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     

Challenge to fortyfold expansion of biodegradable polyester foams by using carbon dioxide as a blowing agent

This paper presents a new foaming technology using supercritical carbon dioxide as a blowing agent to obtain large volume expansions of biodegradable polyester foams of over fortyfold. The basic approach for the promotion of a large volume expansion ratio with carbon dioxide was to prevent cell coalescence by using a branched material, to dissolve carbon dioxide completely in the melt by promoting convective diffusion under a high processing pressure, to reduce the diffusivity of gas by lowering the melt temperature, and to optimize the processing conditions in the die to maximize volume expansion. The desirable composition of the materials includes dehydrated branched biodegradable polyester (polybutylene succinate), CO₂ (blowing agent), and tale (nucleating agent). A single‐screw extrusion system was used for foam processing. A large volume expansion ratio of up to forty‐fivefold was achieved from the biodegradable polyester foams. The morphologies and volume expansion ratios of biodegradable polyester foams at various processing temperatures and pressures were studied.     

Simulation of liquid physical blowing agents for forming rigid urethane foams

A computer‐based simulation for rigid polyurethane foam‐forming reactions was compared with experimental data for six blowing agents including methyl formate and C5‐C6 hydrocarbons. Evaporation of blowing agent was modeled as an overall mass transfer coefficient times the difference in activity of the blowing agent in the gas foam cells versus the resin walls of the cells. Successful modeling hinged upon use of a mass transfer coefficient that decreased to near zero as the foam resin approached its gel point. Modeling on density agreed with experimental measurements. The fitted parameters allowed for interpretations of the final disposition of the blowing agent, especially, if the blowing agent successfully led to larger foam cells versus being entrapped in the resin. The only component‐specific fitted parameters used in the modeling was the activity coefficient that was lower for methyl formate than the value used for hydrocarbons. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42454.     

Chemical and physical blowing agents in structural polyurethane foams: Simulation and characterization

Physical blowing agents such as n‐pentane and methyl formate and, for comparison, chemical blowing agents such as water were used to prepare structural polyurethane rigid foams of different densities by reaction injection molding. Experimental runs were carried out with formulations based on oligomeric isocyanate and a mixture of polyether polyols. The constitutive equations for the vaporization rate of the two blowing agents and the polymerization kinetics data are reported. Experimental results were compared with the prediction of a simplified theoretical model, and they showed a satisfactory agreement in terms of temperatures and density profile. All the specimens were characterized by physical‐mechanical properties such as hardness, impact strength, flexural strength and elastic modulus and the results were reported in function of the densities. The best mechanical performance were obtained with the physical blowing agents, due to a better density distribution profile and a thicker skin layer.     

溢流法测定超临界CO_2在聚己酸内酯中的溶解

以超临界CO2作为溶剂,采用溢流法研究聚己酸内酯(PCL)在CO2中的溶胀过程和超临界CO2/PCL体系的热力学平衡规律。考察了温度、压力对溶解度的变化趋势,分析加入有机溶剂后对CO2在聚合物中的溶解度的影响,并应用P-T(Patel-Teja)方程作为热力学模型分析和计算溶解规律。结果表明:CO2的溶解度随温度升高而降低,随压力增大而增大,有机溶剂的加入能够进一步提高CO2的溶解度,在相同的温度压力条件下,加入相当于CO2质量的2.26%的二氯甲烷,最多可使溶解度增加28.06%。在温度313.15—353.15 K、压力10—20 MPa范围内,P-T方程能较好地预测CO2在PCL中的溶解度,其相对误差在-12.53%—12.01%。     

