Burning Characteristics of Microcellular Combustible Objects Fabricated by a Confined Foaming Process

Microcellular combustible objects for application of combustible case ammunition and caseless ammunition were fabricated by a confined pressure quenching foaming process using supercritical CO₂ as foaming agent. The experimental results showed that the force constant (f) of objects obviously increased with an increasing RDX content and that the force constant of formulation with 55 % RDX is comparable to that of traditional felted case. Pressure histories, dp/dt‐t, and dynamic vivacity curves were investigated and compared by closed vessel tests. The influencing factors such as RDX content, expansion ratio, foaming temperature, sample size, and loading density were analysed. The results revealed that RDX content and expansion ratio significantly affected the burning properties, whereas the foaming temperature did not have obvious influence. Moreover, the burning behavior also changed with sample size and loading density.     

Burning Characteristics of Microcellular Combustible Ordnance Materials

A microcellular combustible ordnance material composed of 70 % RDX (cyclotrimethylene trinitramine) and 30 % PMMA (poly methyl methacrylate) was fabricated using the solvent method and foamed by supercritical CO₂ as foaming agent. This material has a number of advantages and many find potential application in weaponry. In this paper, vented bomb tests were conducted on the porous materials to gain a qualitative understanding of how the material is burning in a gun environment. The extinguish process showed that the microcellular combustible material followed the in‐depth combustion mode, i.e. the combustion products infiltrated through inner pores as well as ignited the inner pore surface. With increasing burning degree, the depth and perforation size of infiltration zone increased. Closed bomb tests were also conducted to investigate the influences of test conditions on the burning behaviors. The results showed that when the ignition pressure was increased from 10.98 MPa to 15.0 MPa, the burning time was shortened, but the mass burning rate and vivacity did not change obviously. Mass burn rates at different loading densities indicated that while the pressure in closed vessel is high enough (p≥40 MPa), hot combustion gases were driven into the inner pores and convectively ignited the inner pores. The closed bomb results conducted at high and low temperature showed no abnormal burning behavior at low and high temperature can be observed.     

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。     

RDX基可燃材料的热力学性能,非等温反应动力学及安全性研究

用TG和DSC研究了RDX基微孔可燃材料的热行为,用非等温DSC研究了其放热反应动力学,用Kissinger和Ozawa方法计算了可燃材料的动力学参数;基于Kissinger方法,研究了组分间的相容性;采用耐热和吸湿试验进行了微孔可燃材料的耐热性和吸湿性评价.结果表明,可燃材料的分解被看作是两步反应:第一阶段是吸热熔融反应,无质量损失,第二阶段是放热反应,有质量损失;用Kissinger和Ozawa方法得到的活化能相近,可燃材料的活化能均低于纯RDX的分解活化能;黏结剂PMMA、CA与固体填料RDX相容性好,相容性等级为1级;热爆炸临界温度与RDX相近.新型微孔可燃材料的其他性能优于传统可燃材料.     

Preparation and morphology characterization of microcellular styrene‐co‐acrylonitrile (SAN) foam processed in supercritical CO2

Microcellular polymeric foam structures have been generated using a pressure‐induced phase separation in concentrated mixtures of supercritical CO₂ and styrene‐co‐acrylonitrile (SAN). The process typically generates a microcellular core structure encased by a non‐porous skin. Pore growth occurs through two mechanisms: diffusion of CO₂ from polymer‐rich regions into the pores and also through CO₂ gas expansion. The effects of saturation pressure, temperature and swelling time on the cell size, cell density and bulk density of the porous materials have been studied. Higher CO₂ pressures (hence, higher fluid density) provided more CO₂ molecules for foaming, generated lower interfacial tension and viscosity in the polymer matrix, and thus produced lower cell size but higher cell densities. This trend was similar to what was observed in swelling time series. While the average cell size increased with increasing temperature, the cell density decreased. The trend of bulk density was similar to that of cell size. © 2000 Society of Chemical Industry     

