Process-structure-property relationship of meltblown poly (styrene–ethylene/butylene–styrene) nonwovens

With the advance of the thermoplastic plastic elastomer (TPE) technology, there are growing interest and needs for using these materials in the meltblowing process where benefits of small fiber diameters of meltblowns can be combined with rubber-like elastic properties of elastomers. Performances and utilities of wide ranges of meltblown products such as facemask, medical barrier, wound-care, diaper can be drastically improved with additions of TPE. In this study, a new elastomeric meltblown fabric was successfully made with the styrene–ethylene/butylene–styrene (SEBS) block copolymer, and the relationship among structure, tensile properties, and meltblowing process parameters are studied. We found that median fiber diameter increases with the polymer mass throughout and decreases with air pressure, and fabric solidity has significantly influenced by die collector distance (DCD). The pore sizes of the fabrics are directly influenced by fiber diameters at the given DCD, but higher DCD increases the pore size due to their open structures. All SEBS nonwovens exhibit high strain at break, larger than 400%. Processing parameters significantly affect tensile properties, and this can be attributed to the fabric structure changes. The reduction of fiber diameter tends to increase the tensile strength of the fabric as it created more fiber-to-fiber bond points.     

Ultra-stretchable thermoplastic elastomeric materials based on styrene–isoprene–styrene triblock copolymer: Influence of calcium copper titanate on mechanical and dielectric properties

Conventional charge storage devices made of ceramic materials have limited deformability and configurability due to their extreme stiffness. The high demand for compliant dielectrics has led researchers to look beyond conventional ceramics, despite their very high dielectric properties. In this work, a mechanically robust, highly-flexible and ultra-stretchable thermoplastic elastomeric material with dielectric characteristics has been fabricated by introducing calcium copper titanate [CaCu₃Ti₄O₁₂] (CCTO) dielectric material onto macromolecular chains of styrene–isoprene–styrene (SIS) triblock copolymer via a solution-based polymer processing technique. CCTO powders have been synthesized using sol–gel technique. The resulting composite is ultra-stretchable with strain at break of ~3200% and has high dielectric permittivity of ~10. High dielectric property is attributed to the well-dispersed dielectric CCTO fillers within the SIS matrix, which provide sites for interfacial polarization and space charge accumulation. The influence of CCTO on dielectric properties has also been validated using the modified Cole–Cole model.     

Non-isothermal crystallization behavior of poly(vinylidene fluoride)/ethylene–vinyl acetate copolymer blends

Non-isothermal crystallization behavior of poly(vinylidene fluoride) (PVDF) and ethylene–vinyl acetate (EVA) copolymer and their binary blends with different blending ratios were investigated by the use of differential scanning calorimetry (DSC). With the increasing cooling rates, PVDF, EVA and their binary blends showed wide crystallization temperature range and high crystalline enthalpy. Jeziorny and Mo’s models were applied to calculate non-isothermal crystallization kinetics parameters of neat PVDF, EVA and their binary blends. By Jeziorny method, the crystallization process of neat PVDF, EVA and PVDF/EVA = 7/3 blend can be divided into two parts: primary and secondary crystallization processes. The Avrami exponent n ₁ indicated that the primary crystallization process was a mixture model of three-dimensional and two-dimensional space extensions. In comparison, PVDF/EVA = 5/5 and PVDF/EVA = 3/7 blends showed a single crystallization process. Through Mo’s analysis, faster cooling rate was demanded to reach higher relative crystallinity. Crystallization rate coefficient (CRC) was used to describe the effect of crystallization rates on the interaction between PVDF and EVA. CRC reached a maximum value when the mass ratio of PVDF and EVA was 7/3. The maximum CRC values of PVDF system and EVA system were 98.1 and 179.9 h^?1, respectively. The activation energy was closely related to the extent of conversion and the neat samples had a maximum value of crystallization activation energy. This was consistent with the observation for the parameters from Jeziorny analysis and could be correlated to the heterogeneous nucleation.     

Correlation of the morphology and thermooxidative degradation behavior of poly(ethylene terephthalate)–nitrile butadiene rubber–polycarbonate ternary blends

In this study, we prepared ternary poly(ethylene terephthalate) (PET)–nitrile butadiene rubber (NBR)–polycarbonate (PC) blends through a molten mixing procedure, and with a corotating extruder, we studied the morphology and thermodynamic properties of each purified polymer and the binary and ternary blends with different compositions. Dynamic mechanical analysis of both the PET–PC and PET–NBR samples showed individual loss peaks for each component, but in different ternary samples, the effects of different percentages of components (PC–PC and PET–NBR) were observed; this revealed changes in the loss peak locations. Individual loss peaks of PET and PC in the ternary PET–NBR–PC blends (81/9/10 and 63/30/7)—proof of the miscibility of the samples—were also observed in this study. The thermal properties of the samples were measured and examined with the thermogravimetric analysis and differential thermogravimetry testing methods. The activation energy and order of reaction values for the samples under an air atmosphere with single-rate methods of heating were studied. Finally, the relation between the type of morphology and the thermal degradation behavior was investigated. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47171.     