Foam extrusion of LDPE with solid phase CO2 as blowing agent

Physical foaming usually requires special metering equipment to inject the blowing agent at high pressures. In this study, low density polyethylene (LDPE) was foamed in the extrusion process using dry ice as physical blowing agent. The blowing agent was metered in form of pellets over the hopper. To determine relevant process parameters and improve the understanding of the process a melting model is applied. The influence of the formation of a melt film and melt pool on the dissolution of the blowing agent is discussed. The theoretical considerations are validated in a design of experiment study. As a result, the efficiency of the process is especially affected by the throughput rate, granules temperature, and blowing agent concentration. Further varied parameters are the barrel temperature in the melting zone and diameter of the dry ice pellets. Fast melting and pressure build‐up were shown to reduce blowing agent losses. POLYM. ENG. SCI., 55:2821–2828, 2015. © 2015 Society of Plastics Engineers     

Extrusion of microcellular polysulfone using chemical blowing agents

Microporous polysulfone hollow fibers were developed with the help of chemical blowing agents by means of extrusion. Two chemical blowing agents, azodicarbonamide and 5-phenyltetrazol, were selected, and the foam morphology dependent on the concentration of blowing agent was examined by scanning electron micrograph. By means of changing the processing parameters, e.g., temperature and screw speed, the structures of the foam, usable as membrane, can be controlled. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 1753–1760, 1998     

New experimental method for determination of effective diffusion coefficient of blowing agents in polyurethane foams

The effective diffusion coefficients of novel, environmentally friendly, hydrofluorocarbon (HFC) blowing agents for polyurethane foam production were measured. The method was based on gas chromatography and infrared spectroscopy measurements. The accuracy and reliability of the procedure developed were confirmed by comparisons of experimental and the predicted thermal aging curves. The slope of the aging curves (i.e., the change in thermal conductivity with time) depended only on the effective diffusion coefficients. The effective diffusion coefficients of the new HFC blowing agents were close to those of conventional hydrochlorofluorocarbon (HCFC) blowing agents, and the aging behavior of foams produced from HFC or HCFC blowing agents were similar. Polym. Eng. Sci. 44:2229–2239, 2004. © 2004 Society of Plastics Engineers.     

Modeling the phase behavior in binary mixtures involving blowing agents and thermoplastic resins

The thermophysical properties of mixtures of thermoplastic resins and blowing agents, together with the knowledge of the solubilities of these components, are the basis for the manufacturing of plastic foams. In this work, the solubilities of blowing agents trichlorofluoromethane, dichlorodifluoromethane, chlorodifluoromehane, and 1,2‐dichloro‐1,1,2,2‐tetrafluoroethane in thermoplastic resins poly(styrene), high density poly(ethylene), low density poly(ethylene), poly(propylene), poly(vinyl chloride), poly(carbonate) and poly(propylene oxide) were modeled by using the Perturbed Chain‐Statistical Associating Fluid Theory (PC‐SAFT) and the Sánchez‐Lacombe equations of state (EoS), fitting a single temperature‐dependent binary interaction parameter. PC‐SAFT is a theoretically based equation of state with three pure component parameters that describe efficiently the thermodynamics of complex systems. Earlier works with this EoS have already predicted the phase coexistence properties of various refrigerants and higher order alkane series compounds, along with their mixtures. The pure component parameters for the blowing agents were obtained by regression of vapor pressure and liquid density data, while the pure component parameters for the thermoplastic resins were obtained by regression of pure liquid PVT data. The parameter estimation was performed by using a modified maximum likelihood method. The solubility results obtained with both EoS have been compared; the results from PC‐SAFT showed a higher accuracy in terms of solubility pressure deviations. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Preparation of low density carbon foams by foaming molten sucrose using an aluminium nitrate blowing agent

Low density carbon foams have been prepared by thermo-foaming of molten sucrose using aluminium nitrate as a blowing agent to produce solid organic foams followed by dehydration and carbonization. Gas bubbles are generated in the molten sucrose due to water vapour produced by the acid catalysed condensation between sucrose hydroxyl groups and NO_x gases produced by the thermal decomposition of the aluminium nitrate. Higher melt viscosity achieved by cross-linking of the condensation products of sucrose through co-ordination of the aluminium ions with the hydroxyl groups stabilizes the bubbles against coalescence and rupture. The foam volume, foaming time and setting time depend on the aluminium nitrate concentrations. The carbon obtained by the pyrolysis of the solid organic foams has turbostratic graphite structure. The foams produced have an interconnected near-spherical cellular structure. The carbon foams prepared at aluminium nitrate concentrations in the range of 0.5–4 wt.% have a density and average cell size in the ranges of 0.085–0.053 g/cc and 1.55–0.83 mm, respectively. The alumina (～0.17–1.34 wt.%) produced from the aluminium nitrate is concentrated more on the surface of cell walls, ligaments, and struts.     

