Soft PVC foams: Study of the gelation,fusion, and foaming processes. I. Phthalate ester plasticizers

The use of foamed plastics gains more and more interest every day. Flexible poly(vinyl chloride) (PVC) foams have excellent mechanical properties and low price, thus their application is extensive. Foams are produced from plastisols, which are based on the suspension of the PVC resin in a plasticizer. Phthalates are the most used plasticizers in flexible PVC foam formation. In this study, we have studied the influence of the phthalate ester‐type plasticizers on the foaming process and the quality of the foams obtained from the corresponding plastisols. For the plastisols prepared with the nine phthalate plasticizers considered, we have studied and discussed the complex and extensional viscosities; the thermal behavior (DSC) including the decomposition of the chemical blowing agent, and the foam production by rotational molding. In addition, we have characterized the foams obtained by thermomechanical analysis, density, and bubble size distribution. As expected, clear correlations have been obtained between the molecular weight and structure of the plasticizer with the rheological behavior of the plastisols. The knowledge of the gelation and fusion processes and evolution of the extensional viscosity of the plastisols combined with the study of the thermal decomposition of the blowing agent in each plastisol allows for better understanding of the complex dynamic behavior of these foaming systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Elaboration and Characterization of Advanced Biobased Polyurethane Foams Presenting Anisotropic Behavior

Biobased and open cell polyurethane (PU) foams are produced from a synthesized sorbitol‐based polyester polyol. Different formulations are developed with various blowing agent systems (chemical vs physical blowing). Synthetized foams are fully characterized and compared. The cell morphology is carefully investigated by tomography and scanning electron microscopy. The chemical nature of the primary compounds, foaming kinetics, density, thermal behavior, and conductivity are fully studied, with also the main transition materials temperatures. It is shown that blowing agents especially impact the foaming kinetics. In the case of chemically blowing foams, higher foaming rate and temperatures are obtained. The mechanical behavior is particularly analyzed using quasi‐static compression tests, according two main axes compared to the rise direction. A direct relationship is observed between the formulation, foam structure, foam morphology, and corresponding mechanical properties. Results clearly highlight unexpected properties of biobased PU foams with unveil anisotropic mechanical properties.     

SiOC Ceramic Foams through Melt Foaming of a Methylsilicone Preceramic Polymer

A process for the production of SiOC ceramic foams has been for the first time developed through melt foaming of a siloxane preceramic polymer with the help of a blowing agent, followed by pyrolysis under an inert atmosphere. The raw material consisted of a methylsilicone resin, a catalyst (which accelerated the cross-linking reaction of the silicone resin) and a blowing agent (which generated gas above 210°C). Methylsilicone resin foams were obtained through controlling the melt viscosity around 210°C, temperature where the blowing agent started to decompose, by varying the initial molecular weight of the preceramic polymer and the amount of the catalyst. The obtained SiOC ceramic foams exhibited excellent oxidation stability up to 1000°C, as shown by thermal gravimetric analysis (TGA). As expected, the mechanical properties of the SiOC ceramic foams varied as a function of their bulk density, possessing a flexural strength up to 5.5 MPa and a compression strength up to 4.5 MPa. The main steps in the process, namely foaming and pyrolysis, were analyzed in detail. The viscosity change was analyzed as a function of temperature by the dynamic shear measurement method. The pyrolysis process of foams was analyzed by TGA coupled with infrared spectroscopy (IR).     

Effect of the nanoparticles on the morphology and mechanical performance of thermally blown 3D printed HIPS foams

Cellular polymer nanocomposites can combine high mechanical performance with low density. However, the manufacturing of porous nanocomposites into complex shapes can represent a challenge. Therefore, this article deals with the preparation, characterization, and 3D printing of porous nanocomposites. The filaments were extruded from the polymer nanocomposite filled by thermal chemical blowing agent, and then processed by 3D printing into the required shapes. In-situ and post-treatment foaming strategies were investigated and compared. The nanoparticles (NPs) significantly affected the processing, structure, thermal and mechanical properties of polymeric foams. The NPs, serving as a nucleating agent, allowed preparation of smaller pores and led to finer and more homogeneous foams. At the same time, they reinforced foam walls and thus improved mechanical properties. Moreover, NPs catalyzed decomposition of the blowing agent grains at lower temperature which brought about faster and more efficient foaming. This study showed the straightforward approach to prepare mechanically robust lightweight 3D printed materials.     

