Modeling the dynamics of reactive foaming and film thinning in polyurethane foams

Flexible polyurethane foams are widely used in cushioning and packaging applications. A model for the dynamics of formation of polyurethane foams is presented, which includes thinning of foam lamellae. Experimental measurements for water blown flexible foam formulations at different water concentrations are presented to validate the model. Adiabatic temperature rise measurements during foaming are used to obtain the kinetic parameters of the reactions of isocyanate with polyol and water. The variation of foam density during foaming is studied by weight loss and video shooting methods and both are compared to estimate the amount of blowing gas lost during foaming. The average thickness of the foam lamellae of the solid foam is obtained by SEM measurements. The predictions of the model show good agreement with the experimental measurements of temperature and density with time and the final lamellar thickness. The results are important for understanding the cell opening process. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Effect of monomer temperature on foaming and properties of flexible polyurethane foams

Polyurethane foam formation involves simultaneous polymerization and expansion. In an open cell foam, foam lamellae rupture at some stage of foam formation, resulting in a foam with continuous air channels. Experiments are carried out to study the effect of initial temperature of monomers on the open cell content of water‐blown flexible polyurethane foams. The change in kinetics of the polymerization and blowing with initial monomer temperature is noted by measuring the gel and rise times during foaming. Both polymerization and blowing reactions are found to be faster with increasing monomer temperature. The cell size is found to increase with initial monomer temperature, and the height of the cured free rise foam is found to decrease. The open cell content of the foam increased considerably with initial monomer temperature, leading finally to the collapse of the foam at the highest temperatures studied. The mechanical properties of the foam at different monomer temperatures are determined by making molded foams. The indentation load deflection decreased with increasing monomer temperature indicating the formation of softer foams, but showed a slight increase near the temperature of collapse. Other mechanical properties showed a small degradation with increase in initial monomer temperatures. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

HCFC—141b发泡聚氨酯硬泡的性能及其改进

讨论了在聚氨酯硬泡发泡剂替代中,ＨＣＦＣ－１４１ｂ与ＣＦＣ－１１发泡体系在与基材的粘接性,组合料的粘度,泡沫制品的热导性,尺寸稳定性,脆性等性能上的差异,提出了相应的调整,改进措施。比较了改进后ＨＣＦＣ－１４１ｂ发泡泡沫与传统ＣＦＣ－１１发泡泡沫的性能。     

Bubble-scale observations of polyurethane foam expansion

We describe experiments designed to inform computational models of the dynamic filling process of chemically blown, polyurethane foams, especially subgrid models to predict bubble size affecting foam properties. Three experimental methods are used to observe the evolution of bubble sizes during blowing. Magnified views of bubbles at a transparent wall of a channel are recorded during the foaming. The bubble sizes in the final frame after the expansion has stopped are compared to scanning electron microscope images of the interior of the cured samples to determine wall effects. In addition, diffusing wave spectroscopy is used to determine the average bubble sizes across the width of a similar channel during foam expansion. We conclude that the bubble size distribution is dependent on the formulation of foam being tested, temperature, the height in the foam bar, the proximity to a wall, and the degree of overpacking.     

Foaming of PS/wood fiber composites using moisture as a blowing agent

This paper presents an experimental study on foam processing of polystyrene (PS) and high‐impact polystyrene HIPS/wood‐fiber composites in extrusion using moisture as a blowing agent. Wood‐fiber inherently contains moisture that can potentially be used as a blowing agent. Undried wood‐fiber was processed together with PS and HIPS materials in extrusion and wood‐fiber composite foams were produced. The cellular morphology and volume expansion ratios of the foamed composites were characterized. Because of the high stiffness of styrenic materials, moisture condensation during cooling after expansion at high temperature did not cause much contraction of the foamed composite and a high volume expansion ratio up to 20 was successfully obtained. The experimental results showed that the expansion ratio could be controlled by varying the processing temperature and the moisture content in the wood fiber. The effects of a small amount of a chemical blowing agent and mineral oil on the cell morphologies of plastic/wood‐fiber composite foams were also investigated.     

