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     

Effects of Process Variables on Microcellular Structure and Crystallization of Polypropylene Foams with Supercritical CO2 as the Foaming Agent—A Study of Microcellular Foaming of Polypropylene

The effects of process variables on the microcellular structure and crystallization of foamed polypropylene (PP) with supercritical CO₂ as the foaming agent were investigated in this article. The cell size increased and the cell density reduced with increased foaming temperature. Differently, both the cell diameter and cell density increased as saturation pressure increased. DSC curves showed that the melting peak was broadened when supercritical CO₂ foaming PP. Furthermore, the width at half-height of the melting peak increased, the melting peak moved to higher temperature, and the melting point and crystallinity enhanced as the foaming temperature lowered and the saturation pressure enhanced.     

黏度对水发泡聚苯乙烯发泡性能的影响

采用水作为物理发泡剂,对聚苯乙烯(PS)进行挤出发泡。研究了低温PS水发泡的流变性能,并研究了黏度对PS发泡制品性能的影响。结果表明:水会影响PS在发泡加工过程中的黏度;在低温情况下,水发泡后的PS仍然具有流动性;其黏度随剪切速率的增大而减小,在相同的剪切速率下,温度越高黏度越低。当模头温度为140℃、螺杆转速为15r/min时,可制备出表面光滑、泡孔细密均匀、质轻的PS水发泡制品。     

碳纤维增强微孔可燃壳体的制备及性能研究

为改善以黑索金(RDX)为含能组分、二醋酸纤维素(CA)为黏结剂的可燃壳体的力学性能,在此基础配方上添加适量碳纤维(CF),然后通过超临界二氧化碳(SC-CO2)发泡技术制备了微孔可燃壳体;采用扫描电子显微镜和落锤冲击试验机,分别研究了发泡前后可燃壳体的断面形貌和力学性能。结果表明,添加适量的CF,可提高可燃壳体的冲击强度,且冲击强度随着CF添加量的增大而增大;当CF的质量分数为1.0%时,未发泡可燃壳体的力学性能最优,冲击强度由5.11kJ/m²提高到8.20kJ/m²,增幅达60.47%;增大饱和压力、发泡温度和发泡时间都能够增大泡孔直径,但发泡温度高于130℃会导致泡孔合并;发泡将降低壳体的力学性能,但采用受限发泡制得的可燃壳体的冲击强度优于自由发泡法,当发泡时间为180s时,受限发泡的冲击强度由自由发泡时的5.93kJ/m²升至6.34kJ/m²。     

水辅助超临界二氧化碳制备TPU发泡颗粒

利用水和超临界二氧化碳作为共发泡剂,采用快速泄压法制备热塑性聚氨酯弹性体(TPU)发泡颗粒,分别考察了加水量、饱和温度和饱和时间对TPU发泡颗粒性能的影响。结果表明,当饱和温度为180℃、饱和时间为30 min时,随着加水量的增加,TPU发泡颗粒的边缘厚度明显降低,当加水量为4 mL时,发泡颗粒的边缘厚度比不添加水时下降了63.0%,同时发泡倍率提高了89.8%。当加水量为2 mL、饱和时间为30 min时,饱和温度的升高使得发泡倍率随之升高,饱和温度为190℃时的发泡倍率比饱和温度为150℃时提高了94.8%。当加水量为2 mL、饱和温度为180℃时,饱和时间超过1 h后,随着饱和时间的延长,发泡倍率和泡孔密度减小,边缘厚度和泡孔平均直径增大,并出现通孔结构。     

Cell evolution and compressive properties of styrene–butadiene–styrene toughened and calcium carbonate reinforced polystyrene extrusion foams with supercritical carbon dioxide

Polystyrene (PS) foams have been used in various fields, whereas its broader application is limited by its low mechanical strength and brittle features. In this study, styrene–butadiene–styrene (SBS) and calcium carbonate (CaCO₃) nanoparticles were melt‐blended with PS and extrusion‐foamed with supercritical carbon dioxide as a blowing agent to simultaneously toughen and reinforce PS foams. Under the same foaming conditions, the addition of SBS and CaCO₃ was shown to have a significant influence on the cell structure and the compressive properties of the composite foams. We found that the cell structure evolution was highly correlated with the system viscosity. When the rubbery‐phase SBS content was 20%, the cell diameter decreased by 20.7%, and the compressive modulus was enhanced by 289.5%. With the further addition of 5% rigid CaCO₃ nanoparticles, the cell diameter was further reduced by 72.2% and the compressive modulus was improved by 379.2%. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43508.     