Chemically foaming of biodegradable poly(propylene carbonate) derived from carbon dioxide and propylene oxide

A composite chemical blowing agent PU8, composed of azodiformamide (AC), N,N′‐dinitroso pentamethylene tetramine (H) and other chemicals, was used to prepare the poly(propylene carbonate) foam material. The decomposition behavior of the blowing agent was investigated. The effect of blowing agent content and the foaming condition on the foaming of poly(propylene carbonate) was studied in detail. The results suggested that 10 phr PU8 is the optimum formulation to afford a desired poly(propylene carbonate) foam. The morphologies and compression strength of the poly(propylene carbonate) foam were studied using a scanning electron microscope and tensile tester, respectively. The foam with a blowing ratio of 16 can be obtained under an optimum foaming condition at 160°C for 30 min. POLYM. ENG. SCI. 46:153–159, 2006. © 2005 Society of Plastics Engineers     

Rheological properties and foam preparation of biodegradable poly(butylene succinate)

To produce biodegradable poly(butylene succinate) (PBS) foam by compression molding, high viscosity PBS was prepared with dicumyl peroxide (DCP) as a crosslinking agent and trimethylolpropane trimethacrylate (TMPTMA) as a curing coagent by crosslink method. The influences of various factors on the foaming process and the properties of PBS foams were investigated. The results show that the use of DCP and TMPTMA simultaneously can effectively increase the melt viscosity of PBS. Zinc oxide/zinc stearate was used to reduce the thermal decomposition temperature of the blowing agent azodicarbonamide, which can balance well the vulcanization of PBS and the decomposition of blowing agent. Finally, closed‐cell PBS foams with degradable property have been successfully prepared by a traditional chemical compression molding foaming way. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Cross-linkable and thermally stable aliphatic polycarbonates derived from CO2, propylene oxide and maleic anhydride

Poly(propylene carbonate maleate) (PPCMA) was successfully synthesized from carbon dioxide with propylene oxide and maleic anhydride using supported zinc glutarate as catalyst. The PPCMA can be readily cross-linked using dicumyl peroxide (DCP) as a cross-linking agent. The gel content, thermal performance and mechanical properties of the cross-linked PPCMA were then investigated. The results showed that the gel content increased with increasing DCP content and reaction temperature. The as-prepared PPCMA showed higher glass transition temperature (T _g) and decomposition temperature compared with uncross-linkable poly(propylene carbonate) (PPC). The introduction of small amount of cross-linkable moiety provides a very effective way to improve the thermal stability and to extend the molecular weight of PPC, consequently extending its application area.     

Mechanical properties of foams comprising virgin and waste polyethylene

Summary This paper addresses the use of waste polyethylene (p-PE) in low-density polyethylene (LDPE) foams with azodicarbonamide as the blowing agent. The amount of blowing agent was fixed at 5% for all mixtures, with 0.5% cross-linking agent, 1.7% zinc oxide and 1.7% stearic acid, by weight. Proportions of LDPE/p-PE (% wt) tested in foams were: 100/0, 85/15, 70/30, 60/40, 50/50 and 30/70. The components used to obtain the foams were processed in a Banbury mixer at 120 °C. The pre-form (non expanded material) was placed in a mold and the foaming was carried out in a hot press at 190 °C. The apparent densities of the foams obtained were 60–65 kg.m^-3. The mechanical properties (compression set under constant deflection, compressive strength and tear resistance) of LDPE foams containing different proportions of p-PE were compared with the LDPE foam obtained from virgin material only. The mechanical properties of foams with p-PE in their formulation were superior in relation to foams made from LDPE, because p-PE contains high-density polyethylene (HDPE), which is more rigid than LDPE.     

