Improving polypropylene microcellular foaming through blending and the addition of nano‐calcium carbonate

This article reports an attempt to improve polypropylene (PP) microcellular foaming through the blending of PP with high‐density polyethylene (HDPE) as a minor component and the incorporation of nano‐calcium carbonate (nano‐CaCO₃) into PP and its blends with HDPE. Three HDPEs were selected to form three blends with a viscosity ratio less than, close to, or greater than unity. Two concentrations of nano‐CaCO₃, 5 and 20 wt %, were used. The blends and nanocomposites were prepared with a twin‐screw extruder. The foaming was carried out by a batch process with supercritical carbon dioxide as a blowing agent. The online shear viscosity during compounding and the dynamic rheological properties of some samples used for foaming were measured. The cell structure of the foams was examined with scanning electron microscopy (SEM), and the morphological parameters of some foams were calculated from SEM micrographs. The rheological properties of samples were used to explain the resulting cell structure. The results showed that the blend with a viscosity ratio close to unity produced a microcellular foam with the minimum mean cell diameter (0.7 μm) and maximum cell density (1.17 × 10¹¹ cells/cm³) among the three blends. A foamed PP/nano‐CaCO₃ composite with 5 wt % nano‐CaCO₃ exhibited the largest cell density (8.4 × 10¹¹ cells/cm³). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

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     

Fabrication of polystyrene/nano‐CaCO3 foams with unimodal or bimodal cell structure from extrusion foaming using supercritical carbon dioxide

The article surveyed the fabrication of polystyrene (PS)/nano‐CaCO₃ foams with unimodal or bimodal cellular morphology from extrusion foaming using supercritical carbon dioxide (sc‐CO₂). In order to discover the factors influenced the cell structure of PS/nano‐CaCO₃ foams, the effects of die temperature, die pressure, and nano‐CaCO₃ content on cell size, density, and morphology were investigated detailed. The results showed that the nano‐CaCO₃ content affected the cell size and morphology of PS/nano‐CaCO₃ foams significantly. When the die temperature and pressure was 150°C and 18 MPa, respectively, the foams with 5 wt% nano‐CaCO₃ exhibited the unimodal cellular morphology. As the nano‐CaCO₃ content increased to 20 wt%, a bimodal cell structure of the foams could be obtained. Moreover, it was found that the bimodal structure correlated more strongly with the pressure drop than the foaming temperature. The article revealed that unimodal or bimodal cellular morphology of PS/nano‐CaCO₃ foams could be achieved by changing the extrusion foaming parameters and nano‐CaCO₃ content. POLYM. COMPOS., 37:1864–1873, 2016. © 2015 Society of Plastics Engineers     

Preparation of poly(propylene carbonate)/nano calcium carbonate composites and their supercritical carbon dioxide foaming behavior

Biodegradable polymer foams are attracting extensive attention in both academic and industrial fields. In this study, an emerging biodegradable polymer, poly(propylene carbonate) (PPC), was compounded with nano calcium carbonate (nano‐CaCO₃) and foamed via supercritical carbon dioxide for the first time. Four concentrations of nano‐CaCO₃, 1, 3, 5, and 10 wt %, were used and the thermal properties of PPC/nano‐CaCO₃ composites were investigated. The glass‐transition temperature and thermal decomposition temperature of the PPC/nano‐CaCO₃ composites increased with the addition of nano‐CaCO₃. The morphologies of the PPC/nano‐CaCO₃ composites and the rheological results showed that homogeneous dispersions of nano‐CaCO₃ and percolated nano‐CaCO₃ networks were achieved at a nano‐CaCO₃ content of 3 wt %. Therefore, the finest cell diameter (3.13 μm) and highest cell density (6.02 × 10⁹ cells/cm³) were obtained at the same nano‐CaCO₃ content. The cell structure dependences of PPC and PPC with a nano‐CaCO₃ content of 3 wt % (PPC‐3) foams on the foaming pressure and temperature were investigated as well. The results suggested that the cell structure of PPC‐3 was more stable at different foaming conditions due to the networks of nano‐CaCO₃. Moreover, the change in pressure was more influential on the cell structure than the temperature. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42248.     

