Improving viscoelasticity and rebound resilience of crosslinked low‐density polyethylene foam by blending with ethylene vinyl acetate and polyethylene‐octene elastomer

To obtain high‐rebound resilience of crosslinking low‐density polyethylene (LDPE) foam and decrease the foam density at the same content of foaming agent, the melt viscoelasticity of LDPE with different compositions (ethylene vinyl acetate [EVA], polyethylene‐octene elastomer, and crosslinking agent) was investigated by dynamic rheology test. Then, LDPE/EVA/(polyethylene‐octene elastomer) foams with different composition ratios were produced by a continuous foaming process and investigated by the rebound resilience test. The results show that the melt viscoelasticity behavior of LDPE and its blends in the molten state possessed more melt elasticity behavior after the crosslinking was introduced. Meanwhile, the rebound resilience of LDPE foam was increased 54% at the lower foam density (0.031 g/cm³). It could meet the requirements of sports mats for high‐rebound resilience (>50%) and decrease the material cost when EVA was introduced into the foaming system. J. VINYL ADDIT. TECHNOL., 22:61–71, 2016. © 2014 Society of Plastics Engineers     

Preparation of microcellular poly(ethylene‐co‐octene) rubber foam with supercritical carbon dioxide

In the past 3 decades, there has been great advancement in the preparation of microcellular thermoplastic polymer foams. However, little attention has been paid to thermoplastic elastomers. In this study, microcellular poly(ethylene‐co‐octene) (PEOc) rubber foams with a cell density of 2.9 × 10¹⁰ cells/cm³ and a cell size of 1.9 μm were successfully prepared with carbon dioxide as the physical blowing agent with a batch foaming process. The microcellular PEOc foams exhibited a well‐defined, closed‐cell structure, a uniform cell size distribution, and the formation of unfoamed skin at low foaming temperatures. Their difference from thermoplastic foam was from obvious volume recovery in the atmosphere because of the elasticity of the polymer matrix. We investigated the effect of the molecular weight on the cell growth process by changing the foaming conditions, and two important effect factors on the cell growth, that is, the polymer matrix modulus/melt viscoelastic properties and gas diffusion coefficient, were assessed. With increasing molecular weight, the matrix modulus and melt viscosity tended to increase, whereas the gas solubility and diffusion coefficient decreased. The increase in the matrix modulus and melt viscosity tended to decrease the cell size and stabilize the cell structure at high foaming temperatures, whereas the increase in the gas diffusion coefficient facilitated cell growth at the beginning and limited cell growth because most of the gas diffused out of the polymer matrix during the long foaming times or at high foaming temperatures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of parameter changes on the structure and properties of low‐density polyethylene foam

Several parameters, such as crosslinking agent concentration, blowing agent concentration, and temperature, were varied to evaluate their effects on the structure and mechanical properties of low‐density polyethylene (LDPE) foams. Dicumyl peroxide (DCP) was used as crosslinking agent, while azodicarbonamide (ADC) was utilized as the blowing agent at different levels. The formulations were prepared by using a thermostatically controlled heated two‐roll mill and foamed by using a compression molding technique via a single‐stage foaming process at three foaming temperatures (165, 175, and 185°C). The resultant LDPE foams were characterized and found to have a closed cell structure. The density and gel content increased proportionally with crosslinking level, whereas density decreased when ADC level and foaming temperature were increased. Another characteristic evaluated was the foam cell size decreased when the crosslinking level and foaming temperature were increased. In contrast, increasing the ADC concentration only gave a maximum cell size increase up to 6 phr that decreased when 8 phr of ADC was used. Results also indicated that compression stress increased proportionally with DCP level and decreased when ADC concentration and foaming temperature were increased. Impact studies on the prepared foams showed that their ability to absorb impact energy decreased with increasing crosslinking level, foaming temperature, and blowing agent concentration. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Cell coalescence suppressed by crosslinking structure in polypropylene microcellular foaming