Copolymerization of propylene oxide and carbon dioxide in the presence of diphenylmethane diisoyanate

To improve the thermal and mechanical properties of poly(propylene carbonate) (PPC), the copolymerization of CO₂ with PO was successfully carried out in the presence of a third monomer, 4,4′-diphenylmethane diisocyanate (MDI) using supported multi-component zinc dicarboxylate as catalyst. Chemical structure, the molecular weight, as well as thermal and mechanical properties of the resulting new copolymers were fully investigated. The experimental results show that the yield increases with increasing MDI feed content from 0 to 2 wt.%. The introduction of MDI leads to an increase in the molecular weight of PPC with light crosslinking. When the MDI feed content is lower than 3 wt.%, the PPC copolymers have number average molecular weight (Mn) ranging from 153 K to 424 K g/mol and molecular weight distribution (MWD) values ranging from 1.71 to 2.79. The resulting PPC copolymers show higher glass transition temperature (Tg) and decomposition temperature compared with poly(propylene carbonate) (PPC) without MDI. Considering the gel content of the resulting copolymers, the optimized MDI feed content should be smaller than 1.5 wt.% based on PO content. The introduction of small amount of MDI provides a very effective way to improve the mechanical properties and thermal stabilities of PPC due to the increase in its molecular weight.     

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     

Foaming of aliphatic polyester using chemical blowing agent

Poly(butylene adipate‐co‐succinate) (PBAS), a saturated aliphatic polyester cured by dicumyl peroxide (DCP), was prepared and the viscoelastic property was investigated. The viscosity of crosslinked PBAS increased, and it exhibited rubbery behavior as the content of curing agent was increased. The results suggested that the viscosity and elasticity of PBAS could be regulated by adding a small amount of DCP; hence, the processibility could be improved. Prior to foaming, a proper formulation of blowing agent (blowing agent/urea activator = 100:8 phr) was examined to prepare expanded PBAS foam. Low‐density PBAS expanded foams were prepared using a chemical blowing agent and DCP. The effect of the foaming temperature, additive content, and curing agent content on the blowing ratio and morphology of expanded PBAS foams was investigated. A closed‐cell structure PBAS foam of high blowing ratio (density about 0.05 g/cm³) could be obtained by adding 3 phr DCP. To manufacture expanded PBAS foam under 0.1 g/cm³ using a chemical blowing agent, the storage modulus of the matrix polymer should exceed the loss modulus by enough to stabilize growing bubbles. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2443–2454, 2001     

Polyurethane foaming with CO2 adducts from C8 alkyl grafted polyethyleneimines: Optimization of the grafting rate and application of the blowing agents

We previously explored a series of CO₂ adducts from alkylated polyethylenimines with C₄ to C₁₆ alkyl side chains, serving as climate-friendly blowing agents for polyurethanes (PUs). Among them, the polyethylenimine with C₈ alkyl (2-ethylhexyl) side chains demonstrated the highest foaming efficiency. In this study, we further changed the grafting rate of the C₈ alkyl, from 7 to 16%, and investigated the effects of the resulting blowing agents on the foaming process. For both foaming systems containing a castor oil-derived polyol (Polycin T-400) or a poly(propylene glycol) polyol (Polyether 4110), the CO₂ adducts with a grafting rate of 13% displayed the best foaming performance in terms of high dispersibility in the foaming systems, homogenous cellular morphology, and good mechanical properties. Moreover, the 13%-C₈-alkylated blowing agent demonstrated high suitability for the foaming systems from biomass-sourced polyols (like Polycin T-400). Therefore, the optimized CO₂-adduct blowing agent could replace the currently used climate-changing hydrochlorofluorocarbons and hydrofluorocarbons, as well as might contribute to the development of future renewable PU foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48752.     