Extraction of anthocyanins from Arrabidaea chica in fixed bed using CO2 and CO2/ethanol/water mixtures as solvents

Leaves of Arrabidaea chica (Humb. Bonpl.) Verlot are rich in anthocyanins and have been used as a medicinal plant in the Amazon region. In order to obtain different extracts from this plant, a sequential extraction in fixed bed was carried out at 40 °C and 300 bar, using supercritical carbon dioxide (scCO₂) in a first step, and a mixture containing CO₂/ethanol/water at mass ratios of approximately 80/20/0, 80/14/6 and 80/10/10 in a second extraction step. The residue from the second step was extracted with water at 40 °C and atmospheric pressure. Ethanolic, aqueous and hydroalcoholic (70:30, v:v) extracts were also obtained by conventional extraction methods at atmospheric pressure. All extracts were analyzed for global extraction yield, total phenolic content, total flavonoids, and carajurin content. High performance liquid chromatography (HPLC) was used both to quantify carajurin, which is the main anthocyanin component of A. chica, and to monitor qualitatively two other anthocyanin pigments found in that plant. The extraction yield in the first step was only 0.65% using pure scCO₂, but this extraction was highly selective to extract carajurin from the three main anthocyanins. The accumulated global yield of the two steps ranged from 3% when the solvent ratio (80/20/0) was used in the second step to about 50% when 6 or 10% water was used, showing the highest yield when the extraction was done with water. The highest contents of total phenolic compounds (178 mg GAE/g extract) and total flavonoids (373 mg EC/g extract) were found in the process performed with the extraction mixture (80/20/0), and the highest carajurin content was obtained in the ethanolic extracts.     

CO2/N2开关型脒基表面活性剂软模板制备介孔二氧化硅

模板法是制备介孔SiO₂的常用方法之一,而模板法通常需要脱除模板后才能得到介孔结构。以传统表面活性剂为模板合成介孔二氧化硅,除模板方法还有高温焙烧、溶剂萃取等,但这些方法均存在一定的缺点,如导致结构坍塌、消耗大量溶剂等。本文采用开关型表面活性剂N'-十二烷基-N,N-二甲基乙基脒碳酸氢盐为模板剂,以正硅酸四乙酯(TEOS)为硅源在碱性条件下合成SiO₂。与常规除模板法不同,本实验在反应结束后加热并通入N₂使表面活性剂分解失去表面活性,用水和丙酮洗涤后得到了形貌规整、孔道有序、具有较高比表面积和孔容的介孔SiO₂。同时还研究了有机盐乙二胺四乙酸二钠(Na₂EDTA)对介孔有序度、所得介孔材料比表面积、孔容孔径和模板残留量的影响。     

CO2/N2可逆单层囊泡-网状结构转变研究

以聚乙二醇6000与α-溴代异丁酰溴进行酯化反应得到大分子引发剂PEG6000-Br,使用原子转移自由基聚合(ATRP)法合成了对称三嵌段且聚合度相等的聚甲基丙烯酸二甲胺乙酯-聚乙二醇-聚甲基丙烯酸二甲胺乙酯(PDM_(165)-PEG_(165)-PDM_(165))。利用FTIR和~1HNMR对其结构进行了表征。以p H、电导率测试证明了聚合物溶液的CO_2/N_2循环可逆性,聚合物溶液中通入CO_2后,5 min内,溶液p H值即从7.74下降至5.47,溶液电导率从0.176 m S/cm迅速上升至0.405 m S/cm;继而向溶液中通入N_2,经过30 min后,溶液的p H值和电导率都恢复到初始值。冷冻透射电镜(Cryo-TEM)观察得知,聚合物在水中可自组装形成单层囊泡,通入CO_2后,叔胺被质子化,囊泡解离形成网状结构,导致溶液黏度从3 m Pa·s上升至12 m Pa·s,叔胺质子化由~1HNMR证明,N原子附近的氢位移从δ2.3、2.7、4.1向低场分别移动至δ2.8、3.2、4.3。     