Physical Blowing Agent Residence Conditions Stimulated Morphological Transformations in Extrusion Foaming

In this study, influence of blowing agent residence conditions on foam attributes has been investigated in extrusion foaming process. The blowing agent injection location in the extrusion barrel was found to affect the residence time inside the barrel, which in turn significantly transformed the foam microstructure. The injection location providing higher gas residence time resulted in foams with lower cell size, higher expansion ratio, and enhanced cell density. Further studies were performed to analyze the synergistic influence of residence time variation on foam attributes at different screw rotational speeds, die temperatures, and blowing agent contents.     

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%。     

Effect of auxiliary blowing agents on properties of rigid polyurethane foams based on liquefied products from peanut shell

The bio‐based rigid polyurethane (PU) foams were successfully prepared based on liquefied products from peanut shell with water as the blowing agent. The influence of reaction parameters on properties of rigid PU foams was investigated. Rigid PU foams showed excellent compressive strength and low shrinkage ratio, whereas their open‐cell ratio and water absorption were higher. Therefore, rigid PU foams were synthesized with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents and their inner temperature, shrinkage performance, density, compressive strength, water absorption, and open‐cell ratio were determined. The results indicated that above rigid PU foams showed lower compressive strength than the original foam but their water absorption and close‐cell ratio were improved. Compared with the original foam, the highest inner temperature of rigid PU foams with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents was reduced by 11, 19, and 23 °C, respectively. Typically, foams with petroleum ether as auxiliary blowing agent displayed better water absorption and swelling ratio in water and exhibited obvious improvement in close‐cell ratio. These foams were preferable for application in thermal insulation materials because of low thermal conductivity and better corrosion resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45582.     

Twin‐screw extrusion production and characterization of starch foam products for use in cushioning and insulation applications

Cylindrical starch foam shapes were produced on a small scale (～11–12 kg/hr) Werner Pfleiderer ZSK‐30 twin‐screw extrusion (TSE) process using water, which functions as a plasticizer as well as a blowing agent. The properties of the starch foams depend on the type of starch used (hydroxypropylated high amylose corn starch, 70% amylose), the amount of water and additives (poly(hydroxyamino ether)) (PHAE) used, and extrusion conditions such as temperature and the screw configuration. PHAE offers the adhesion and durability of epoxy resins with the flexibility and processibility of thermoplastic resins. PHAE was successful in imparting mechanical strength and toughness, cell integrity, weather and water resistance to the foam structure. The purpose of this work was to study the effects of the extrusion (melt) temperature, amount of water added and the screw configuration on the density of starch foams. The water externally added was varied from 3% to 12%, while the PHAE content was varied from 3% to 15% of the starch used (on a wet basis). The foaming was carried out at melt temperatures in the range from 85 to 145°C. A match of material properties with process engineering conditions was achieved to facilitate the control of expansion to a structure with valuable commercial properties. The effects of processing conditions on the foaming process were studied using a Werner Pfleiderer ZSK‐30 twin screw extruder. The optimum temperature, blowing agent content, and PHAE content were determined. The density of the cylindrical foam extrudates obtained was 22–25 kg/m³. The screw configuration, temperature and pressure profiles, and additives affected the morphology, expansion ratio (ER), resilience, and compressibility of the product. These results were then employed on an industrial scale (410–420 kg/hr) twin‐screw food extruder, a Wenger‐80, to manufacture foam sheets. The density of the foam sheets was 27–30 kg/m³. The cushioning and insulation properties were studied and are reported. POLYM. ENG. SCI., 46:438–451, 2006. © 2006 Society of Plastics Engineers     

低CFC发泡工艺

介绍了减少75％CFC－11的聚氨酯硬质泡沫塑料的发泡工艺，对影响工艺参数和泡沫性能的一些因素进行了讨论。该泡沫的密度与导热系数较全CFC－11发泡泡沫均增大15％～20％。     

Rigid polyurethane foams: A model of the foaming process

A model of the manufacture of rigid polyurethane foams by free rising is presented. The extent of cream and rise periods as well as the amount of blowing agent necessary to give the desired foam density are theoretically predicted. The rate of blowing agent evaporation is calculated from an experimental boiling temperature vs. composition curve. Experimental runs were carried out with a formulation consisting of a polymeric isocyanate, a polyether polyol based on sorbitol, a silicone-polyol block-copolymer as surfactant, dibutyltin dilaurate as catalyst, and trichlorofluoromethane as blowing agent. Mixing was performed in situ in the mold using a commercial foaming machine. Experimental results gave a satisfactory agreement with model predictions. A diagram containing all the relevant information may be theoretically built and used for the selection of adequate operating parameters for a given formulation.     