A series of crosslinked polypropylene samples with increased melt strengths were prepared via a copolymerization reaction, followed by melt processing. These crosslinked PP samples (PP‐Cs) were foamed by a temperature rising process using supercritical CO₂ as the physical blowing agent. The introduction of crosslinking structure resulted in PP‐Cs foams with well‐defined closed cell structure, decreased cell size, and increased cell density in comparison with a linear PP, which were attributed to the suppressed cell coalescence due to the significant increase in melt strength of PP‐Cs. Further increasing the crosslinking degree tended to enhance the suppression effect on the cell coalescence, and hence increase the cell density of PP foams under the same foaming conditions, especially at the longer foaming times. The well‐defined closed cell structure was observed at the foaming temperature of 170–250°C and saturation pressure of 12–20 MPa. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Rheological properties and foam preparation of biodegradable poly(butylene succinate)

To produce biodegradable poly(butylene succinate) (PBS) foam by compression molding, high viscosity PBS was prepared with dicumyl peroxide (DCP) as a crosslinking agent and trimethylolpropane trimethacrylate (TMPTMA) as a curing coagent by crosslink method. The influences of various factors on the foaming process and the properties of PBS foams were investigated. The results show that the use of DCP and TMPTMA simultaneously can effectively increase the melt viscosity of PBS. Zinc oxide/zinc stearate was used to reduce the thermal decomposition temperature of the blowing agent azodicarbonamide, which can balance well the vulcanization of PBS and the decomposition of blowing agent. Finally, closed‐cell PBS foams with degradable property have been successfully prepared by a traditional chemical compression molding foaming way. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Numerical simulation of polymer foaming process in extrusion flow

Computer simulations of polymer foaming processes in extrusion flow have been carried out in order to improve current understanding of viscoelasticity and bubble growth effects on die-swelling in the production of polymer foam. The linear and non-linear viscoelastic materials functions of a commercial low density polyethylene (LDPE) melt have been extracted by fitting its rheometric data with constitutive models including a simple viscoelastic model (SVM), the exponential Phan-Thien–Tanner (EPTT) model and the double convected pom–pom (DCPP) model. Simulations of LDPE melt under extrusion flow without foaming show that the predictions of the die-swell by the SVM are in reasonably good agreement with the results obtained from the EPTT and DCPP models. By comparison of the simulation results of LDPE foaming in extrusion flow using the Bird–Carreau model and the SVM, a cooperative effect of polymer viscoelasticity and bubble growth on the die-swell has been quantified. The numerical results also show that the density of polymeric foam decreases significantly with the increasing concentration of foaming agent, and that the combination of the SVM and bubble growth model can account for some essential physics of polymer foaming process in extrusion flow.     

Reactively Modified Poly(lactic acid): Properties and Foam Processing

Summary: In order to produce modified poly(lactic acid) (PLA) resins for applications requiring high melt viscosity and elasticity (e.g., low‐density foaming, thermoforming), a commercial PLA product has been reactively modified in melt by sequentially adding 1,4‐butanediol and 1,4‐butane diisocyanate as low‐molecular‐weight chain extenders. By varying amounts of the two chain extenders associated to the end group contents of PLA, three resulted samples were obtained. They were then structurally characterized by FTIR spectroscopy and molecular structure analysis. Their thermal, dynamic mechanical thermal properties and melt viscoelastic properties were investigated and compared along with unmodified PLA. The results indicated that chemical modification may be characterized as chain scission, extension, crosslinking, or any combination of the three depending on the chain extender amounts. The increase of PLA molecular weight could be obtained by properly controlling amounts of two chain extenders. The samples with increased molecular weights showed enhanced melt viscosity and elasticity. Such property improvements promised a successful application for modified PLA in a batch foam processing by producing foams with reduced cell size, increased cell density and lowered bulk foam density in comparison with plain PLA foam.

Cellular morphology of a modified PLA foam.     