Controlling sandwich‐structure of PET microcellular foams using coupling of CO2 diffusion and induced crystallization

Controlling sandwich‐structure of poly(ethylene terephthalate) (PET) microcellular foams using coupling of CO₂ diffusion and CO₂‐induced crystallization is presented in this article. The intrinsic kinetics of CO₂‐induced crystallization of amorphous PET at 25°C and different CO₂ pressures were detected using in situ high‐pressure Fourier transform infrared spectroscopy and correlated by Avrami equation. Sorption of CO₂ in PET was measured using magnetic suspension balance and the diffusivity determined by Fick's second law. A model coupling CO₂ diffusion in and CO₂‐induced crystallization of PET was proposed to calculate the CO₂ concentration as well as crystallinity distributions in PET sheet at different saturation times. It was revealed that a sandwich crystallization structure could be built in PET sheet, based on which a solid‐state foaming process was used to manipulate the sandwich‐structure of PET microcellular foams with two microcellular or even ultra‐microcellular foamed crystalline layers outside and a microcellular foamed amorphous layer inside. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2512–2523, 2012     

Production and Characterization of Composite Nano‐RDX by RESS Co‐Precipitation

Nanoscale composites of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and polymeric binders were produced by co‐precipitation using rapid expansion of supercritical solutions (RESS). The binders used in this study are poly (vinylidene fluoride‐co‐hexafluoropropylene) (VDF‐HFP₂₂) and polystyrene (PS). The RDX/VDF‐HFP₂₂ and RDX/PS co‐precipitated nanoparticles were characterized by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The average size of produced nanoparticles is ca. 100 nm. TEM analysis of RDX/PS nanocomposite shows a core‐shell structure with RDX as the core material and the shell consisting of the polymeric binder. X‐ray Powder Diffraction (XRPD) analysis indicates polycrystalline structure of RDX in the product with a crystallite size of 42 nm. The content of RDX in the composite particles is in the range of 70–73 % by mass as determined by Gas Chromatography Mass Spectroscopy (GCMS) and by XRPD.     

Extrusion foaming behavior of a polypropylene/nanoclay microcellular foam

With maleic anhydride grafted polypropylene (PP‐g‐MAH) as a compatibilizer, composites of block‐copolymerized polypropylene (B‐PP)/nanoclay were prepared. The effects of the PP‐g‐MAH and nanoclay content on the crystallization and rheological properties of B‐PP were investigated. The microcellular foaming behavior of the B‐PP/nanoclay composite material was studied with a single‐screw extruder foaming system with supercritical (SC) carbon dioxide (CO₂) as the foaming agent. The experimental results show that the addition of nanoclay and PP‐g‐MAH decreased the melt strength and complex viscosity of B‐PP. When 3 wt % SC CO₂ was injected as the foaming agent for the extrusion foaming process, the introduction of nanoclay and PP‐g‐MAH significantly increased the expansion ratio of the obtained foamed samples as compared with that of the pure B‐PP matrix, lowered the die pressure, and increased the cell population density of the foamed samples to some extent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44094.     

Novel injection molding foaming approaches using gas‐laden pellets with N2, CO2, and N2 + CO2 as the blowing agents

A novel method of producing injection molded parts with a foamed structure has been developed. It has been named supercritical fluid‐laden pellet injection molding foaming technology (SIFT). Compared with conventional microcellular foaming technologies, it lowers equipment costs without sacrificing the production rate, making it a good candidate for mass producing foamed injection molded parts. Both N₂ and CO₂ can be suitably used in this process as the physical blowing agent. However, due to their distinct physical properties, it is necessary to understand the influence of their differences over the process and the outcomes. Comparisons were made in this study between using CO₂ and N₂ as the blowing agents in terms of the part morphologies, as well as the shelf life and gas desorption process of the gas‐laden pellets. After gaining a good understanding of the SIFT process and the gas‐laden pellets, a novel foam injection molding approach combining the SIFT process with microcellular injection molding was proposed in this study. Both N₂ and CO₂ can be introduced into the same foaming process as the coblowing agents in a two‐step manner. Using an optimal content ratio for the blowing agents, as well as the proper sequence of introducing the gases, foamed parts with a much better morphology can be produced by taking advantage of the benefits of both blowing agents. In this study, the theoretical background is discussed and experimental results show that this combined approach leads to significant improvements in foam cell morphology for low density polyethylene, polypropylene, and high impact polystyrene using two different mold geometries. POLYM. ENG. SCI., 54:899–913, 2014. © 2013 Society of Plastics Engineers     