In‐situ grown silica/water‐borne epoxy shape memory composite foams prepared without blowing agent addition

Shape memory (SM) silica/epoxy composite foams were successfully synthesized via latex technology and prepared without blowing agent addition. Silica was synthesized via tetraethoxysilane (TEOS) hydrolysis. Silica/epoxy foams were obtained from the TEOS solution and water‐borne epoxy mixtures after freeze‐drying and foaming in the presence of residual moisture as the blowing agent under a vacuum at 110°C. The morphologies of the resulting foams were evaluated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Compression and thermo‐mechanical cycle tests were performed to measure the mechanical and SM properties of the foams. Experimental results indicated that the micrographs and mechanical properties of the foams were closely related to freeze‐drying time. The final composite foams exhibited high shape recovery and fixity ratios and could maintain both properties at more than 90% even after five thermo‐mechanical cycles. The properties obtained in the epoxy foams may offer new opportunities for their use in future structural applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42599.     

Microcellular foaming of silicone rubber with supercritical carbon dioxide

In spite of great concern on the industrial application of microcellular silicone rubber foams, such as in electric and medical devices, only a few works can be found about the foaming of silicone rubber. In this study, microcellular silicone rubber foams with a cell size of 12 μm were successfully prepared with curing by heat and foaming by supercritical CO₂ as a green blowing agent. The microcellular silicone rubber foams exhibited a well-defined cell structure and a uniform cell size distribution. The crosslinking and foaming of silicone rubber was carried out separately. After foaming, the silicone rubber foam was cross-linked again to stabilize the foam structure and further improve its mechanical properties. Foaming process of cross-linked silicone rubber should be designed carefully based on the viscoelastic properties because of its elastic volume recovery in the atmosphere. The basic crosslinking condition for small cell size and high cell density was obtained after investigating the rheological behavior during crosslinking.     

Influences of high-impact polystyrene loading on the foaming behavior and flame-retardant properties of polyphenylene oxide composites blown with CO2

Polymeric foam with high expansion ratio, well-defined cell structure, and excellent flame retardant properties is essential for broadening its applications. Polyphenylene oxide (PPO) is a kind of cost-effective engineering plastic with excellent flame retardancy, anti-dripping behavior, and good mechanical strength, but suffers from its poor processability. In this study, microcellular PPO composite foams were fabricated by applying a solid-state foaming technology using compressed CO₂ as the blowing agent. High-impact polystyrene (HIPS) phase was introduced with the aim to improve the fluidity and foaming ability of PPO composites. It was interesting to find that the 18–48% HIPS loading significantly increased the expansion ratio, that is, 1.8–3.3 versus, 10.8–14.3, and broadened the optimum foaming temperature of PPO composite foams, attributing to the miscible character between PPO and HIPS and excellent foaming ability of HIPS. Furthermore, the as-prepared PPO/HIPS composite foams exhibited high limited oxygen index (LOI) of 22.0–29.9%, low horizontal flammability rate (HFR) of 60.5–141.2 mm/min, and anti-dripping behavior, and the void fraction was verified to be a critical parameter to determine the flame retardant performance of the composite foam. Besides its lightweight and excellent flame retardant properties, PPO composite foams also presented uncompromised tensile properties and well-defined thermal insulation properties.     

Production of low-density LLDPE foams in rotational molding

This paper describes plastic foam processing for the manufacture of LLDPE foams in rotomolding. In order to better understand the mechanisms of foaming, a fundamental study on the foaming process in rotomolding has been conducted. First, the decomposition behavior of the chemical blowing agents was studied by a thermogravimetric analyzer (TGA). The zero-shear viscosity of LLDPEs was measured using a rotational stress rheometer. Also, an optical microscope with a hot stage was used to study cell nucleation, growth, coalescence, and coarsening in LLDPE melts, which provide an improved understanding of the foaming dynamics with a chemical blowing agent in rotational molding. Finally, the actual foaming behavior in rotomolding has also been studied. The experimental results indicate that the amount of blowing agent, the heating time, and the processing temperature play important roles in determining the cell morphology in rotational foam molding.     