Solid‐state foaming of carbon fiber/polypropylene/nano‐CACO3 composite using supercritical CO2

In this work, nano‐CaCO₃ was used to improve the foamability of carbon fiber (CF)/polypropylene (PP) composite in solid‐state foaming using supercritical CO₂. The CF content was maintained at 15 wt% and four concentrations of nano‐CaCO₃ content, 1, 3, 5 and 8phr, were used. The surface of nano‐CaCO₃ was firstly treated by silane coupling agent. By the way, the properties of the nano‐composites with various nano‐CaCO₃ contents were analyzed by scanning electron microscope (SEM), differential scanning calorimeter (DSC), and torque rheometer. Before foaming, the gas absorption experiment was done using gravimetric method. Concerning on determination of the foaming conditions, it is found that 175°C and 60s were suitable as foaming temperature and time. Furthermore, we can also find that the foamed composites with 3phr nano‐CaCO₃ showed the smallest mean cell diameter and largest cell density compared with the other nano‐CaCO₃ contents under the given saturation condition. In addition, the mean cell diameter decreased while cell density increased as saturation pressure increased because of the higher gas solubility in the composites. When the saturation pressure was 25MPa, the mean cell diameter and cell density with 3phr nano‐CaCO₃ were 17μm and 2.20×10⁷cells/cm³, respectively. POLYM. COMPOS., 35:1723–1735, 2014. © 2013 Society of Plastics Engineers     

Structure and Properties of Radiation Cross-Linked Polypropylene Foam

Polypropylene (PP) sheets obtained through a two-step process (masterbatch method) were crosslinked by electron beam irradiation. The crosslinked PP sheets were foamed in an oven under different processing conditions. The effects of foaming temperature and time on the mechanical properties and cell structure of PP foams were studied. With the foaming temperature increasing and foaming time lengthening, both the compression modulus and compression strength dropped. Scanning electron microscope (SEM) was employed to study the morphology and cell structure of different samples and the related morphology parameters were acquired. The results showed there was an optimum temperature and time that produced the maximum expansion ratio or the minimum foam density. As foaming temperature or time increased, the cell size increased and the cell density decreased regularly. Excessively high foaming temperature and overly long foaming time caused the coalescence and even the collapse of the cells.     

本征特性对聚苯乙烯及聚丙烯发泡行为的影响

以化学发泡注塑成型技术为主线,在二次开模条件下制备微发泡聚苯乙烯（PS）及微发泡聚丙烯（PP）;通过流变性、加工性分析了树脂本征特性对PS及PP发泡行为的影响。结果表明：本征特性对气泡的长大和定型过程、气体扩散具有明显的影响;熔体强度越高的材料,阻碍泡孔长大的趋势越明显,所得到的泡孔越细小而均匀;PS具有合适的熔体强度和熔体流动速率（MFR）,发泡质量较理想,泡孔直径和泡孔密度分别为41.4μm、8.7×106个/cm3;PP（K9026）熔体强度较低,而熔体流动速率过大,发泡质量明显降低,泡孔直径和泡孔密度分别为65.94μm、5.82×105个/cm3。     

发泡工艺对超临界CO2／PP微孔发泡泡孔形态的影响

研究了超临界CO2／PP微孔发泡过程中发泡温度和饱和压力对结晶性聚合物PP泡孔形态的影响。结果表明，温度对泡孔形态影响很大，温度升高，熔体黏度和表面张力降低，泡孔变大，泡孔密度减小。与发泡温度相比，CO2饱和压力对泡孔结构的影响较小。压力太低，CO2的溶解度小，泡孔壁太厚，泡孔分布不均匀。随着压力升高，CO2的溶解度增加，熔体黏度减小，所以泡孔直径和泡孔密度都增加，泡孔壁变薄。     

Diffusion and desorption of CO2 in foamed polystyrene film

Based on the existence of the pores in foamed polystyrene (PS), foamed‐non‐Fickian diffusion (FNFD) model was proposed, for the first time, to regress the desorption data obtained by gravimetric method. Results showed that FNFD model could accurately describe the diffusion behavior of CO₂ out of foamed PS, and well predict the solubility of CO₂ in foamed PS. The characterization of scanning electron microscopy indicated that there were abundant pores in the foamed PS, and the pores store most of CO₂, which would diffuse in the pores, adsorb to the wall of the pores, penetrate across walls of the pores, diffuse in the matrix of PS, and desorb out of PS. The mass of CO₂ in the pores of foamed PS was expressed as a function of foaming pressure and temperature according to foaming kinetics. Results showed that the values calculated by this function agreed well with the values obtained from the FNFD model. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45645.     