Research on Titanium‐Containing Micro‐Porous Propellants with Rapid Burning Rate

Micro‐porous propellants containing titanium powder were obtained by supercritical CO₂ (SC CO₂) foaming technique. The morphologies of the micro‐porous propellants were characterized by scanning electron microscopy (SEM) and energy‐dispersive X‐ray spectroscopy (EDS) measurement. The burning rate, the impetus, and the heat of explosion of the micro‐porous propellants were measured by the closed vessel test and the calorimetric bomb test. The results show that the porosity increased with increasing titanium powder content; compared with Benite, the burning rate was substantially improved, and the maximum values of the impetus and the isochoric heat of explosion increased by 51.4 % and 6.5 %, respectively. The Ti‐containing micro‐porous propellants with rapid burning rate and better energetic properties described in this paper may have the potential to replace Benite as igniter material in a flame igniter of a gun propellant charge.     

Microcellular foams of glass–fiber reinforced poly(phenylene sulfide) composites generated using supercritical carbon dioxide

Microcellular foaming of poly(phenylene sulfide) (PPS) and its glass–fiber (GF) reinforced composites using supercritical CO₂ as a blowing agent presents a promising approach to produce novel cellular materials with tailored microstructures. This study investigated the effects of the material composition and process conditions on the foaming behaviors and final morphologies of the microcellular foamed PPS and PPS/GF composites. The rheological and thermal properties as well as the saturation and desorption behaviors of CO₂ in the pure PPS and PPS/GF composites were also detailedly discussed. The results show that microcellular foams with various relative densities, cell sizes, cell‐size distributions, and cell densities can be attained by tailoring the fiber content and key process parameters. At low foaming temperatures below the cold crystallization temperature, the microcellular foamed PPS and PPS/GF composites both present a unimodal cell‐size distribution. At elevated temperatures, the generated crystalline superstructures including spherulites in the polymer matrix and transcrystals around the GF will cause a secondary heterogeneous cell nucleation. This leads to the observations of bimodal and trimodal cell‐size distributions in the pure PPS and the PPS/GF composites, respectively. The mechanisms for the solid‐state foaming behaviors of pure PPS and PPS/GF composites have been illustrated by establishing theoretical models. POLYM. COMPOS., 37:2527–2540, 2016. © 2015 Society of Plastics Engineers     

N2‐filled hollow glass beads as novel gas carriers for microcellular polyethylene

N₂‐filled hollow glass beads (HGB) were first used as novel gas carriers to prepare microcellular polymers by compression molding. Dicumyl peroxide was acted as crosslink agent to control the produced microcellular structure of low density polyethylene (LDPE)/HGB. The effect of temperature, pressure and the content of gel on the embryo‐foaming, and final‐foaming structure are investigated. Scanning electronic microscopy shows that the average cell size of microcellular LDPE ranges from 0.1 to 10 μm, and the foam density is about 10⁹–10¹¹ cells/cm³. A clear correlation is established between preserving desirable micromorphologies of microcellular LDPE in different processing stage and tuning processing factors. The pertinent foaming mechanism of microcellular materials foamed with HGB is proposed. Because of the good mechanical strength, low density, weak water‐absorption, and excellent heat insulate ability, microcellular LDPE has great potential application in energy building materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mesoporous silica particles grafted with polystyrene brushes as a nucleation agent for polystyrene supercritical carbon dioxide foaming