The experimental results and simulation of temperature dependence of brittle‐ductile transition in PVC/CPE blends and PVC/CPE/nano‐CaCO3 composites

The effect of chlorinated polyethylene (CPE) content and test temperature on the notched Izod impact strength and brittle‐ductile transition behaviors for polyvinylchloride (PVC)/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites is studied. The CPE content and the test temperature regions are from 0–50 phr and 243–363 K, respectively. It is found that the optimum nano‐CaCO₃ content is 15 phr for PVC/CPE/nano‐CaCO₃ ternary composites. For both PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites, the impact strength is improved remarkably when the CPE content or test temperature is higher than the critical value, that is, brittle‐ductile transition content (C_BD) or brittle‐ductile transition temperature (T_BD). The T_BD is closely related to the CPE content, the higher the CPE content, the lower the T_BD. The temperature dependence of impact strength for PVC/CPE blends and PVC/CPE/nano‐CaCO₃ ternary composites can be well simulated with a logistic fitting model, and the simulation results can be illustrated with the percolation model proposed by Wu and Jiang. DMA results reveal that both PVC and CPE can affect the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. When the CPE content is enough (20 phr), the CPE is more important than PVC for determining the T_BD of PVC/CPE blends and PVC/CPE/nano‐CaCO₃ composites. Scanning electron microscopy (SEM) observations reveal that the impact fractured mechanism can change from brittle to ductile with increasing test temperature for these PVC systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

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     

Mechanical properties,thermal stability,and crystallization kinetics of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)/calcium carbonate composites

Bacterial polyester poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3/4HB) containing 5 mol% 4HB was composited with different calcium carbonate (CaCO₃) fillers. The effect of CaCO₃ contents on thermal properties, mechanical property, and crystallization kinetics was evaluated. The thermal stability of P3/4HB was reduced by mixing with CaCO₃ particles. With increasing CaCO₃ content, the elongation at break, tensile strength, and impact strength decrease; however, elastic modulus increases. When P3/4HB with 20 mol% 4HB was added into the P3/4HB/CaCO₃ composite, the impact strength were enhanced significantly; however, the elongation at break and tensile strength were only slight to moderate improvements. However, when compared with nano‐ and light‐CaCO₃, heavy CaCO₃ had the best mechanical properties. The nonisothermal and isothermal crystallization results demonstrated that the crystallization rate of P3/4HB was reduced and the highest crystallinity was obtained for all kinds of CaCO₃ fillers at 40 phr content. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Processing characteristics of low‐density polyethylene filled with calcium carbonate of different size distributions

Low‐density polyethylene (LDPE) was filled with blends of different proportions of two sizes of calcium carbonate (CaCO₃; 600 and 2500 mesh). The torque of the LDPE/CaCO₃ samples was measured with a torque rheometer. The results showed that the process torque values of the LDPE/CaCO₃ samples obviously decreased when LDPE was filled with a blend of two sizes of CaCO₃ (600‐ and 2500‐mesh CaCO₃ blend) in comparison with samples filled with CaCO₃ of a single size (600 or 2500 mesh). When the ratio of 600‐mesh CaCO₃ to the total CaCO₃ was in the range of 40–60 wt %, the lowest torque value of the LDPE/CaCO₃ samples was achieved. When the content of CaCO₃ in a sample was 30 wt %, LDPE filled with CaCO₃ of different size distributions showed the largest decrease in the torque ratio in comparison with the samples filled with CaCO₃ of a single size. The torques of LDPE samples filled with CaCO₃ of a single size and those filled with CaCO₃ of different size distributions at different temperatures were also studied. The results showed that the flow activation energy and flow activation entropy of LDPE samples filled with CaCO₃ of different size distributions increased obviously. The increase in the flow activation entropy was used to explain the phenomenon of the process torque decreasing for LDPE samples filled with CaCO₃ of different size distributions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of nanocalcium carbonate on the impact strength and accelerated weatherability of rigid poly(vinyl chloride)/acrylic impact modifier