Development of water‐blown bio‐based thermoplastic polyurethane foams using bio‐derived chain extender

Water‐blown bio‐based thermoplastic polyurethane (TPU) formulations were developed to fulfill the requirements of the reactive rotational molding/foaming process. They were prepared using synthetic and bio‐based chain extenders. Foams were prepared by stirring polyether polyol (macrodiol), chain extender (diol), surfactant (silicone oil), chemical blowing agent (distilled water), catalyst, and diisocyanate. The concentration of chain extender, blowing agent, and surfactant were varied and their effects on foaming kinetics, physical, mechanical, and morphological properties of foams were investigated. Density, compressive strength, and modulus of foams decrease with increasing blowing agent concentration and increase with increasing chain extender concentration, but are not significantly affected by changes in surfactant concentration. The foam glass‐transition temperatures increase with increasing blowing agent and chain extender concentrations. The foam cell size slightly increases with increasing blowing agent content and decreases upon surfactant addition (without any dependence on concentration), whereas chain extender concentration has no effect on cell size. Bio‐based 1,3‐propanediol can be used successfully for the preparation TPU foams without sacrificing any properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

The importance of timely polymer sintering while processing polypropylene foams in rotational molding

Producing polypropylene (PP) foams with satisfactory cell morphologies in rotational foam molding is feasible. However, the narrow interval between the melting temperature of PP and the onset decomposition temperature of the applicable chemical blowing agent (CBA), and the relatively low melt strength of PP at elevated temperatures are considered the greatest obstacles in processing PP foams. The experimental results revealed that the morphology of the foams obtained by processing PP pellets that have been pre‐compounded with a CBA could be governed by either pellet sintering or cell coalescence. The viscosity of the basic PP resin and the processing temperature determine which of these two key factors will assume a predominating influence towards the foaming process. The desired volume expansion ratio (VER) of the foam also plays an important role since it determines the formulation of the foamable resin and the shot size. Desirable PP foam structures in compounding based rotational foam molding can be obtained only if pellet sintering takes place prior to the decomposition of the CBA and if the processing temperature during the foaming process is kept lower than the temperature of cell coalescence.     

Rigid polyurethane foams based on soybean oil

Both HCFC‐ and pentane‐blown rigid polyurethane foams have been prepared from polyols derived from soybean oil. The effect of formulation variables on foam properties was studied by altering the types and amounts of catalyst, surfactant, water, crosslinker, blowing agent, and isocyanate, respectively. While compressive strength of the soy foams is optimal at 2 pph of surfactant B‐8404, it increases with increasing the amount of water, glycerin, and isocyanate. It also increases linearly with foam density. These foams were found to have comparable mechanical and thermoinsulating properties to foams of petrochemical origin. A comparison in the thermal and thermo‐oxidative behaviors of soy‐ and PPO‐based foams revealed that the former is more stable toward both thermal degradation and thermal oxidation. The lack of ether linkages in the soy‐based rather than in PPO‐based polyols is thought to be the origin of improved thermal and thermo‐oxidative stabilities of soy‐based foams. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 467–473, 2000     

Effect of foaming temperature and rubber grades on properties of natural rubber foams

Foaming temperature and grade of dry natural rubber were varied to evaluate their effects on the morphology and mechanical properties of natural rubber (NR) foams. Three different grades of NR were used; namely ENR‐25, SMR‐L, and SMR‐10. NR foams from these grades were produced at three different foaming temperatures, i.e. 140, 150, and 160°C. The study was carried out using formulated compositions containing sodium bicarbonate as the chemical blowing agent and were expanded using conventional compression molding technique via a heat transfer foaming process. The NR foams were characterized with respect to their relative foam density, density of crosslinking, cell size, compression stress, and compression set. Increase in foaming temperature resulted in lower relative density and larger cell size. It was also discovered that the crosslink density slightly decrease with increasing foaming temperature. For mechanical properties, the highest foam density resulted in the highest compression stress. Compression stress at 50% strain increased with increasing foaming temperature and ENR‐25 foam has the highest compression stress among the produced foams. The results showed that the morphology, physical, and mechanical properties of the rubber foams can be controlled closely by the foaming temperature and rubber grades. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Generation of low‐density high‐performance poly(arylene ether sulfone) foams using a benign processing technique

