The effect of curing system on the properties of the thermoplastic elastomer foams of ethylene‐vinyl acetate copolymer and styrene‐butadiene and ethylene‐propylene‐diene monomer rubbers

Thermoplastic elastomer (TPE) foams have important application in electrical, toys, and other industries. Several foams were prepared by ethylene‐vinyl acetate copolymer (EVA) lonely, and in combination with styrene‐butadiene and ethylene‐propylene‐diene monomer rubbers (SBR and EPDM). The effects of crosslinking and foaming agents and EVA type on density and mechanical properties of the cured foams with two curing systems, peroxide and sulfur‐peroxide with potential use in automotive applications, were studied. The results showed that proposed compounds formulations were foamed properly. The viscosity of the EVA was a key factor for the density values of the formed foams. The densities of the cured foams with peroxide system with various SBR contents were higher when compared with cured foams with sulfur‐peroxide system. With increasing foaming agent, the densities of the foams were reduced for studied curing systems. The densities of the EVA–EPDM foams were lower than those of the EVA–SBR foams in the same studied conditions. Increasing rubber in foam formulation had adverse effect on tensile properties of the foams. The existence of the talc powder in foam formulation had important role on the shape and type of the formed cells and resulted in foams with mostly closed cells. The results of this study help the automotive article designer to produce suitable TPE foam. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45357.     

Physicomechanical,friction, and abrasion properties of EVA/PU blend foams foamed by supercritical nitrogen

Elastomer foams based on EVA, PU, and EVA/PU blends formulated for shoe‐sole applications were prepared by a supercritical N₂ batch foaming process and characterized for physicomechanical, friction and abrasion properties. The blending of EVA with PU was aimed for improving the friction and wear characteristics of the EVA based foams. All of the foams prepared showed spherical cells with closed‐cell morphology and the cell sizes varied with varying the EVA/PU blend ratio and CaCO₃ content of the foams. The properties such as hardness and resilience, friction coefficients and abrasion resistance improved for the EVA/PU blend foams compared to the EVA foam, but their compression set, tensile strength, and tear strength were inferior to the EVA foam. The incorporation of CaCO₃ filler increased density, hardness, tensile strength, and tear strength of the EVA/PU blend foams but decreased resilience, compression set, friction coefficients, and abrasion resistance. The improvement in friction coefficients and wear resistance obtained in the EVA/PU blend foams was significant for shoe‐sole applications. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Batch foaming of SAN/clay nanocomposites with scCO2: A very tunable way of controlling the cellular morphology

This paper aims at elucidating some important parameters affecting the cellular morphology of poly(styrene-co-acrylonitrile) (SAN)/clay nanocomposite foams prepared with the supercritical CO₂ technology. Prior to foaming experiments, the SAN/CO₂ system has first been studied. The effect of nanoclay on CO₂ sorption/desorption rate into/from SAN is assessed with a gravimetric method. Ideal saturation conditions are then deduced in view of the foaming process. Nanocomposites foaming has first been performed with the one-step foaming process, also called depressurization foaming. Foams with different cellular morphology have been obtained depending on nanoclay dispersion level and foaming conditions. While foaming at low temperature (40 °C) leads to foams with the highest cell density (∼10¹²-10¹⁴ cells/cm³), the foam expansion is restricted (d∼0.7-0.8 g/cm³). This drawback has been overcome with the use of the two-step foaming process, also called solid-state foaming, where foam expansion occurs during sample dipping in a hot oil bath (d∼0.1-0.5 g/cm³). Different foaming parameters have been varied, and some schemes have been drawn to summarize the characteristics of the foams prepared - cell size, cell density, foam density - depending on both the foaming conditions and nanoclay addition. This result thus illustrates the huge flexibility of the supercritical CO₂ batch foaming process for tuning the foam cellular morphology.     

Nanoplatelet reinforcement of cavity cell walls in polymer foams using carbon dioxide supercritical fluid

Reinforcing the cavity cell walls of polymer foams using nanoparticles can offer a new era for the property‐structure‐processing field in the development of functionalized ultra‐light components and devices manufactured from foam. When the nanoparticles are exfoliated in polymers, the viscosity substantially increases and thus mixing or foaming usually becomes almost impossible. We use CO₂ supercritical fluid (CO₂ SCF) for the mixing and foaming of poly(ethylene‐vinyl acetate) copolymer (EVA) with montmorillonite (MMT) nanoplatelets. The in situ evaporation of CO₂ induces robust cavity cells of the EVA/MMT nanocomposite foam in a stable form of spherical shapes, which are seldom achieved by other methods. As the bubble grows and becomes stabilized in CO₂ SCF, the exfoliated MMT nanoparticles are aligned at the cell walls by the Gibbs adsorption principle to minimize the surface energy at the gas–liquid interface and increase the rupture strength of the cavity walls. It is demonstrated that the developed methodology can be successfully used for foaming EVA containing high vinyl acetate (VA) content (>40%). Since EVA is too soft to construct cell walls of foam using conventional methods, the applicability of the developed methodology is extensively broadened for superior adhesion and compatibility with other materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46615.     