High‐density polyethylene foams. I. Polymer and foam characterization

The density and morphology of closed‐cell high‐density foams were investigated with four different molecular weights of high‐density polyethylene (HDPE). The characterization of polyethylene via rheological methods was used to determine its influence on foam density and morphology. We found that foaming grade decreased with increasing molecular weight and increased with blowing agent content. The average cell size was also a strong function of molecular weight and blowing agent content. Increasing both the molecular weight and amount of blowing agent decreased the cell size. Cell size also increased for our lowest molecular weight HDPE but decreased for the others. Cell density also increased with increasing HDPE molecular weight. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2111–2119, 2003     

Evaluation of the salt leaching method for the production of ethylene propylene diene monomer rubber foams

The thermomechanical behavior of ethylene propylene diene monomer (EPDM) foams produced with the salt leaching method has been investigated and compared with the behavior of EPDM foams obtained from conventional blowing agents. Moreover, the salt-leaching process has been optimized to minimize salt residues and the influence of different parameters (such as average particle size and particle size distribution) has been investigated. Scanning electron microscopy and density measurements highlighted that salt-leaching leads to the formation of open-cell porosity with cell dimensions of around 60 to 80 μm, while foams obtained with the two traditional foaming agents lead to closed-cell porosity. Compression set values indicate that the behavior of the foams produced with salt leaching are more similar to the unfoamed rubber, characterized by higher elasticity and low residual deformation. Two theoretical models were successfully applied to the compression curves (Mooney-Rivlin and Exponential-Logarithmic) and they highlighted the effect of foaming on the properties of EPDM rubber and in particular the higher chain extensibility obtained through the salt leaching foaming method.     

Thermally stable poly(propylene carbonate) synthesized by copolymerizing with bulky naphthalene containing monomer

To enhance the thermal and mechanical properties of poly(propylene carbonate) (PPC), the terpolymers were synthesized from carbon dioxide, propylene oxide, and a third monomer, [(2‐naphthyloxy)methyl]oxirane (NMO) using supported zinc glutarate as catalyst. The structure of these terpolymers was confirmed by ¹H NMR spectroscopy. The catalytic activity, molecular weight, carbonate unit content, as well as thermal and mechanical properties were investigated extensively. The experimental results showed that the catalytic activity, molecular weight, and carbonate unit content decreased with the incorporation of NMO. DSC measurements indicated that the introduction of NMO increased the glass transition temperature from 38 to 42°C. TGA tests revealed that the thermal decomposition temperature (T_g?5%) of the synthesized terpolymer increased significantly, being 34°C higher than that of pure PPC. Accordingly, the mechanical properties proved also to be enhanced greatly as evidenced by tensile tests. These thermal and mechanical improvements are of importance for the practical process and application of PPC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of foaming temperature and rubber grades on properties of natural rubber foams

Foaming temperature and grade of dry natural rubber were varied to evaluate their effects on the morphology and mechanical properties of natural rubber (NR) foams. Three different grades of NR were used; namely ENR‐25, SMR‐L, and SMR‐10. NR foams from these grades were produced at three different foaming temperatures, i.e. 140, 150, and 160°C. The study was carried out using formulated compositions containing sodium bicarbonate as the chemical blowing agent and were expanded using conventional compression molding technique via a heat transfer foaming process. The NR foams were characterized with respect to their relative foam density, density of crosslinking, cell size, compression stress, and compression set. Increase in foaming temperature resulted in lower relative density and larger cell size. It was also discovered that the crosslink density slightly decrease with increasing foaming temperature. For mechanical properties, the highest foam density resulted in the highest compression stress. Compression stress at 50% strain increased with increasing foaming temperature and ENR‐25 foam has the highest compression stress among the produced foams. The results showed that the morphology, physical, and mechanical properties of the rubber foams can be controlled closely by the foaming temperature and rubber grades. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008