In this study, spherical ordered mesoporous silica (s‐OMS) was applied as a new type of nucleating agent in polystyrene (PS) foaming with supercritical CO₂ as a blowing agent. These s‐OMS particles were modified by the selective grafting of PS brushes on the outside surface, by which the mesoporous structure inside particles could be maintained. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller surface area analysis were used to characterize the structure of the original and modified particles; these indicated that the PS brushes were grafted on the outside surface and the inside porous structure were maintained. PS/s‐OMS–PS composites were prepared by a solution blending method, and the s‐OMS–PS particles could have been well dispersed in the PS matrix because of the surface modification. Subsequently, PS and composite microcellular foams were prepared by a batch foaming process, and the morphology characterization on these foams showed that the s‐OMS particles exhibited an excellent heterogeneous effect on PS foaming. The heterogeneous effect became more significant when the foaming temperature or saturation pressure was low. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4308–4317, 2013     

Microcellular foaming of low‐density polyethylene using nano‐CaCo3 as a nucleating agent

In this study, microcellular foaming of low‐density polyethylene (LDPE) using nano‐calcium carbonate (nano‐CaCO₃) were carried out. Nanocomposite samples were prepared in different content in range of 0.5–7 phr nano‐CaCO₃ using a twin screw extruder. X‐ray diffraction and scanning electron microscopy (SEM) were used to characterize of LDPE/nano‐CaCO3 nanocomposites. The foaming was carried out by a batch process in compression molding with azodicarbonamide (ADCA) as a chemical blowing agent. The cell structure of the foams was examined with SEM, density and gel content of different samples were measured to compare difference between nanocomposite microcellular foam and microcellular foam without nanomaterials. The results showed that the samples containing 5 phr nano‐CaCO₃ showed microcellular foam with the lowest mean cell diameter 27 μm and largest cell density 8 × 10⁸ cells/cm³ in compared other samples. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Polycarbonate foams with tailor-made cellular structures by controlling the dissolution temperature in a two-step supercritical carbon dioxide foaming process

Closed-cell polycarbonate foams were prepared using a two-step foaming process, which consisted of the initial dissolution of supercritical CO₂ (scCO₂) into PC foaming precursors and their later expansion by heating using a double contact restriction method. The effects of the parameters of both CO₂ dissolution and heating stages on the cellular structure characteristics as well as on the physical aging of PC in the obtained foams were investigated. A higher amount of CO₂ was dissolved in PC with increasing the dissolution temperature from 80 to 100 °C, with similar CO₂ desorption trends and diffusion coefficients being found for both conditions. PC foams displayed an isotropic-like microcellular structure at a dissolution temperature of 80 °C. It was shown that it is possible to reduce their density while keeping their microcellular structure with increasing the heating time. On contrary, when dissolving CO₂ at 100 °C and later expanding, PC foams presented a cellular morphology with bigger cells and with an increasingly higher cell elongation in the vertical growth direction with increasing the heating time. Comparatively, PC foams obtained by dissolving CO₂ at 100 °C presented a more marked physical aging after CO₂ dissolution and foaming, although this effect could be reduced and ultimately suppressed with increasing the heating time.     

Effects of clay dispersion on the foam morphology of LDPE/clay nanocomposites

Intercalated and exfoliated low‐density polyethylene (LDPE)/clay nanocomposites were prepared by melt blending with and without a maleated polyethylene (PE‐g‐MAn) as the coupling agent. Their morphology was examined and confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of clay content and dispersion on the cell morphology of nanocomposite foams during extrusion foaming process were also thoroughly investigated, especially with a small amount of clay of 0.05–1.0 wt%. This research shows the optimum clay content for achieving microcellular PE/clay nanocomposite foams blown with supercritical CO₂. It is found that < 0.1 wt% of clay addition can produce the microcellular foam structure with a cell density of > 10⁹ cells/cm³ and a cell size of ～ 5 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2129–2134, 2007     

