Isothermal Crystallization and Miscibility of Isotactic Polypropylene/Poly(cis-butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR) blends were prepared by melt mixing. Isothermal crystallization and miscibility for neat iPP and blends of iPP/PcBR were investigated by differential scanning calorimetry. The presence of PcBR remarkably affected isothermal crystalline behaviors of iPP. An addition of PcBR caused shorter crystallization time and a faster overall crystallization rate, meaning a heterogeneous nucleation effect of PcBR upon crystallization of iPP. For the same sample, the crystallization peak was broader and the supercooling decreased as the crystallization temperature increased. The Avrami equation was suitable to describe the primary isothermal crystallization process of iPP and blends. The addition of PcBR led to an increase of values of the Avrami exponent n, which we suggest was because the blends had a stronger trend of instantaneous three-dimensional growth than neat iPP. The equilibrium melting point depression of the blends was observed, indicating that the blends were partly miscible in the melt.     

Unusual Phase Separation Kinetics in Poly(Methyl Methacrylate)/Poly(Styrene-co-Acrylonitrile) (PMMA/SAN) Blends with PMMA of Different Molecular Weights

The influence of molecular weight of poly (methyl methacrylate) (PMMA) on the thermodynamics and dynamics of phase separation in PMMA/poly (styrene-co-acrylonitrile) (SAN) blends was investigated via optical microscopy, time-resolved small-angle light scattering (SALS), and dynamic rheological measurements. It was found that the cloud point temperature of the blends decreased with an increase in the molecular weight of the PMMA. The phase separation rates of PMMA 48K/SAN and PMMA 85K/SAN blends with the near-critical composition were almost the same at small quench depths due to the limited mobility of molecular chains at low temperatures. However, an unexpected phase separation dynamics was observed at larger quench depths. Not only the morphology evolution but also the apparent diffusion coefficient D_app calculated from SALS revealed that the phase separation rate was faster in the PMMA 85K/SAN blend than in the PMMA 48K/SAN blend. The possible reasons for this unusual rapid kinetics of phase separation observed in the higher molecular weight blend were discussed in terms of molecular mobility and viscoelasticity.     

Thermoplastic Vulcanizate Based on Poly(lactic acid) and Acrylic Rubber Blended with Ethylene Ionomer

A new thermoplastic vulcanizate (TPV) was developed by meltblending of poly(lactic acid) (PLA), acrylic rubber (ACM), and ethylene-methacrylic acid with sodium ions (EMAA-Na). The PLA/ACM/EMAA-Na blend showed low-yield strength, low modulus, and excellent strain recovery. It also demonstrated an increase in complex viscosity and decrease in melting temperature due to the interfacial reaction between the PLA and the ACM phases. The Fourier transform infrared spectroscopy results indicate that EMAA-Na can interact with both PLA and ACM, and that the Na⁺ ions act as a catalyst for the interfacial reaction between PLA and ACM, while PLA does not react with ACM without EMAA-Na. Moreover, the tensile strength at break of the PLA/ACM/EMAA-Na blend was observed to be extremely improved by the addition of hexamethylenediaminecarbamate (HMDC) due to the increasing of the cross-link density inside the rubber phase. The morphology of the PLA/ACM/EMAA-Na blend with HMDC was finer than that of PLA/ACM/EMAA-Na without HMDC. From the results, it is suggested that the interfacial reaction between the PLA and the ACM phases, the cross-linking in the ACM phase, and the finer morphology improved the mechanical properties of the blend.     

Mechanical Behavior of Bulk Poly(Ethylene Terephthalate) Subjected to Simple Shear

Abstract

Mechanical behavior of bulk semicrystalline poly(ethylene terephthalate) (PET) processed through simple shear is investigated. The equal channel angular extrusion (ECAE) process was used to achieve the simple shear condition. The PET samples were processed in one and two ECAE passes in the same direction, with the sample rotated 180° about the extrusion axis for the second pass. Microstructural features at the nanometer and micrometer scales were studied by small‐angle x‐ray scattering (SAXS) and scanning electron microscopy (SEM). SAXS results showed that at the nanometer scale, two types of lamellar orientations are induced in both samples, but with different extents of orientation. In the ECAE‐oriented PET structures on the micrometer scale, as revealed by SEM, are well‐defined macrofibrils. However, the fibrillar structures in the sample extruded once are more oriented than those in the sample extruded twice. Fractography investigations suggest that the ECAE‐induced fibrillar structure and stretched amorphous chains are responsible for the change in mechanical properties.     

天然橡胶与合成聚异戊二烯橡胶的红外光谱鉴定

本文通过用红外光谱法，利用蛋白质的红外吸收光谱特征，准确，快速地鉴定天然橡胶与合成聚异戊二烯橡胶。     

Thermal Decomposition Behavior of Poly (Vinyl Alcohol) with Different Hydroxyl Content

The thermal decomposition behavior of poly(vinyl alcohol) (PVA) with two different hydroxyl contents, 88 and 99%, was investigated. UV-Vis spectroscopy, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and TGA-FTIR were used to detect the volatile and nonvolatile products of the thermal decomposition of PVA. The results suggest that the PVA, after thermal treatment, can form chromophoric polyene structure, as well as carbonyl groups. The PVA with 88% hydroxyl content underwent slower decomposition below 280°C and generated water and carboxyl acid as the dominant volatile products, however, as for the PVA with 99% hydroxyl content, the dominant volatile products were water, unsaturated aldehydes, and other unsaturated compounds.     