Preparation Process Orthogonal Optimization and Mechanical Properties of Microcellular Foam Polypropylene

Melt strength, pressure and the amount of gas have significant effects on the foaming of polypropylene (PP). It is convenient to study the influence of these factors on foaming effect by orthogonal test. The experiment result shows that within the set factors and levels, the improvement of melt and the concentration of foaming masterbatch has the greatest influence on the cell size and density of foamed PP, respectively. When the concentration of azodicarbonamide (ADC) is 15 %, PP/ethylene-propylene terpolymer (EPDM) = 90:10, and SiO₂ content is 3%, the foaming effect is the best. At this time, the cell diameter decreases by 42.7%, cell density increases by more than 7.5 times compared with that without optimization. Material density decreases from 0.92 to 0.56 g cm⁻³. It is also found that good closed-cell structure can improve the bending and impact properties of PP in varying degrees, especially the impact strength is 55.7% higher than that of neat PP. Finally, the promoting mechanism of cell structure on mechanical properties of materials is discussed, which is of great significance for the preparation of microfoamed PP materials and the deep research of its cell structure.     

基于超临界CO2间歇法制备超轻TPU颗粒的研究

采用超临界流体间歇式微发泡技术制备了超轻热塑性聚氨酯弹性体(TPU)颗粒,利用扫描电子显微镜等研究了发泡温度、饱和时间及饱和压力对制备超轻TPU颗粒密度和性能的影响。结果表明,发泡温度和饱和压力是影响颗粒泡孔结构分布和粒料性能的主要因素;当饱和压力为11 MPa、发泡温度为145 ℃时,所得的超轻TPU颗粒密度较小、粒径较大,其内部泡孔数量较多,泡孔结构分布均匀。     

Effect of processing parameters on cell morphology of polycarbonate foam

Abstract

The purpose of this research is to investigate the effect of processing parameters on the cell morphology of polycarbonate (PC) foam. In this study, foamed PC was prepared using a dynamic simulation foaming set-up. The cell morphology was compared at different temperatures, pressures, gas saturation times, pressure drop rates and shear rates. The cell morphology of foamed samples was characterised using SEM. It was found that foamed samples with better morphology could be obtained by varying mechanical properties, such as pressure, pressure drop rate and gas saturation time. Optimum temperature and shear rate for microcellular foaming of PC are presented.     

基于废旧轮胎胶粉的热塑性弹性体的制备及发泡性能研究

通过沥青改性胶粉及采用相容剂与聚丙烯共混制备了性能优良的热塑性弹性体(TPE)材料,并以超临界流体为发泡剂对其发泡性能进行了研究。实验结果表明,胶粉通过沥青改性后,可以明显地提高TPE的拉断伸长率,并且发泡TPE的泡孔平均直径增大,泡孔密度减少,相对密度减小,但是随着沥青用量的增加,材料的粘度降低,从而出现泡孔破裂和塌陷现象,最后导致泡孔平均直径和泡孔密度减小,相对密度增加。相容剂苯乙烯嵌段共聚物接枝马来酸酐(SEBS-g-MA)可以提TPE的拉断伸长率并改善泡孔结构。温度的升高和饱和压力的增大,都导致了发泡弹性体的泡孔增大,泡孔密度和相对密度减小。     

Micro/nanocellular polyprolene/trans-1,4-polyisomprene (PP/TPI) blend foams by using supercritical nitrogen as blowing agent

Toughed polypropylene (PP) foams, with the combination of blending with trans-1,4-polyisoprene (TPI) and micro/nanocellular structure in the matrix, were prepared using a batch foaming process and N₂ as the blowing agent. The incorporation of TPI in the PP matrix induces the enhanced formability and the slightly improved ductility and toughness compared to the neat PP. The simultaneous existence of the TPI phase and micro/nanocellular structure makes the fracture behavior follow the shear yielding of a bundle of fibrils in the tensile load direction. The results of mechanical properties measurements show that the notched Izod impact strengths of foamed PP/TPI blend are two to three times larger than those of the unfoamed counterparts. The PP/TPI blend foam with 5phr TPI content shows the highest impact strength when the foaming temperature is 140°C, which is fivefold increase over that of the neat PP. The enhanced ductility and toughness of PP/TPI foams were found with the increasing foaming temperature. The insert of micro−/nanocellular in PP/TPI blends simultaneously makes the notched impact strength increase significantly, tensile strength decrease, and elongation at break increase obviously, which provides the possibility to combine the higher impact strength and toughness with the advantage of microcellular foaming. POLYM. ENG. SCI., 60:211–217, 2020. © 2019 Society of Plastics Engineers     