Equilibrium solubility of CO2 in rubbery EVA over a wide pressure range: effects of carbonyl group content and crystallinity

The equilibrium CO₂ sorption isotherms and isobars for rubbery EVA containing various amounts of vinyl acetate (VA) over a wide pressure range 10-340 atm and 25-52 °C were investigated. The normalized CO₂ sorption concentration (in cm³ (STP) CO₂/mole VA) isotherms of these polymers as a function of pressure consisted of two distinct regions turning at near P_c. The normalized sorption isotherms in these two distinct regions could be fairly described by two respective power laws: C=K_aP^n_a for above P_c and C=k_bP^n_b for below P_c. The normalized CO₂ sorption isotherms were found to be about the same for four EVA samples having different VA contents for below P_c, suggesting that the sorption process at below P_c may be mainly driven by the presence of carbonyl groups. At above P_c, the degree of crystallinity of the polymer appeared to be a major factor to affect the sorption process, with the higher the degree of crystallinity, the lower the normalized CO₂ sorption concentration in the polymer. The sorption isobars of the polymer as a function of temperature were governed by the interplay of density, viscosity, and diffusivity of CO₂ depending on the pressure studied.     

Stability improvement of CO2 foam for enhanced oil‐recovery applications using polyelectrolytes and polyelectrolyte complex nanoparticles

CO₂ foam for enhanced oil‐recovery applications has been traditionally used in order to address mobility‐control problems that occur during CO₂ flooding. However, the supercritical CO₂ foam generated by surfactant has a few shortcomings, such as loss of surfactant to the formation due to adsorption and lack of a stable front in the presence of crude oil. These problems arise because surfactants dynamically leave and enter the foam interface. We discuss the addition of polyelectrolytes and polyelectrolyte complex nanoparticles (PECNP) to the surfactant solution to stabilize the interface using electrostatic forces to generate stronger and longer‐lasting foams. An optimized ratio and pH of the polyelectrolytes was used to generate the nanoparticles. Thereafter we studied the interaction of the polyelectrolyte–surfactant CO₂ foam and the polyelectrolyte complex nanoparticle–surfactant CO₂ foam with crude oil in a high‐pressure, high‐temperature static view cell. The nanoparticle–surfactant CO₂ foam system was found to be more durable in the presence of crude oil. Understanding the rheology of the foam becomes crucial in determining the effect of shear on the viscosity of the foam. A high‐pressure, high‐temperature rheometer setup was used to shear the CO₂ foam for the three different systems, and the viscosity was measured with time. It was found that the viscosity of the CO₂ foams generated by these new systems of polyelectrolytes was slightly better than the surfactant‐generated CO₂ foams. Core‐flood experiments were conducted in the absence and presence of crude oil to understand the foam mobility and the oil recovered. The core‐flood experiments in the presence of crude oil show promising results for the CO₂ foams generated by nanoparticle–surfactant and polyelectrolyte–surfactant systems. This paper also reviews the extent of damage, if any, that could be caused by the injection of nanoparticles. It was observed that the PECNP–surfactant system produced 58.33% of the residual oil, while the surfactant system itself produced 47.6% of the residual oil in place. Most importantly, the PECNP system produced 9.1% of the oil left after the core was flooded with the surfactant foam system. This proves that the PECNP system was able to extract more oil from the core when the surfactant foam system was already injected. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44491.     

A study of cell nucleation in the extrusion of polypropylene foams

An investigation has been performed of the cell nucleation and initial growth behaviors in the foam processing of polypropylene (PP) in both the linear and branched forms. These materials were foamed in extrusion with the two blowing agents, CO₂ and isopentane. The cell density generally increased with an increased content of the blowing agent, for both CO₂ and isopentane. The effect of processing pressure on the cell density was distinct when CO₂ was used, whereas no pressure effect was observed in the foam processing with isopentane. The cell morphologies for the two PPs were found to be significantly different. A slightly lower nuclei density was observed in the branched PP foams than in the linear PP foams. However, the phenomenon of cell coalescence was observed much less in the branched PP foams. Most cells in the branched PP foams were closed, whereas in the linear PP foams they were connected to each other. The experimental results indicated that the branched structure played an important role in determining the cell morphologies through its effects on the melt strength and/or melt elasticity.     