Supercritical CO2 intercalation of polycaprolactone in layered silicates

Supercritical carbon dioxide (scCO₂) intercalation of polycaprolactone (PCL) in layered silicates (clay) is studied. Wide angle X-ray diffraction patterns find that PCL is slightly intercalated in unmodified montmorillonite clay (NaMMT) but considerably intercalated in organic-modified montmorillonite clay (OMMT). The interlayer spacing in OMMT increases considerably from 1.94 nm in OMMT to 3.58 nm in the OMMT/PCL 10/90 sample. PCL8 having molecular weight of 80,000 is harder to intercalate into OMMT than PCL1 having molecular weight of 10,000. Higher scCO₂ pressures at a temperature allow larger intercalations of PCL in OMMT to exhibit larger interlayer spacings in OMMT. The interlayer spacings in OMMT, however, are not clearly found to relate with the CO₂ temperature at a given pressure. TGA data show that OMMT enhances the thermal stability of PCL1, with a higher content of OMMT giving a higher amount of PCL1 residue. DSC data find that the PCL1-intercalated OMMT expedites the melt-crystallization rate of PCL1 from the melt but suppresses the crystallinity of PCL1. Study of Avrami's rate constants k and exponent n finds that the PCL1-intercalated OMMT enhances the isothermal crystallization rate of PCL1 and that the crystal growth dimension is 3 for pure PCL1 but decreases with increasing OMMT content in the blends. Modulus data find that the PCL1-intercalated OMMT is an effective reinforcement for PCL8.     

Electrospinning of polycaprolactone nanofibers using H2O as benign additive in polycaprolactone/glacial acetic acid solution

Considerable efforts have been devoted to the production of polycaprolactone (PCL) nanofibrous structures by electrospinning. However, some toxic solvents have often been used to achieve bead‐free nanofibers. At present, a benign solvent such as glacial acetic acid (GAC) only leads to beaded or microscale fibers. Therefore a study is done to extend the electrospinnability of the PCL/GAC system by the addition of H₂O. The solution properties of conductivity, viscosity, and surface tension were altered by the addition of H₂O, especially increasing the conductivity and viscosity. These properties essential to electrospinning could remain stable for 6 h when the H₂O content was less than or equal to 9 vol %. Then ultrafine PCL fibers with diameters from 188 to 200 nm, 10 times smaller than when dissolved in pure GAC, were electrospun from solutions of PCL with concentrations in the range of 17 to 20 wt % with H₂O content at 9 vol %. Finally, the crystallinity and crystallite size of the resulting fibers were smaller than that of raw PCL pellets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45578.     

Preparation and characterization of foams from sheet glass and fly ash using carbonates as foaming agents

Glass foams were produced using sheet glass cullet and fly ashes from thermal power plant with added carbonates (commercial dolomite- and calcite-based sludges) as foaming agents. The influence of type and amount of carbonates as well as of the sintering temperature on the apparent density, compressive strength, microstructure and crystalline phases was evaluated. The experimental results showed that homogenous microstructures of large pores could be obtained by adding just 1–2 wt.% carbonates and using low sintering temperature (850 °C), leading to foams presenting apparent density and compressive strength values of about 0.36–0.41 g/cm³ and 2.40–2.80 MPa, respectively. Good correlations between compressive strength, apparent density and microstructure (pore size, struts’ thickness and internal porosity) were observed.     