Preparation and properties of foamed cellulose acetate/polylactic acid blends

In order to improve the foaming performance of pure cellulose acetate (CA), blends were prepared by mixing polylactic acid (PLA) in CA and foamed by supercritical CO₂ (ScCO₂) in this study. The effect of PLA content (percentage by mass of blend) on structure, thermal properties, rheological properties, foaming properties and mechanical properties of the blends was investigated. The results showed that the addition of PLA destroyed the original hydrogen bonds of CA, while the blends had good crystallization properties. At the same time, compared with pure CA, the glass transition temperature (T_g) of the blends decreased, and the initial decomposition temperature (T₀) was reduced from 349.41°C (pure CA) to 334.68°C (CA/20%PLA). In addition, the rheological properties of the blends were improved, and the viscosity was reduced, which was obviously beneficial to foaming process. The pore size and density of the foamed blends both reached the maximum value at 20%PLA. The presence of PLA could degrade the mechanical properties of the blends. However, the overall drop (1.01 KJ/m²) of impact strength of the blends after foaming is much smaller than that before foaming (12.11 KJ/m²), indicating that the improvement of foaming performance was beneficial to improve its impact strength.     

Performance optimization of acrylonitrile butadiene styrene/thermoplastic polyurethane composite foams blown with carbon dioxide using Taguchi technique

In this study, acrylonitrile butadiene styrene (ABS)/thermoplastic polyurethane (TPU) composite foam blown with CO₂ was fabricated. Optimization was done by design of experiment (DOE) on the cellular structure using the Taguchi method. Foaming time (20, 40, and 80 s), saturation pressure (4, 5.5, and 7 MPa), and foaming temperature (80, 90, and 120°C) are the input parameters. The results obtained from the signal-to-noise (S/N) analysis showed that the most effective factor on the cell density (CD) was the saturation pressure and its influence rate was 48.05%, and also, the CD improved with the increase in the saturation pressure because the high saturation pressure leads to an enhancement in gas solubility and the rate of cell nucleation. Moreover, the foaming temperature and the foaming time had a noteworthy impact on the void fraction and the cell size (CS), and they should be controlled accurately. The impression rate of the foaming time on the CS was 50.86%, and also, with increase in the temperature and the time of foaming, the void fraction showed an increasing trend. The optimal values for the CD, the CS, and the void fraction were predicted to be 1.18 × 10⁹ cells/cm³, 5.37 μm, and 0.5744%, respectively.     

Research on Preparation of Perfusion Explosive Using Foamed SF‐3 Double‐Base Propellant

Perfusion explosives were prepared using foamed SF‐3 propellants, which were synthesized by a two‐stage batch foaming process with different saturation time in supercritical fluid CO₂ as a foaming agent. The foamed SF‐3 propellants were characterized by scanning electron microscopy (SEM). Underwater detonation tests and test‐board detonation tests were carried out to investigate detonation performance of the prepared perfusion explosives. Results showed that more saturation time during the foaming process leads to more pores and cracks. Perfusion explosives prepared using foamed SF‐3 propellants exhibited much higher shock wave energy and stronger damage effectiveness than those using unfoamed SF‐3 propellants. Perfusion explosives prepared using foamed SF‐3 propellants with a saturation time of 2 h exhibited the highest shock wave energy and damage effectiveness, which decreased as the saturation time increased.     

A Taguchi analysis on structural properties of polypropylene microcellular nanocomposite foams containing Fe2O3 nanoparticles in batch process

Polypropylene (PP) as a thermoplastic polymer has been foamed using batch foaming process. CO₂ is used as the blowing agent of the foaming. Ferrous oxide nanoparticles (nano Fe₂O₃) are also added as reinforcement. Effect of different parameters including nanoparticle weight percentage, foaming temperature and time on the structural properties of PP/nano Fe₂O₃ nanocomposites is investigated using Taguchi approach. Scanning electron microscope results depict that an appropriate microcellular structure is obtained with the cell density of 10⁹ cells/cm³ and almost 1 μm of cell size. Analysis of variance results indicated that foaming temperature is the most significant parameter on the structural properties. Cell density and expansion ratio are decreased by increasing foaming temperature. This phenomenon could be due to the reducing melt strength of polymer/gas mixture. It was also inferred that adding 2 wt% of nanoparticles leads to 80% improvement in cell density while cell size and expansion ratio was decreased.