The comparison of experimental and calculated pore size distributions of activated carbons

Activated carbons are disorganized materials with variable pore size distributions (PSD). If one assumes that the porosity consists mainly of locally slit-shaped micropores, model isotherms can be obtained by computer simulations and used to assess the PSD on the basis of experimental isotherms. In the present study, CO₂ isotherms have been measured at 273 K on seven well-characterized microporous carbons with average micropore widths between 0.65 and 1.5 nm and analysed with model isotherms obtained with standard Monte Carlo simulations. The resulting PSD are in good agreement with those obtained from a modified Dubinin equation, from liquid probes of molecular dimensions between 0.4 and 1.5 nm, from STM and from modelling based on CH₄ adsorption at 308 K. The present study validates the determination of micropore distributions in active carbons based on CO₂ isotherms, provided that no gate effects are present.     

Preparation and characterisation of carbon-coated ceramic foams for organic vapour adsorption

Ceramic foam substrates of various porosities were coated with novolak resin, which was then subsequently carbonised and activated to develop a pore structure. The carbon forming the layer was characterised by thermal analysis, TPD and N₂, CO₂ and hexane vapour adsorption. It was found to be microporous with a high surface area (up to 1400 m² g⁻¹), which made it a good adsorbent for hexane vapour at ambient temperature. The carbon-ceramic interface was examined using SEM. The coated foams displayed a reduced pressure drop compared to carbon granules and had good dynamic hexane vapour adsorption characteristics. Depending on the foam architecture, hexane breakthrough was delayed for up to 78 min.     

Processing of nanocomposite foams in supercritical carbon dioxide. Part I: Effect of surfactant

Polystyrene-clay nanocomposites were prepared by in situ polymerization to achieve the better dispersion of lamellar silicates i.e. montmorillonite and fluorohectorite and were used to process foams with supercritical CO₂. Clay-Polymer interactions were modulated by varying the surface treatment of clays: a physical interface was formed with the compatible surfactant showing aromatic groups (MMT-benz) and a chemical interface was created after reaction of methacrylate group (MMT-MHAB) with the styrene monomer. The dispersion of nanocomposites and the microstructure of resulting foams are very dependent on the quality of the clay/matrix interface. With the compatible clay, exfoliation of aromatic clay in polystyrene matrix is obtained at all scales. On the other hand, with the reactive clay, intercalated primary particles are obtained but the size of foam cells is the smallest and cell density is the highest. Our results suggest that the nucleation occurs primarily on physico-chemical nucleation sites that are the carbonyl group of the tethered copolymers synthesized on reactive clay and that present a strong affinity for CO₂. The relaxation times determined by using solid-state NMR spectroscopy are consistent with the formation of the in situ copolymers.     

Processing and properties of an ethylene–vinyl acetate blend foam incorporating ethylene–vinyl acetate and polyurethane waste foams

Waste polyurethane foam (w‐PU) and waste ethylene–vinyl acetate foam (w‐EVA) were used as fillers for the production of an ethylene–vinyl acetate (EVA) blend foam. Two different foaming techniques (single‐stage and heat–chill processes) were used for this purpose. The waste foam concentration was varied up to 30 wt % of the original EVA. The physical, mechanical, and morphological properties of the filled foam were studied. The single‐stage process produced blend foams with a lower density and a greater cell size than the foams obtained by the heat–chill process. The density and compression strength of the blend foam increased as the percentage of w‐PU foam increased. However, for the w‐EVA/EVA blend foams, the addition of w‐EVA foam did not significantly affect the density or compression strength compared to the original EVA foams. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44708.     