Effect of clay dispersion on the cell structure of LDPE/clay nanocomposite foams

In this study, the effect of clay and its dispersion state on the cell morphology and foaming behavior of chemically crosslinked polyethylene (PE) foams were examined. In addition, the effect of foaming process on the clay morphology was also considered. It was shown that the morphology of the clay before the foaming process and its compatibility with PE matrix play a major role in determining the final foam properties. A PE‐g‐MA compatibilizer was used to increase the melt intercalation of PE onto the clay galleries and to improve clay dispersion in the PE matrix. The uniform dispersion of clay provided greater and well‐ dispersed nucleation sites. This led to smaller cell size, narrower cell size distribution, and higher cell density, and lower foam density. During the foaming process, intercalated clays were delaminated due to the rapid polymer melt expansion that inhibited gas release and increased foam expansion ratio. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

热塑挤出制备无机阻燃聚乙烯醇泡沫材料及其影响因素的研究

以水为增塑剂兼物理发泡剂,氢氧化铝(ATH)为无机阻燃剂兼异相成核剂,通过热塑挤出方法制备了无机阻燃聚乙烯醇/氢氧化铝(PVAL/ATH)复合泡沫材料,采用扫描电子显微镜(SEM)等研究了水和ATH含量、口模温度、螺杆转速、交联剂对复合泡沫材料泡孔结构的影响。结果表明,适当的口模温度和螺杆转速是实现体系中水的可控、连续、稳定发泡的关键因素,适量添加的阻燃剂能够起到良好异相成核剂的作用,在最佳工艺条件下,当PVAL/ATH/水为100/80/30,口模温度为125℃,螺杆转速为30 r/min时,制备得到综合性能优异的无机阻燃PVAL/ATH泡沫材料,泡沫材料的表观密度为0.32 g/cm3,膨胀倍率为10.0,泡孔密度约为1.6×105个/cm3。此外,引入硼酸作为交联剂,有效提高了熔体强度并改善了泡孔结构,交联后泡沫材料的拉伸强度和断裂伸长率分别提高到6.3 MPa和59.2%。     

Plasticization effects on bubble growth during polymer foaming

During polymer foaming with physical blowing agents, plasticization affects the melt viscosity, gas diffusivity in the melt, and the gas–melt interfacial tension. In this paper, we propose a model for plasticization during bubble growth, and estimate its effects under typical foaming conditions. The theoretical model incorporates well‐established mixture theories into a recent model for diffusion‐induced bubble growth. These include the free‐volume theories for the viscosity and diffusivity in polymer‐blowing agent mixtures and the density gradient theory for the interfacial tension. The viscoelasticity of the melt is represented by an Oldroyd‐B constitutive equation. We study the radial growth of a single bubble in an infinite expanse of melt, using parameter values based on experiments on polystyrene–CO₂ systems. Our results show that even at relatively low gas concentrations, plasticization increases the blowing‐agent diffusivity markedly and thus boosts the rate of bubble growth. In contrast, the reduction in melt viscosity and interfacial tension has little effect on bubble growth. Though not intended as quantitative guidelines for process design, these results are expected to apply qualitatively to typical foaming conditions and common polymer‐blowing agent combinations. POLYM. ENG. SCI., 46:97–107, 2006. © 2005 Society of Plastics Engineers     

Study of the effect of different electron irradiation doses on the decomposition temperature of azodicarbonamide

Azodicarbonamide (ADCA) is a well‐known chemical blowing agent used in the fabrication of polyolefin foams which decomposes into gases at temperatures above the melting temperature of the polymer. In these polymer foams, the polymer is usually crosslinked before or during the foaming process to increase its viscosity and make it capable of supporting the pressure of the gas during foaming. This crosslinking process allows producing low‐density foams with homogeneous cellular structures. A typical procedure to crosslink the polymer is to irradiate it using a high energy‐electron beam. When ADCA is incorporated into the polymer before the irradiation process, it is also exposed to the high energy electron beam. However, the effect of the irradiation on the decomposition process of ADCA has not been explored yet. In this research, it has been found that there is a reduction of the thermal decomposition temperature of ADCA when this material is electron irradiated with different doses ranging from 25 to 150 kGy, being this reduction higher when the irradiation dose is increased. It has also been found, that the reduction of the decomposition temperature is due to a modification of the lattice parameters of the crystalline structure of ADCA. POLYM. ENG. SCI., 59:791–798, 2019. © 2018 Society of Plastics Engineers     

Thermally expandable microcapsules for polymer foaming—Relationship between expandability and viscoelasticity