聚乳酸/聚氨酯复合多孔材料制备及吸油性能研究

以聚乳酸（PLA）为基体,添加不同含量聚氨酯（TPU）熔融共混制备具有不同相形态的PLA/TPU共混物,基于超临界二氧化碳（scCO₂）微孔发泡工艺,研究不同发泡温度下PLA/TPU复合多孔材料泡孔结构、发泡倍率和开孔率对样品吸油性能的影响。结果表明,随着TPU含量从10 %（质量分数,下同）增加到50 %,共混物从典型的“海?岛”相形态转变为部分共连续相形态,PLA基体黏弹性提升,结晶能力下降;PLA70组分发泡后泡孔结构更为均匀,随着发泡温度的增加,泡孔尺寸和发泡倍率先增大后减小,在94 ℃发泡温度下发泡样品发泡倍率达到29.1倍,最大开孔率75 %;TPU的加入显著增加了PLA基体的弹性回复能力,94 ℃发泡温度下的发泡样品具有最大的抗压强度,永久形变量最小;针对硅油和环己烷的吸油测试发现对硅油的吸油量大于环己烷,发泡材料的吸油量与发泡倍率和开孔率的乘积成正比,针对硅油单次最大吸油量为10.4 g/g。     

Microcellular foaming of poly(phenylene sulfide)/poly(ether sulfones) blends using supercritical carbon dioxide

Microcellular foaming of poly(phenylene sulfide)/poly(ether sulfones) (PPS/PES) blends presents a promising approach to produce high‐performance cellular materials with tailored microstructures and enhanced properties. This study investigated the effects of multiphase blend composition and process conditions on the foaming behaviors and final cellular morphology, as well as the dynamic mechanical properties of the solid and microcellular foamed PPS/PES blends. The microcellular materials were prepared via a batch‐foam processing, using the environment‐friendly supercritical CO₂ (scCO₂) as a blowing agent. The saturation and desorption behaviors of CO₂ in PPS/PES blends for various blend ratios (10 : 0, 8 : 2, 6 : 4, 5 : 5, 4 : 6, 2 : 8, and 0 : 10) were also elaborately discussed. The experimental results indicated that the foaming behaviors of PPS/PES blends are closely related to the blend morphology, crystallinity, and the mass‐transfer rate of the CO₂ in each polymer phase. The mechanisms for the foaming behaviors of PPS/PES blends have been illustrated by establishing theoretical models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42634.     

Carbon dioxide foaming of glassy polymers

The mechanism of foaming a glassy polymer using sorbed carbon dioxide is studied in detail. A glassy polymer supersaturated with nitrogen forms a microcellular foam, if the polymer is quickly heated above its glass transition temperature. A glassy polymer supersaturated with CO₂ forms this foam-like structure at much lower temperatures which indicates the T_g-depressing effect of CO₂. Having this interpretation in mind, the overall sample morphology, i.e., a porous foam enclosed by dense outer skins, can be completely explained. The dense skins, however, are not homogeneous but show a nodular structure when analyzed by SEM and AFM. Foaming experiments with samples having a different thermal history suggest that the nucleation mechanism underlying the foaming process is heterogeneous in nature. © 1994 John Wiley & Sons, Inc.     

Microcellular foam of polymer blends of HDPE/PP and their composites with wood fiber

In this study, the effects of batch processing conditions (foaming time and temperature) and blend composition as well as the effect of incorporating wood fiber into the blends on the crystallinity, sorption behavior of CO₂, void fraction, and cellular morphology of microcellular foamed high‐density polyethylene (HDPE)/polypropylene (PP) blends and their composites with wood fiber were studied. Blending decreased the crystallinity of HDPE and PP and facilitated microcellular foam production in blend materials. The void fraction was strongly dependent on the processing conditions and on blend composition. Foamed samples with a high void fraction were not always microcellular. The addition of wood fiber inhibited microcellular foaming. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2842–2850, 2003