Stabilization of natural gas foams using different surfactants at high pressure and high temperature conditions

Natural gas foam can be used for mobility control and channel blocking during natural gas injection for enhanced oil recovery, in which stable foams need to be used at high reservoir temperature, high pressure and high water salinity conditions in field applications. In this study, the performance of methane (CH₄) foams stabilized by different types of surfactants was tested using a high pressure and high temperature foam meter for surfactant screening and selection, including anionic surfactant (sodium dodecyl sulfate), non-anionic surfactant (alkyl polyglycoside), zwitterionic surfactant (dodecyl dimethyl betaine) and cationic surfactant (dodecyl trimethyl ammonium chloride), and the results show that CH₄-SDS foam has much better performance than that of the other three surfactants. The influences of gas types (CH₄, N₂, and CO₂), surfactant concentration, temperature (up to 110°C), pressure (up to 12.0 MPa), and the presence of polymers as foam stabilizer on foam performance was also evaluated using SDS surfactant. The experimental results show that the stability of CH₄ foam is better than that of CO₂ foam, while N₂ foam is the most stable, and CO₂ foam has the largest foam volume, which can be attributed to the strong interactions between CO₂ molecules with H₂O. The foaming ability and foam stability increase with the increase of the SDS concentration up to 1.0 wt% (0.035 mol/L), but a further increase of the surfactant concentration has a negative effect. The high temperature can greatly reduce the stability of CH₄-SDS foam, while the foaming ability and foam stability can be significantly enhanced at high pressure. The addition of a small amount of polyacrylamide as a foam stabilizer can significantly increase the viscosity of the bulk solution and improve the foam stability, and the higher the molecular weight of the polymer, the higher viscosity of the foam liquid film, the better foam performance.     

Supercritical CO2-assisted extrusion foaming: A suitable process to produce very lightweight acrylic polymer micro foams

A strategy of CO₂-assisted extrusion foaming of PMMA-based materials was established to minimize both foam density and porosities dimension. First a highly CO₂-philic block copolymer (MAM: PMMA-PBA-PMMA) was added in PMMA in order to improve CO₂ saturation before foaming. Then the extruding conditions were optimized to maximize CO₂ uptake and prevent coalescence. The extruding temperature reduction led to an increase of pressure in the barrel, favorable to cell size reduction. With the combination of material formulation and extruding strategy, very lightweight homogeneous foams with small porosities have been produced. Lightest PMMA micro foams (ρ = 0.06 g cm⁻³) are demonstrated with 7 wt% CO₂ at 130°C and lightest blend micro foams (ρ = 0.04 g cm⁻³) are obtained at lower temperature (110°C, 7.7 wt% CO₂). If MAM allows a reduction of T^foaming, it also allows a much better cell homogeneity, an increase in cell density (e.g., from 3.6 10⁷ cells cm⁻³ to 2 to 6 10⁸ cells cm⁻³) and an overall decrease in cell size (from 100 to 40 μm). These acrylic foams produced through scCO₂-assisted extrusion has a much lower density than those ever produced in batch (ρ ≥ 0.2 g cm⁻³).     

Extrusion of poly(ether imide) foams using pressurized CO2: Effects of imposition of supercritical conditions and nanosilica modifiers

Foams of an engineering plastic, poly(ether imide), were extruded using a single screw extruder employing pressurized CO₂ as the blowing agent. The porosity, pore size distributions, and the density of the foams were especially affected by the pressure drop, the pressure loss rate, and temperature at the die. Significant increases in porosity and pore size and corresponding decreases in density were observed when the pressure imposed on CO₂ became greater than the critical pressure values of CO₂ (i.e., the temperature was always greater than the critical temperature of the CO₂ in the extruder and the die). The viscoelastic material functions of the extruded foams depended especially on the density of the foam, with the elastic modulus increasing with density. The incorporation of nanosilica particles in the 0.08–0.6% by weight range increased only the density of the foam and did not provide any benefits in controlling of the nucleation rate and the pore size distribution, presumably due to their poor dispersibility and agglomerated state in the single screw extruder. POLYM. ENG. SCI., 54:2064–2074, 2014. © 2013 Society of Plastics Engineers     

A new microcellular foam injection‐molding technology using non‐supercritical fluid physical blowing agents

A new foam injection‐molding technology was developed to produce microcellular foams without using supercritical fluid (SCF) pump units. In this technology, physical blowing agents (PBA), such as nitrogen (N₂) and carbon dioxide (CO₂), do not need to be brought to their SCF state. PBAs are delivered directly from their gas cylinders into the molten polymer through an injector valve, which can be controlled by a specially designed screw configuration and operation sequence. The excess PBA is discharged from the molten polymer through a venting vessel. Alternatively, additional PBA is introduced through the venting vessel when the polymer is not saturated with PBA. The amount of gas delivered into the molten polymer is controlled by the gas dosing time of the injector valve, the secondary reducing pressure of the gas cylinder and the outlet (back) pressure of the venting vessel. Microcellular polypropylene foams were prepared using the developed foam injection‐molding technology with 2–6 MPa CO₂ or 2–8 MPa N₂. High expansion foams with an average cell size of less than 25 μm were prepared. The developed technology dispels arguments for the necessity to pressurize N₂ or CO₂ to the SCF to prepare microcellular foams. POLYM. ENG. SCI., 57:105–113, 2017. © 2016 Society of Plastics Engineers     