A new thermally expandable microcapsule was developed for use with foaming polypropylene (PP) by injection molding and extrusion processes at operating temperatures above 200°C. The microcapsule consists of a blowing agent as the core and a shell polymer. The rheological properties of the shell polymer were controlled by a crosslinking agent to design the expandability and shrinkage. The effects of rheological properties on the expandability and the surface appearance of foam products were thoroughly investigated. It was found that storage modulus G′ and tan δ significantly affected the expandability and shrinkage and were controllable through crosslinking polymerization. Visual observation of batch foaming, rheological measurement, and experiments of foam injection molding and extrusion elucidated the existence of the optimal degree of crosslinking that could realize more than 30% density reduction while maintaining a smoothsurface at PP foam injection molding and extrusion. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Foaming of aliphatic polyester using chemical blowing agent

Poly(butylene adipate‐co‐succinate) (PBAS), a saturated aliphatic polyester cured by dicumyl peroxide (DCP), was prepared and the viscoelastic property was investigated. The viscosity of crosslinked PBAS increased, and it exhibited rubbery behavior as the content of curing agent was increased. The results suggested that the viscosity and elasticity of PBAS could be regulated by adding a small amount of DCP; hence, the processibility could be improved. Prior to foaming, a proper formulation of blowing agent (blowing agent/urea activator = 100:8 phr) was examined to prepare expanded PBAS foam. Low‐density PBAS expanded foams were prepared using a chemical blowing agent and DCP. The effect of the foaming temperature, additive content, and curing agent content on the blowing ratio and morphology of expanded PBAS foams was investigated. A closed‐cell structure PBAS foam of high blowing ratio (density about 0.05 g/cm³) could be obtained by adding 3 phr DCP. To manufacture expanded PBAS foam under 0.1 g/cm³ using a chemical blowing agent, the storage modulus of the matrix polymer should exceed the loss modulus by enough to stabilize growing bubbles. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2443–2454, 2001     

Crosslinking of rotational molding foams of polyethylene

Rotational molding of foamed polyethylene has increasingly become an important process in industry due to its ability to produce innovative and high added value parts with little specialist equipment required. The polyolefin foam production tends to achieve the highest possible cell size uniformity and cell size reduction. To improve the cell morphology of the PE foams, the cell coalescence and coarsening might be suppressed, which can be accomplished preserving the melt strength of the polymer during processing. With this aim, in this work two peroxides have been used to enhance the melt strength of a linear low‐density polyethylene by chemical crosslinking. The moldings have been processed at different oven residence times and they have been characterized according to their density, gel content, bubble size distribution and impact strength. Despite the lower crosslinking degree attained by the crosslinked foams, the results show an enhancement in the cell morphology of these moldings, which are able to keep their cell size distribution even with the longest processing times and consequently the processing window of these rotational molding foams is widened. POLYM. ENG. SCI., 47:1804–1812, 2007. © 2007 Society of Plastics Engineers     

交联剂对聚乳酸流变性能及其发泡材料泡孔结构的影响

在研究交联剂对聚乳酸(PLA)流变性能影响的基础上,采用间歇发泡方法研究交联PLA发泡材料的泡孔结构。结果表明,交联剂可提高低频区PLA的损耗角正切和复数黏度以及PLA的熔体强度和拉伸黏度。交联PLA的复数黏度高,使泡孔长大初期的长大速率较低;泡孔长大后期泡孔壁被拉伸时,熔体强度和拉伸黏度的急剧提高使泡孔壁强度增加而不会被撕裂,大大减小泡孔的合并,形成较均匀且较规则的泡孔结构。交联PLA高的熔体强度可明显减少发泡时二氧化碳扩散至空气中的量,从而增加PLA发泡样品的体积膨胀率;加入0.4 phr的交联剂时,样品的体积膨胀率最大(达41)。     

模压法制备高发泡聚丙烯/木粉复合泡沫材料

为制备出高发泡倍率的聚丙烯(PP)/木粉复合泡沫材料,对其在制备过程中所面临的发泡剂分解温度太高、PP熔体强度过低及木粉与PP界面相容性差这三大关键难题进行分析并解决。结果表明:当活化剂ZnO添加量为发泡剂AC的0.3倍时,AC分解温度符合发泡过程的要求,提高温度有利于缩短发泡剂分解前诱导期及发泡剂的分解时间;交联剂添加量为9份,助交联剂添加量为7份时,材料的交联效果最好,交联时间控制在7min左右最佳;当偶联剂添加量2份时处理木粉最为合适,此时木粉与PP的界面相容性的改善效果最佳。     

