nanofillers showed a positive effect on the compressive response of the foams. However, the nanocomposite foams were found to decrease the acoustic absorption with nanofiller content probably due to the variable foam structure and improved stiffness.     

Improvement of the surface of polyethylene foamed sheet by irradiation

The manufacturing methods of cross-linked polyethylene foams are classified into two categories based on a type of cross-linking. One is chemical cross-linking by using peroxide as a cross-linking agent. The other method is cross-linking by irradiation. As for chemical cross-linking, a fairly thick foam sheet can be produced, and a comparatively high degree of cross-linking can be achieved. This means chemical cross-linking excels in thermo-forming but, due to a rough surface, the product is lacking in adhesive property and printability. We studied how to improve the surface condition of foam sheet without damaging the features proceeding from chemical cross-linking. As a result, it has been revealed that at the pre-stage of foaming, and by irradiating the surface at low voltage, the resultant foamed sheet with smooth surfaces and excelling in mechanical properties can be produced.     

Effect of biopolymer blends on physical and Acoustical properties of biocomposite foams

Bio‐based foams are the solution to environmental concerns raised by petrochemical‐based open cell foams used in various industries for sound absorption. While conventional petrochemical‐based polymers take centuries to degrade or may not degrade at all, bio‐based polymers decompose to biomass, water, and carbon dioxide in a matter of months when exposed to proper environment. To increase the potential of replacing current petrochemical foams, mechanical as well as acoustic characteristics of bio‐based foams need to be improved. This article studies the effect of blending two bio‐based polymers and physics of the blends on acoustic and mechanical properties of resulting polymer composite foams. Different blends of polylactide with three grades of polyhydroxyalkanoates were foamed and characterized based on acoustic and mechanical performance. Rheological properties of pure polymers as well as their blends were studied and effect of polymer blends on acoustic absorption of the resulting foams was investigated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1002–1013     

Preparation of PMMA Foam by Supercritical CO_2 with Ethanol

Supercritical (SC) CO2 can plasticize many amorphous polymers, which reduce the glass transition temperature of the polymers significantly. Recently, it was used as blowing agent to foam amorphous materials such as poly(methyl methacrylate) (PMMA)1,2, polystyrene (PS)3, polycarbonate (PC)4 and poly(ethylene terephthalate) (PET)4. In this foaming process, a polymer is saturated with SC CO2, and followed by rapid depressurization to atmospheric pressure. The microcellular foams can be ob…     

水发泡淀粉挤出泡沫的结构与性能

以水为发泡剂,普通玉米淀粉为原料,采用双螺杆挤出机制备淀粉泡沫材料,研究了发泡剂用量及聚乙烯醇的加入量对泡沫材料结构与性能的影响。 用扫描电子显微镜观察了泡沫材料截面的形态,用万能材料试验机测试了泡沫材料的力学性能。 结果表明,水的质量分数为8%时淀粉泡沫径向膨胀率和发泡倍率最高,分别为22倍和17.6倍,压缩模量最高（4.07 MPa）。 加入质量分数10%的聚乙烯醇(PVA)使淀粉泡沫的孔径变大至1.29 mm,壁厚增加至82.43 μm,同时压缩模量增加至9.70 MPa。     

Understanding Behavior of Polycaprolactone–Gelatin Blends under High Pressure CO<Subscript>2</Subscript>

Polycaprolactone (PCL) is widely used in biomedical applications as electrospun fibers or porous foams. As PCL is synthetic polymer, many researchers have explored blends of PCL–gelatin to combine mechanical and bioactive properties of individual components. High pressure carbon dioxide (CO2) has been studied to foam and impregnate many biocompatible polymers. In case of PCL–gelatin blends, certain compositions can be swelled reversibly under high pressure CO₂ without permanent deformation. This allows successful impregnation of PCL–gelatin blends under CO₂. This study summarizes effect of different treatments adopted during impregnation process including high pressure CO2 on several blend compositions of PCL–gelatin blends. Stress relaxation, polymer melting and dissolution were observed during several treatments which affects porosity and scaffold structure significantly. Results summarized in this study will aid in optimum selection of PCL–gelatin blend composition for biomedical applications. Furthermore, CO₂ solubility in polymers is restricted due to thermodynamic limitations but can be altered in the presence of a co-solvent to produce better foams. PCL can be foamed using supercritical CO₂. However, CO₂ foaming of PCL–gelatin blend becomes challenging to simultaneous swelling of PCL and compression of gelatin providing blend structural stability. This study has demonstrated ability of supercritical CO₂ to foam PCL–gelatin blends in presence of water to create porous structure. These foams were subjected post-fabrication crosslinking and supercritical CO₂ without losing porosity of foams. Thus, creating a strategy to use environmentally benign processes to fabricate, crosslink and impregnate porous scaffolds for biomedical applications.     