Influence of maleation of polypropylene on the interfacial properties between polypropylene and ethylene–vinyl alcohol copolymer

In order to improve the miscibility between the components of a blend, it is possible to modify the chemical structure by functionalizing one or more of the components. This results in better adhesion at the interface between the components and, consequently, in better mechanical properties. In this work, the influence of maleation of polypropylene on the interface between polypropylene and ethylene–vinyl alcohol copolymer was studied using the measurement of interfacial tension, surface analysis with electron spectroscopy for chemical analysis (ESCA), and morphological observation, using scanning electron microscopy (SEM). The interfacial tension between a 0.1-wt % maleated polypropylene and ethylene–vinyl alcohol copolymer was shown to be 25% lower than the interfacial tension between nonmaleated polypropylene and ethylene–vinyl alcohol copolymer. This resulted in better adhesion between maleated polypropylene and ethylene–vinyl alcohol copolymer. The surface analysis indicates that this decrease of interfacial tension is due to migration of the maleic groups of the maleated polypropylene to the interface between the 2 polymers and that, probably, a chemical interaction occurs at the interface between maleated polypropylene and ethylene–vinyl alcohol copolymer. It is also shown in this work that additives, such as SiO₂, found in commercial polymers, can influence the interfacial tension between 2 polymers. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 75–87, 1998     

Carbon black reinforced thermoplastic vulcanisates based on ethylene–vinyl acetate copolymer/styrene–butadiene rubber blends

Thermoplastic vulcanisates (TPVs) based on ethylene–vinyl acetate copolymer (EVA)/styrene–butadiene rubber (SBR) blends were prepared by dynamic vulcanisation, with the TPVs being reinforced by carbon black (CB). Experimental results indicated that the mechanical properties of dynamically vulcanised EVA/SBR blends were enhanced remarkably by the incorporation of CB. Morphology study showed that the SBR particles with average diameter of 20?μm were dispersed evenly on the etched surface of EVA/SBR/CB TPVs. The Mullins effect could be observed in the stress–strain curves of EVA/SBR TPVs and EVA/SBR/CB TPVs during the uniaxial loading–unloading cycles. Compared with EVA/SBR TPVs, CB reinforced EVA/SBR TPVs had the relatively higher stress, residual deformation and internal friction loss.     

Influence of nano–micrometre powder blends on microstructure and mechanical properties of silicon nitride

Abstract

A well known route to making tough silicon nitride compositions is to control the grain size and aspect ratio distributions. This is usually done by choosing the appropriate powder characteristics, sintering conditions, as well as sintering additives. The effect of hot pressing a blend of nano and micrometre scale silicon nitride powder is explored here. Microstructures and mechanical properties are determined for these hot pressed ceramics and are compared with a reference silicon nitride. Hardness and fracture toughness are determined at room temperature using hardness indents produced by a macro Vickers hardness indenter. Grain size and aspect ratio distributions and their impact on mechanical properties are presented. Blending of nano and micrometre scale powder is shown to result in a refined microstructure with an increase in the area/volume fraction of finer grains. Rising R curves are established for these ceramics demonstrating toughening behaviour. Crack bridging and crack path deviation are identified as possible toughening mechanisms.     

Rheological and mechanical properties of polycarbonate–liquid-crystalline polymer blends with controlled chemical reactions

Chemical reactions can occur during the melt blending of polymers containing an ester group because ester groups are usually unstable at high temperatures; this instability generally deteriorates the mechanical properties of blends. Here, effects of chemical reactions on the rheological and mechanical properties of polycarbonate (PC)/liquid-crystalline polymer (LCP) blends are carefully investigated to determine a method for minimizing such undesirable impacts. For comparison, a physical blend, in which chemical reactions were minimized, was prepared at 300 °C in a twin-screw extruder. Both shear viscosity and complex viscosities of reactive blends were lower than those of physical blends, being almost proportional to [M_w ]^3.4 as a result of depolymerization and transesterification. Because of the enhanced miscibility, the tensile modulus of reactive blends increased compared with that of physical blend, according to the increase in the degree of incorporation (DI). It was also possible to increase tensile modulus if triester was added to the reactive blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2799–2807, 2001     