In this study, a benign process was used to successfully produce low density foam from poly(arylene ether sulfone) (PAES). Both carbon dioxide (CO₂) and water as well as nitrogen and water were used as physical blowing agents in a one‐step batch process. A large amount of blowing agents (up to 7.5%) was able to diffuse into the PAES resin in a 2‐h saturation time. Utilizing water and CO₂ as the blowing agents yielded foam with better properties than nitrogen and water because both the water and CO₂ are plasticizers for the PAES resin. PAES foam produced from CO₂ and water had a large reduction in foam density (～80%) and a cell size of ～50 μm, while maintaining a primarily closed cell structure. The small cell size and closed cell structure enhanced the mechanical properties of the foam when compared with the PAES foam produced from nitrogen and water. The tensile, compressive, and notched izod impact properties of the PAES foams were examined, and the compressive properties were compared to commercially available structural foams. With reduced compression strength of 39 MPa and reduced compression modulus of 913 MPa, the PAES foam is comparable to polyetherimide and poly(vinylchloride) structural foams. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Bubble Size Distribution and Elastic Retraction in Crosslinked Metallocene Polyolefin Elastomer Foams

The effects of crosslink density and blowing pressure on the cell size of m-POE (metallocene polyolefin elastomer) foams are presented. The crosslink density and the blowing pressure were controlled by varying the loadings of the crosslinking agent and the chemical blowing agent, respectively, in the m-POE foam compounds. The cell size distributions were obtained by optical microscopic observations along with an image analysis software. After comparing the foam piece density before and after high-temperature heating, it was deduced that the foaming of m-POE is a highly elastic process. The equation for the inflation of an elastic spherical cavity was thus adopted in relating the cell size to the blowing pressure and the crosslink density. The average cell size can be roughly scaled by a single parameter: the ratio of blowing pressure to crosslink density.     

Density modeling of polyurethane box foam

A model based on about a dozen fundamental differential equations is used to evaluate and simulate the urethane reactions and physical processes of urethane box foaming. This work focuses on quantitative modeling of foam density for foams using water and physical blowing agents. The final densities of foams range from 30 to 90% of the density as projected with full utilization of the blowing agent. The primary sources of inefficient use of blowing agent are loss of the physical blowing during open‐air mixing and degassing—basically, physical blowing agents with boiling points between 25 and 80°C will evaporate and experience cell rupture in box foams. This loss of blowing agent would not apply to in‐line mixers used for commercial production and should be taken into account with scaling up box or cup foams commercial processes. POLYM. ENG. SCI., 54:1503–1511, 2014. © 2013 Society of Plastics Engineers     

Study on foaming kinetics and preparation of EPDM foams

Abstract

The ethylene–propylene–diene terpolymer (EPDM) foam article was prepared by mixing a compound in a two roll mill, extruding the compound through a cold feed extruder and finally vulcanising the extrudate in a circulating hot air oven. The blowing kinetics of EPDM compounds was studied using a moving die rheometer, and the effect of blowing agent content and process temperature on the cell structures was investigated. The results show that kinetic parameters determined from the autocatalystic model equation have good agreement with the experimental results. The calculated activation energy of azodicarbonamide (AC) decomposition is higher than that of rubber cure, which indicates the rate of blowing agent AC decomposition accelerates more quickly than that of rubber vulcanisation with increasing temperature. The density of foam article decreases with increasing blowing agent content or elevated temperature. The foams have a closed cell structure and the larger cells inlay among the smaller cells, which shows cell materials with structural multihierarchy. This shows the rubber vulcanisation and blowing agent decomposition could match only using extremely slow accelerator diphenylguanidine (DPG), which is dissimilar to the conventional EPDM sponge requiring very quick scorch.