Strategies for achieving ultra low‐density polypropylene foams

The volume expansion behavior of low‐density polypropylene foams in extrusion is investigated in this paper. Since escape of blowing agent from the foam would cause the foam to contract, and to have low expansion, efforts were made to prevent gas loss during foaming. The basic strategies to the promotion of a large volume expansion ratio are: to use a branched material for preventing cell coalescence; to use a long‐chain blowing agent with low diffusivity; to lower the melt temperature for decreasing gas loss during expansion; and to optimize the processing conditions in the die for avoiding too‐rapid crystallization. Use of a branched polypropylene resin was required to achieve large volume expansion because prevention of cell coalescence will retard gas loss from the extruded foam to the environment. The foam morphologies of linear and branched polypropylene materials at various processing temperatures were studied using a single‐screw tandem foam extrusion system and their volume expansion behaviors were compared. Ultra lowdensity, fine‐celled polypropylene foams with very high expansion ratio up to 90 fold were successfully produced from the branched polypropylene resins.     

热塑性聚酯弹性体TPEE挤出发泡研究

通过单螺杆熔融挤出制备了热塑性聚酯弹性体(TPEE)发泡片材.研究了复合发泡剂偶氮二甲酰胺(AC)/碳酸氢柠檬酸配比、发泡剂包覆体以及TPEE交联剂对发泡片材性能的影响.表观密度、力学性能和SEM结果显示:复合发泡剂AC/碳酸氢钠/柠檬酸的最佳质量比为15/5/5,丙烯酸酯包覆体可使TPEE发泡效果变好.凝胶含量和压缩永久形变结果显示:凝胶含量随交联剂用量的增加而增大,环氧交联剂用量为0.8份和异氰酸酯交联剂用量为1份时,发泡片材的压缩永久形变最小.动态力学分析(DMA)显示:交联发泡片材的损耗因子(tanδ)大于0.25,峰值温度130℃.扫描电镜和光学显微镜结果显示:异氰酸酯交联剂用量为1份时,发泡片材的泡孔直径大小均匀,分布集中.     

低密度交联硬质聚氯乙烯泡沫塑料的研究

以酸酐和异氰酸酯为交联组分,糊用聚氯乙烯为基体树脂,制备了低密度交联硬质聚氯乙烯(Crosslinked-PVC)泡沫塑料。考察了甲基六氢苯酐、偏苯三酸酐和对苯二甲酸与甲苯二异氰酸酯及多亚甲基多苯基多异氰酸酯的不同官能度配比对模压块和泡沫塑料交联度的影响,酸酐/异氰酸酯配比对泡沫塑料的性能影响,不同[K]值PVC树脂对泡沫塑料的性能影响。研究表明,异氰酸酯和酸酐的官能度对模压块和泡沫塑料的交联度影响十分显著,模压块中过早产生交联对后续发泡过程不利。随着酸酐/异氰酸酯摩尔比的增加,泡沫密度减小,压缩强度降低,且泡沫密度达到最低密度的时间缩短。当糊用PVC树脂[K]值过小时,发泡体系容易发生并泡和中间鼓泡;当[K]值过大时,压缩性能反而下降。制备的Crosslinked-PVC泡沫塑料具有半互穿聚合物网络结构。     

PVC-U低发泡制品中常用发泡剂性能分析

介绍了PVC-U低发泡制品中常用的发泡剂及其发展趋势,分析了不同发泡剂对生产加工及制品性能的影响。结果表明,NaHCO3发泡剂和ADC发泡剂复合使用,可以使热量的吸热、放热互补,形成平衡,发泡易于控制;ADC发泡剂的粒径越细,产品发泡越均匀、细密,密度越小,材料性能越好;当熔体强度适宜时,ADC发泡剂添加量越多,在熔体中形成的气泡也越多,制品的密度越小。