Die Träume von den Schäumen. Detergenzien und Tenside

Foams can be found in many different applications in both industry and private households, that is, in dishwashing detergent, shampoos, or also in producing foamed plastic. But it is still not clear why some foams are stable over a certain period of time while others are not. Therefore, it is of great interest to know about the properties responsible for the stability of foams in order to save both time and money on trial-and-error experiments aimed at finding the right composition. If one wants to find out about the properties of foams, he also have to consider the properties of thin foam films because they represent the smallest building blocks of foams. The type and the concentration of the surfactant, undoubtedly, have the biggest influence on the stability of a foam. However, additives like perfumes or alcohols obviously play a significant role, too. This paper deals with some results on foam and foam film investigations and establish some correlations; on the other hand, it highlights a number of questions which are still unanswered.     

Poly(lactic acid)/organoclay nanocomposites: Thermal,rheological properties and foam processing

In this study, polymer nanocomposites based on poly(lactic acid) (PLA) and organically modified layered silicates (organoclay) were prepared by melt mixing in an internal mixer. The exfoliation of organoclay could be attributed to the interaction between the organoclay and PLA molecules and shearing force during mixing. The exfoliated organoclay layers acted as nucleating agents at low content and as the organoclay content increased they became physical hindrance to the chain mobility of PLA. The thermal dynamic mechanical moduli of nanocomposites were also improved by the exfoliation of organoclay; however, the improvement was reduced at high organoclay content. The dynamic rheological studies show that the nanocomposites have higher viscosity and more pronounced elastic properties than pure PLA. Both storage and loss moduli increased with silicate loading at all frequencies and showed nonterminal behavior at low frequencies. The nanocomposites and PLA were then foamed by using the mixture of CO₂ and N₂ as blowing agent in a batch foaming process. Compared with PLA foam, the nanocomposite foams exhibited reduced cell size and increased cell density at very low organoclay content. With the increase of organoclay content, the cell size was decreased and both cell density and foam density were increased. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 689–698, 2005     

Morphology and Orientation of PP-Structural Foam Moldings

Abstract

An experimental study was conducted to investigate the interaction between the macrostructure and morphology of PP-structural foam moldings made by gas-counter pressure process by egression of foamed melt from the core of the molding. The structural foam moldings, center-gated cylindrical plate “disc” (diameter 1800 mm. high 11 mm) were produced on an in-line injection molding machine KuASY 800/250, varying the shot weight and melt temperature. The polymer used was isotactic polypropylene “Buplen” 7523 with 1 wt% chemical blowing agent (azodicarbonamide) added. The morphology, orientation, and processes of non isothermal phase transition have been studied using polarized optical microscopy, SALS, DSC and birefringence. Samples were cut from the discs at different distances from the gate. The presence of a two-layered structure was observed in the solid skin: an outer smectic layer and an inner particular crystalline layer. The thickness of the smectic layer and size of spherulites from skin to the foamed core were determined. The orientation in radical and tangential direction of the flow and perpendicular to the disc surface were studied in mold filling and egression stage. The fixed orientation in final moldings is a complex picture of bubble growth, bubble orientation and shear flow. It was found that the radical orientation decreases with the distance from the gate. Maximum orientation is located in the solid skin, and minimum in the foamed core, and was shown by means of a birefringence profile.     

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.     

Study of Cryostructuring of Polymer Systems: 25. The Influence of Surfactants on the Properties and Structure of Gas-Filled (Foamed) Poly(vinyl alcohol) Cryogels

Foamed poly(vinyl alcohol) (PVA) cryogels are studied. Such heterogeneous gel composites are formed as a result of the cryogenic treatment (freezing—storage in a frozen state—thawing) of water— PVA liquid foams in the absence and presence of surfactants. It is shown that the addition of ionic and nonionic surfactants to an aqueous PVA solution and its subsequent foaming result in the formation of liquid foam whose stability is lower than that of the foam prepared from an aqueous PVA solution in the absence of surfactant, i.e., surfactants cause a destabilizing effect on the foams containing PVA. Gas-filled PVA cryogels formed as a result of freezing—thawing of such foams contain large (up to ～180 μm) pores (air bubbles incorporated into the matrix of heterogeneous gel). Mechanical and thermal properties of cryogels depend on the nature and concentration of surfactants, as well as on the regime of cryogenic treatment. The rigidity of foamed PVA cryogels prepared in the presence of sodium dodecyl sulfate and cetyltrimethylammonium bromide ionic surfactants is lower and that in the presence of nonionic decaoxyethylene cetyl ether is higher than for equiconcentrated (by the polymer) foamed PVA cryogel containing no surfactant. Microscopic studies and the analysis of obtained images of cryogel structure demonstrate that the effect of surfactant on the morphology of freezing foam can be different, depending on the type of surfactant added to the initial system. This leads to foam-destabilizing effects such as the collapse, deformation, and coalescence of air bubbles; the failure of gel phase structure near the bubble surface; etc. However, the complete disintegration of the foamed structure is prevented by a very high viscosity of the unfrozen liquid microphase of a macroscopically solid sample and by the cryotropic PVA gelation that fixes the structure of partially destroyed foam.