Effects of modified silica on the co-vulcanization kinetics and mechanical performances of natural rubber/styrene–butadiene rubber blends

Rubber blends are widely used for combining the advantages of each rubber component. However, to date, how to determine and distinguish the vulcanization kinetics for each single rubber phase in rubber blends during the co-vulcanization process is still a challenge. Herein, high-resolution pyrolysis gas chromatography–mass spectrometry (HR PyGC-MS) was employed for the first time to investigate the vulcanization kinetics of natural rubber (NR) and styrene–butadiene rubber (SBR) in NR/SBR blends filled with modified silica (SiO₂). The reaction rates of crosslinking of each rubber phase in NR/SBR were calculated, which showed that the crosslinking rates of NR were much lower than those of SBR phase in the unfilled blends and blends filled with unmodified and silane modified silica. Interestingly, the vulcanization rates of NR and SBR phase were approximately same in the vulcanization accelerator modified silica filled blends, showing better co-vulcanization. In addition, the vulcanization accelerator modified silica was uniformly dispersed and endowed rubber blends with higher mechanical strength compared to the untreated silica. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48838.     

Review on transesterification in polycarbonate–poly(butylene terephthalate) blend

Various polycarbonate - poly(butylene terephthalate) polyester (PC-PBT) blend prepared by reactive melt blending primarily in extruder with range of temperature and time are discussed in this review article. In the melt blended PC-PBT blend system, transesterification plays a major role in formation of PC-PBT blend. Transesterification reactions between these two polymers have been analyzed by proper polymer sample, end-capped or having reactive chain end group. The kinetics of mechanism is a function of temperature and PC-PBT ratio. Trace catalyst residue present in PBT catalyzes the transesterification reaction. As the extent of transesterification is increased, it forms various composition of copolymer. Inhibition in the transesterification reaction of PC-PBT blend has been observed when different type of alkyl, aryl, and alkyl-aryl group of phosphite are introduced into it, otherwise there has been collateral change in the morphology, thermal, and mechanical property of blend. Therefore, this PC-PBT blend has been an interesting topic of research in academia and industries.     

Impact of organoclays on the phase morphology and the compatibilization efficiency of immiscible poly(ethylene terephthalate)/poly(ε-caprolactone) blends

Adding nanofillers Cloisite 30B (C30B) and Cloisite 15A (C15A) to poly(ethylene terephthalate) (PET)/poly(ε-caprolactone) (PCL) (70/30, wt/wt) blends via melt blending can improve their phase morphology and change their interface properties. The effects of the different selective localization of clay on the structure and the morphologies are studied and evaluated by theoretical and experimental methods. It is found that C30B is selectively localized in PET and at the PET-PCL interface, whereas C15A is mainly localized at the interface. Moreover, the changes in the rheological behavior of the blends are attributed to the formation of clay network-like structures. X-ray diffraction, scanning electron microscope, and transmission electron micrograph observations also evidenced an exfoliated and/or intercalated structure of C30B, and intercalated structure of C15A in the blend, together with significant morphology changes of the initially immiscible blend. The relative permeability to PET/PCL of the nanocomposites decreased with the increasing of nanoclays content. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48812.     

Melting and crystallization behaviors of compatibilized poly(trimethylene terephthalate)/acrylonitrile–butadiene–styrene blends

The melting and crystallization behaviors of poly(trimethylene terephthalate) (PTT)/acrylonitrile–butadiene–styrene (ABS) blends were investigated with and without epoxy or styrene–butadiene–maleic anhydride copolymer (SBM) as a reactive compatibilizer. The existence of two separate composition-dependent glass-transition temperatures (T_g's) indicated that PTT was partially miscible with ABS over the entire composition range. The melting temperature of the PTT phase in the blends was also composition dependent and shifted to lower temperatures with increasing ABS content. Both the cold crystallization temperature and T_g of the PTT phase moved to higher temperatures in the presence of compatibilizers, which indicated their compatibilization effects on the blends. A crystallization exotherm of the PTT phase was noticed for all of the PTT/ABS blends. The crystallization behaviors were completely different at low and high ABS contents. When ABS was 0–50 wt %, the crystallization process of PTT shifted slightly to higher temperatures as the ABS content was increased. When ABS was 60 wt % or greater, PTT showed fractionated crystallization. The effects of both the epoxy and SBM compatibilizers on the crystallization of PTT were content dependent. At a lower contents of 1–3 wt % epoxy or 1 wt % SBM, the crystallization was retarded, whereas at a higher content of 5 wt %, the crystallization was accelerated. The crystallization kinetics were analyzed with a modified Avrami equation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enhanced properties of poly(styrene–b–ethylene–co–butylene–b–styrene) nanocomposites with in situ construction of interconnected graphene network