Some thermodynamic and kinetic properties of the system PETG-CO2, and morphological characteristics of the CO2-blown PETG foams

The solubility of CO₂ in PETG, a glycol-modified PET, was measured at different temperatures and over a broad pressure range, and diffusion coefficients were derived at the corresponding conditions. The solubility of CO₂ is quits high. For example, almost 15 wt% CO₂ can be dissolved in PETG at 35°C and 6.0 MPa. Consequently, CO₂ is good blowing agent for PETG. Cellular foams in the density range of about 0.04 to 1.2 g/cm³ and diameters in the range of about 10 to 150 µm were produced. The foam density and the cell size were found to depend on the foaming temperature and time, with larger cells obtained at higher temperatures or when the sample was foamed for a longer time. The foam density decreased with an increase in the foaming temperature to about 90°C, beyond which the density tended to increase slightly due to the cell collapse or coalescence. The density reduction also depended on the pressure at which the polymer was saturated with CO₂; the higher the saturating pressure at a given temperature, the greater the density reduction.     

Effective diffusion coefficient for the gas contained in closed cell polyethylene-based foams subjected to compressive creep tests

In this paper, a new method to obtain the effective diffusion coefficient of the gas contained in closed cell foams under static loading is presented. Compressive creep experiments were performed on six low-density polyethylene (LDPE) and two polyethylene-co-vinyl acetate (EVA) foams of different densities using a home-designed compressive creep apparatus. The modelling of the evolution of pressure inside the cells was performed using an isothermal compression model. The effective diffusion coefficients were obtained from pressure decrease with time using an analytical solution of the diffusion equation. The values obtained agreed with those in literature and were dependent on both foam density and chemical composition.     

Effect of compatibilizer and silane coupling agent on physical properties of ethylene vinyl acetate copolymer/ethylene‐1‐butene copolymer/clay nanocomposite foams

In this study an attempt was made to obtain lower density of ethylene‐vinyl acetate copolymer (EVA)/ethylene‐1‐butene copolymer (EtBC) foams without sacrificing mechanical properties. For this purpose EVA/EtBC/clay nanocomposite foams were prepared. To investigate the effect of compatibilizer and silane coupling agent on the physical properties of the EVA/EtBC/clay foams, maleic anhydride‐grafted EtBC (EtBC‐g‐MAH) and the most commonly used silane coupling agent in rubbers, bis(3‐triethoxysilylpropyl) tetrasulfide (Si‐69) were used in the preparation of EVA/EtBC/clay nanocomposite foams. The formation of EVA/EtBC/clay nanocomposite foams was supported by X‐ray diffraction results. And, using a compatibilzer and silane coupling agent, lower density of EVA/EtBC/clay nanocomposite foams were obtained without sacrificing mechanical properties except compression set. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3259–3265, 2006     

Generation and characterization of carbon nano-fiber-poly(arylene ether sulfone) nanocomposite foams

In this study, carbon nano-fibers (CNFs) were used to increase the compressive properties of poly(arylene ether sulfone) (PAES) foams. The polymer composite pellets were produced by melt blending the PAES resin with CNFs in a single screw extruder. The pellets were saturated and foamed with water and CO₂ in a one-step batch process method. Dynamic mechanical thermal analysis (DMTA) was used to determine the reduced glass transition temperature (T_g) of the CNF-PAES as a result of plasticization with water and CO₂. Sharp transitions were observed as peaks in the tan δ leading to accurate quantitative values for the T_g. By accurately determining the reduced T_g, the foaming temperature could be chosen to control the foam morphology. Foams were produced which ranged in density from 290 to 1100 kg/m³. The foams had cell nucleation densities between 10⁹ and 10¹⁰ cells/cm³, two orders of magnitude higher than unreinforced PAES foam, suggesting that the CNFs acted as heterogeneous nucleating agents. The CNF-PAES foam exhibited improved compressive properties compared to unreinforced PAES foam produced from a similar method. Both the specific compressive modulus and strength increased by over 1.5 times that of unreinforced PAES foam. The specific compressive strength of 59 MPa for the CNF-PAES foam is similar to that of commonly used high performance structural foam, poly(methacrylimide foam).     

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