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     

不同发泡剂及工艺条件对BR／SBR／NR发泡材料相结构及尺寸稳定性的影响

分别采用一段和两段模压法制备了以顺丁橡胶（BR）／丁苯橡胶（SBR）／天然橡胶（NR）为基体的橡胶发泡材料,研究了三种化学发泡剂N,N＇-二甲基戊次甲基四胺（H）、4,4＇-氧代双（苯磺酰肼）（OBSH）以及H／OBSH（质量比1：1）复配对发泡及硫化特性的影-向,以及3种发泡剂和2种成型工艺对收缩率及相结构的影响。结果表明,发泡剂H对硫化性能影响最大,含发泡剂H的混炼胶在分解过程中释放的热量最多;加入3种发泡剂都具有一种较大的泡孔镶嵌在较小的泡孔丛中的泡孔形态;密度和线收缩率均随着时间的增加而增加,经H／OBSH复配的发泡剂更适合该体系成型,材料线收缩率均比单独使用H和OBSH小,两段模压法可以有效地提高发泡材料的尺寸稳定性,收缩率降低至3．88％,同时发泡剂使用率最多可提高31．67％。     

Preparation of carbon foams with enhanced oxidation resistance by foaming molten sucrose using a boric acid blowing agent

Boric acid was used as a blowing agent as well as a boron precursor for the preparation of boron-doped carbon foams from molten sucrose. The H⁺ generated, due to the formation of a complex between sucrose and boric acid, catalyzes the –OH to –OH condensation reaction leading to the polymerization and the foaming of the molten sucrose. The char yield of the solid organic foams increased from 24 to 39 wt.% when the boric acid concentration increased from 0 to 8 wt.%, due to the formation of the B–O–C cross-links between sucrose polymer by B–OH to C–OH condensation. The inductively coupled plasma analysis showed the presence of 0.44–3.4 wt.% boron in the carbon foams. The density and compressive strength decreased and cell size increased with boric acid concentration. The room temperature thermal conductivity of the boron-doped carbon foams was in the range of 0.057–0.043 W m⁻¹ K⁻¹. The weight loss studies by dynamic and isothermal heating showed the increased oxidation resistance with boron concentration.     

热塑性聚醚酯弹性体硬段含量对其超临界CO 2发泡行为的影响

研究了以聚对苯二甲酸丙二醇酯(PBT)为硬段,聚四氢呋喃醚(PTMG)为软段的热塑性聚醚酯弹性体（TPEE）在超临界CO ₂作用下的固态发泡行为,考察了硬段含量的差异对结晶行为,CO ₂在TPEE中溶解度及扩散行为,以及固态发泡行为的影响。发现硬段含量的差异对TPEE结晶行为影响尤为显著,当硬段含量由29%上升到65%时,其熔点从162.6℃上升至201.9℃,且结晶度由20%上升到40%。结晶的存在抑制了CO ₂在基体内的溶解度且阻碍了其在基体内的扩散。由不同硬段的TPEE中CO ₂溶解度和扩散过程的变化可知,CO ₂更倾向于溶解在TPEE软区内,而由结晶为主构成的硬区中CO ₂溶解量较低。通过研究高压CO ₂环境下的TPEE等温结晶过程发现,经扩散进入TPEE软区内的CO ₂可以提升TPEE链段运动能力,诱导未结晶链段通过规整堆叠而结晶。在CO ₂压力15 MPa经快速降压发泡聚醚酯弹性体,发现随着硬段含量的增加,其温度发泡窗口向高温区移动,当硬段含量为29%时,发泡温度区间为50~160℃,平均孔径4.6~16.5 μm,泡孔密度8.1×10 ⁷~7.5×10 ⁸cells/cm ³,发泡倍率1.1~5.8;当硬段含量为65%时,发泡温度区间为165~195 ℃,平均孔径1.8~6.8 μm,泡孔密度2.6×10 ⁸~1.1×10 ¹¹ cells/cm ³,发泡倍率1.0~4.2。