In this work, such elastomeric nanocomposites were fabricated with graphene (GE) sheets selectively distributing between polymer matrices and forming three-dimensional networks. The solvent evaporation process was first introduced to produce poly(styrene–ethylene–co–butadiene–b–styrene) (SEBS) microspheres and then reduced GE oxide attached to the surface of SEBS microspheres via electrostatic interaction and sonication-assisted reduction. The microstructure of nanocomposites, prepared by compression molding using SEBS/GE microspheres, was investigated using scanning electron microscopy and transmission electron microscopy. The results showed that interconnected GE networks formed in heat-pressing composite and was destroyed after twin-roll mixing. The SEBS/GE nanocomposites showed enhanced electrical, thermal, and mechanical properties. The electrical resistivity of nanocomposites obtained via heat-pressing reached to 1.1 × 10³ Ω m at a 2.5 wt % (1.07 vol %) content of GE. The thermal and mechanical properties were also characterized. It was found that the initial degradation temperature increased by nearly 40 °C and the mechanical properties continued to rise with GE content below 0.5 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47118.     

Photocrosslinking of styrene–isoprene–styrene; effect of benzoin and ethylene glycol dimethacrylate on physical properties

Crosslinking reaction of polymer by ultraviolet (UV) irradiation has been important in industries. In this work, photocrosslinking of styrene–isoprene–styrene (SIS) triblock copolymer in the presence of benzoin photoinitiator and a dimethacrylate monomer as crosslinking agent was investigated. Curing of samples was initiated under UV irradiation. Benzoin was used as photoinitiator because it contains chromophore group that could absorb UV irradiation. Ethylene glycol dimethacrylate (EGDMA) was used as crosslinking agent, since it has alkene functional groups that could react with the alkene group of SIS. ATR-FTIR spectra of samples show that absorption band of double bond at 1500–1600?cm^?1 decreases after UV exposure. Increasing the concentration of benzoin (0.1–1?phr) and EGDMA (1–10?phr) leads to an increase in gel content and hardness, while swelling ratio decreases. After 5?min heating at 150?°C, about 20%wt of the unirradiated compound became insoluble, because heating of compound at 150?°C causes crosslinking reaction without any irradiation.     

A quantitative analysis of the effect of interface delamination on the fracture behavior and toughness of multilayered propylene–ethylene copolymer/low density polyethylene films by the essential work of fracture (EWF)

The multilayered propylene–ethylene copolymer (CPP)/low density polyethylene (LDPE) composite sheets were prepared by the microlayered coextrusion system. The essential work of fracture (EWF) method was firstly used to quantitatively evaluate the fracture behavior of layered materials. The experimental results indicated that the two-dimensional layered interfaces in the multilayered materials could play an important role in the fracture behavior. The specific essential work of fracture, w_e, increased with the layers due to interfacial delamination. Additionally, the different testing speeds had a dual effect on the increscent trend of the specific essential work of fracture, w_e, with increasing layers.     

Synergistic toughening effects of nucleating agent and ethylene–octene copolymer on polypropylene

The synergistic toughening effect of nucleating agent (NA) and ethylene–octene copolymer (POE) on polypropylene was studied in the present work. Two different nucleating agents, such as α-form nucleating agent 1,3 : 2,4-bis (3,4-dimethylbenzylidene) sorbitol (DMDBS, Millad 3988) and β-form nucleating agent aryl amides compounds (TMB-5), were selected to blend with PP or PP/POE blends, respectively. The results show that PP containing 0.5–0.25 wt % DMDBS or 0.5–0.25 wt % TMB-5 has relatively low impact strength. For PP/POE blends, although the impact strength increases gradually with the increasing of POE content, high content of POE is needed to obtain the available PP toughness. However, once nucleating agent and POE are simultaneously added into PP, PP/POE/NA blends show great improvement of toughness even at low POE content. Furthermore, the synergistic toughening effect of POE/TMB-5 is more apparent than that of POE/DMDBS. SEM results show that whether DMDBS or TMB-5 has no apparent effect on the morphologies of POE in the PP/POE/NA blends. Further investigations using DSC and POM indicate that both DMDBS and TMB-5 induce the apparent enhancement of the crystallization temperature of PP and the sharp decrease of spherulites size of PP in the PP/POE/NA blends. The possible synergistic toughening mechanism is discussed in the work. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of carbon black on uncompatibilised and compatibilised SBR–NBR blends