Poly(vinyl chloride) (PVC) composites filled with nano‐ and micro‐CaCO₃ particles were prepared via a melt blending method. Transmission electron microscopy images revealed better dispersion of nano‐CaCO₃ than micro‐CaCO₃ in the PVC matrix. With more than 5 phr (parts per 100 parts of resin) of nano‐CaCO₃ content, both impact strength and heat stability were improved. Accelerated weathering tests were performed to investigate UV stability. The impact strength and white index obtained upon weathering exposure of PVC/(80 μm CaCO₃) nanocomposites showed a significant improvement upon incorporating nano‐CaCO₃. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

微发泡LDPE复合材料发泡行为的研究

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低密度聚乙烯(LDPE)复合材料;通过材料的本征特性分析了弹性体对微发泡LDPE复合材料发泡行为的影响规律。结果表明:LDPE中,弹性体含量为15%时,发泡质量较为理想,泡孔呈规则的圆形,泡孔直径和泡孔密度分别为35.32μm、8.217×106个/cm3;弹性体含量低于和高于15%时,发泡质量较差,不适合于LDPE复合材料的发泡。     

Extrusion of polystyrene nanocomposite foams with supercritical CO2

Intercalated and exfoliated polystyrene/nano‐clay composites were prepared by mechanical blending and in situ polymerization respectively. The composites were then foamed by using CO₂ as the foaming agent in an extrusion foaming process. The resulting foam structure is compared with that of pure polystyrene and polystyrene/talc composite. At a screw rotation speed of 10 rpm and a die temperature of 200°C, the addition of a small amount (i.e., 5 wt%) of intercalated nano‐clay greatly reduces cell size from 25.3 to 11.1 μm and increases cell density from 2.7 × 10⁷ to 2.8 × 10⁸ cells/cm³. Once exfoliated, the nanocomposite exhibits the highest cell density (1.5 × 10⁹ cells/cm³) and smallest cell size (4.9 μm) at the same particle concentration. Compared with polystyrene foams, the nanocomposite foams exhibit higher tensile modulus, improved fire retardance, and better barrier property. Combining nanocomposites and the extrusion foaming process provides a new technique for the design and control of cell structure in microcellular foams.     

Manufacture of rigid PVC/wood‐flour composite foams using moisture contained in wood as foaming agent

Relatioships between the density of foamed rigid PVC/wood‐flour composites and the moisture content of the wood flour, the chemical foaming agent (CFA) content, the content of all‐acrylic foam modifier, and the extruder die temperature were determined by using a response surface model based on a four‐factor central composite design. The experimental results indicated that there is no synergistic effect between teh CFA content and the moisture content of the wood flour. Wood flour moisture could be used effectively as foaming agent in the production of rigid PVC/wood‐flour composite foams. Foam density as low as 0.4 g/cm³ was produced without the use of chemical foaming agents. However, successful foaming of rigid PVC/wood‐flour composite with moisture contained in wood flour strongly depends upon the presence of all‐acrylic foam modifier in the formulation and the extrusion die temperature. The lowest densities were achieved when the all‐acrylic foam modifier concentration was between 7 phr and 10 phr and extruder die temperature was as low as 170°C.     