Abstract

Elastomeric blends based on SBR and NBR have been prepared, giving emphasis to differences in blend composition. It was observed from dynamic mechanical analysis that the SBR–NBR blends can be compatibilised by addition of 5 pphr dichlorocarbene modified styrene/butadiene rubber. The efficiency of carbon black in uncompatibilised and compatibilised blends was evaluated with reference to their processing characteristics and technological properties and the resistance of the vulcanisates towards thermal and oil aging was analysed. The changes in technological properties have been correlated with variations in crosslink density estimated from stress–strain and swelling behaviour. The swelling studies are also extended to evaluate the reinforcing nature of the filler. The results of the study reveal that compatibilised blends show enhanced mechanical properties in the presence of HAF carbon black in comparison with uncompatibilised samples.     

Influence of modified fiber–MHSH hybrids on fire hazards,combustion dynamics,and mechanical properties of flame-retarded poly(butylene succinate) composites

Environmental problems caused by polymers and polymers have historically dominated both academic and industrial attention. Sustainable biodegradable wood-plastic composites (WPCs) as an optimum can solve the environmentally critical problems caused by petroleum-based polymers. However, they are flammable, prone to fire accidents, and often have a contradiction between mechanical performance and flame-retardant properties, which limits their range of applications. Here, we reported a flame-retarded poly(butylene succinate) (PBS) WPC prepared with modified natural fiber-magnesium hydroxide sulfate whisker (MHSH) hybrids and intumescent flame retardant s (IFRs). The mechanical performance, flame-retardant properties , thermal stability, and actual fire simulation parameters of composites were investigated. Owing to the unique composition characteristics of modified cassava dregs-MHSH hybrids, the mechanical properties (70P/23I/5C/2M, flexural strength was 39.2 ± 1.960/MPa, impact strength was 7.95 ± 0.3975/ [KJ/m²]), flame retardant properties (70P/23I/5C/2M, the limiting oxygen index value was 39.6%, UL-94 was V0) and thermal stability of WPC have been improved. Thereby, the balance between mechanical performance and flame retardant properties of biocomposites has been achieved in the practical engineering requirements. Furthermore, cone calorimeter data indicated that modified cassava dregs–MHSH hybrids played a role in improving the fire safety of composites. The total heat release, total smoke produce, toxic gas release, and total oxygen consumed of 70P/23I/5C/2M were lowered compared with those of 70P/25I/5C. Dynamics analysis indicated that the addition of modified cassava dregs–MHSH hybrids increased the activation energy of composites. Based on the experimental and analyses data, especially the morphological characterization of char residue analysis, it illustrated that modified cassava dregs–MHSH hybrids have a reinforcement and flame-retardant effect. The combusted residue of the incorporated modified cassava dregs–MHSH hybrids could support the three-dimensional charred layer formed by the combustion products of the IFR and the PBS. Thus, the more stable three-dimensional charred layer could not only effectively reduce thermal conductivity of composites but also hinder the propagation of heat into the interior substrate, thereby improving the flame-retardant properties of the WPC. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48490.     

Reactive processing of polyethylene and polyethylene–ethylene/propylene/dicyclopentadiene blends under static and dynamic conditions

Abstract

Dicumyl peroxide induced reactive melt processing of polyethylene (PE) in a shear mix at 170°C in the absence or presence of selected acrylic monomers (acrylic acid, ethyl acrylate, and butyl acrylate) has been studied. The acrylic graft copolymers of PE showed development of higher shear stress compared with the control PE when studied rheologically in a plate and cone viscometer at 160–190°C. All the modified PE products retained the pseudoplastic flow behaviour of PE. Measure of rupture shear parameters and of thixotropic and relaxation behaviour of the different modified PEs and of the control PE were also evaluated and compared. The observed effects and unexpected trends were analysed and interpreted.

The comparative effects of sulphur vulcanisation of polyethylene–ethylene/propylene/dicyclopentadiene terpolymer (PE–EPDM) blends by static and dynamic techniques were also studied using both a conventional curative system and a silane curative system. Rheometric studies indicated development of a co-continuous phase morphology for the 30/70 PE–EPDM blend. For a given blend, cured under given conditions, tensile strength and elongation at break at 25°C were higher for vulcanisates obtained statically than for those obtained dynamically, while the corresponding modulus values followed the opposite trend. The conventional curative usually cured at a higher rate. The property differences from static and dynamic vulcanisation are explained in the light of the differences in the developed morphology.