Mechanical properties and morphology of polypropylene‐calcium carbonate nanocomposites prepared by dynamic packing injection molding

In this article, dynamic packing injection molding (DPIM) technology was used to prepare injection samples of Polypropylene‐Calcium Carbonate (PP/CaCO₃) nanocomposites. Through DPIM, the mechanical properties of PP/nano‐CaCO₃ samples were improved significantly. Compared with conventional injection molding (CIM), the enhancement of the tensile strength and impact strength of the samples molded by DPIM was 39 and 144%, respectively. In addition, the tensile strength and impact strength of the PP/nano‐CaCO₃ composites molded by DPIM increase by 21 and 514%, respectively compared with those of pure PP through CIM. According to the SEM, WAXD, DSC measurement, it could be found that a much better dispersion of nano‐CaCO₃ in samples was achieved by DPIM. Moreover, γcrystal is found in the shear layer of the DPIM samples. The crystallinity of PP matrix in DPIM sample increases by 22.76% compared with that of conventional sample. The improvement of mechanical properties of PP/nano‐CaCO₃ composites prepared by DPIM attributes to the even distribution of nano‐CaCO₃ particles and the morphology change of PP matrix under the influence of dynamic shear stress. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ethylene–propylene‐diene terpolymer/halloysite nanocomposites: Thermal,mechanical properties,and foam processing

Ethylene–propylene‐diene terpolymer (EPDM)/halloysite nanotube (HNT) nanocomposites were prepared by melt mixing in an internal mixer using a commercially available maleated semicrystalline EPDM and HNT. Transmission electron microscopy analysis of the EPDM/HNT composites revealed that the HNTs are uniformly dispersed at a nanometer scale in the matrix. Differential scanning calorimeter studies indicated that the HNT caused an increase in the nonisothermal crystallization temperature of the EPDM. Tensile and dynamic mechanical analysis exhibited that a small amount of the HNTs effectively enhanced the stiffness of the EPDM without adversely affecting its elongation‐at‐break. The EPDM/HNT nanocomposites were used to produce foams by using a batch process in an autoclave, with supercritical carbon dioxide as a foaming agent. The nanocomposite foams showed a smaller cell size and higher cell density as compared to the neat EPDM foam, and the nanocomposite with 10 phr HNT produced a microcellular foam with average cell size as small as 7.8 μm and cell density as high as 1.5 × 10¹⁰ cell/cm³. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40307.     

Investigation of a strategy for well controlled inducement of microcellular and nanocellular morphologies in polymers

This study is an effort to modify conventional batch processes to be able to produce polymeric foams with high cell density and small cell size, which cannot be reached by conventional batch foaming processes. This has been attained by controlling the foaming temperature and controlled stabilization of the cellular structure. The method was tested for both with and without addition of nanosized particles in polymeric matrix. The desired morphologies were obtained using a novel apparatus with the capability of instantaneous pressure drop and controlling stabilization of the foam structure. The design of the said apparatus was based on the idea that in a foaming process, nucleation is the predominant mechanism that determines the final foam structure. The produced foam products have uniform structures without any unfoamed skin. Results show that the control of the foaming temperature and the cell stabilization are the predominant factors in adjustment of the final foam morphology. A wide range of microcellular structures with cell densities between 10⁷ and 10¹² bubbles/cm³ and average cell sizes of 500 nm–20 μm were produced. Foaming of polystyrene‐nano‐silica nano‐composites with the same method showed that nanoparticles act as nucleating agent and increase the cell density in the final foam products compared with that of neat polystyrene. POLYM. ENG. SCI., 50:1558–1570, 2010. © 2010 Society of Plastics Engineers     

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     

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     

改性剂和增塑剂对PVC微孔泡沫塑料形态影响

以超临界CO2为发泡剂,用自制的动态模拟发泡装置研究了聚氯乙烯(PVC)配方中改性剂丙烯酸酯类高分子聚合物(ACR)含量和增塑剂邻苯二甲酸二辛酯(DOP)含量对PVC微孔塑料泡孔形态的影响.结果表明,在其他工艺条件和配方相同的情况下,ACR为4份时得到的PVC微孔泡沫塑料泡孔密度最大,泡孔粒径最小,DOP为2～6份时比较适合PVC微孔发泡,并且振动力场的引入有利于得到细小均匀的微孔结构.