In Situ Dynamic Vulcanization of Poly(Vinyl Chloride)/Acrylonitrile-butadiene Rubber Blends

Poly(vinyl chloride) (PVC)/acrylonitrile-butadiene rubber (NBR) blends can be obtained through a dynamic vulcanization process as a melt-processible thermoplastic elastomer which produces parts that look, feel and perform like vulcanized rubber with the advantage of being processible as a thermoplastic material. In this study, a vulcanized thermoplastic was obtained by in situ dynamic vulcanization of PVC/NBR blends using a sulphur/ tetramethylthiuram disulphide (TMTD) and mercaptobenzothiazyl disulphide (MBTS) curative system during processing at the melt state. The blends were melt-mixed using a Haake Rheomix 600. The curing behavior of NBR was then investigated by a Monsanto rheometer. The thermal analyses were performed and the cross-linking at different mixing times was calculated using DSC. FT-IR was also performed for characterization of the blends. The cross-link densities of the samples were measured by a swelling method. The degree of cure increases with the mixing time. The cross-linking formation was verified through the formation of C─ S bonds in the blends.     

Influence of Mixing Technique on Microstructure and Impact Properties of Isotactic Polypropylene/ Poly(Cis-Butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR vol%: 80/20) blends were prepared by melt mixing with various mixing rotation speeds. The effect of mixing technique on microstructure and impact property of blends was studied. Phase structure of the blends was analyzed by scanning electron microscopy (SEM). All of the blends had a heterogeneous morphology. The spherical particles attributed to the PcBR-rich phase were uniformly dispersed in the continuous iPP matrix. With increase of the mixing rotation speed, the dispersed phase particle's diameter distribution became broader and the average diameter of the separated particles increased. The spherulitic morphology of the blends was observed by small angle light scattering (SALS). Higher mixing rotation speed led to a more imperfect spherulitic morphology and smaller spherulites. Crystalline structure of the blends was measured by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). The introduction of 20 vol% PcBR induced the formation of iPPβ crystals. Higher rotation speed led to a decrease in microcrystal dimensions. However, the addition of PcBR and the increase of mixing rotation speed did not affect the interplanar distance. The long period values were the same within experimental error as PcBR was added or the mixing rotation speed quickened. The normalized relative degree of crystallinity of the blends slightly increased under lower rotation speeds (30 and 45 rpm) and decreased under higher rotation speeds. The notched Izod impact strength of the blends was enhanced as a result of the increase of mixing rotation speed.     

Study on Phase Formation and Evolution of High Impact Polystyrene with Poly(Cis‐Butadiene) Rubber Blends

Phase formation and evolution of high‐impact polystyrene with poly(cis‐butadiene) rubber blends was studied. The characteristic length, L, was defined to describe the size of particles, and the graph‐estimation method was introduced to determine the width of the distribution of L. Based on the method, the distribution of L proved to be a log‐normal distribution and the distribution width of L was calculated. The phase structure was also discussed in the wave‐number space. The correlation distance, a _c , was defined and computed, applying light‐scattering theory to power spectrum images obtained by 2‐dimensional Fourier transformation (2DFT). The change of a _c was in accord with that of L, which meant 2DFT was valid to study the phase structure. A fractal dimension, D _c , was introduced to describe the uniformity of the spatial distribution. The result showed that D _c was an effective parameter to study the distribution of particles of the dispersed phase.     

Synergistic Effect of Polycarbonate on Reactive Core-Shell Particles Toughened Poly(Butylene Terephthalate)

Glycidyl methacrylate functionalized methyl methacrylate-butadiene-styrene copolymer (MBS-g-GMA) core-shell particles were prepared via an emulsion polymerization process. MBS-g-GMA was used to toughen poly(butylene terephthalate) (PBT) and the synergistic toughening effect of polycarbonate (PC) on PBT/MBS-g-GMA blends were investigated. Notched impact tests showed the percolation threshold became lower with the increase of PC content. Transmission electron microscopy displayed a very good dispersion of MBS-g-GMA particles in the PBT matrix with the different PC contents. The synergistic toughening effect was due to the encapsulation structure of PC which could facilitate the whole PBT matrix to yield. The more perfect the encapsulation structure formed, the more obvious the synergistic toughening the PC achieved. Sufficient strength of the phase interface was important to ensure the stress transfer effectively and facilitate the whole PBT matrix to yield. The interface strength between PC and MBS-g-GMA could be ensured by the good miscibility between Poly(methyl methacrylate) (PMMA) (grafted onto the polybutadiene-based rubber core) and PC. For the PBT/PC, the transesterification between PBT and PC improved the interface strength of the PBT and PC phases, as demonstrated by Fourier transform infrared spectroscopy (FTIR) scans. Scanning electron microscopy results showed shear yielding of the matrix and cavitation of the rubber particles were the major toughening mechanisms.     

Crystallization Behavior of Amorphous Poly(l-Lactide)

Amorphous poly(l-lactide) (PLLA) was annealed in two different ways: amorphous samples were heated at a given temperature to induce crystallization (one-step annealing); and amorphous samples were first crystallized at a low temperature and subsequently annealed at a higher temperature than the crystallization temperature. Samples thus prepared were measured by DSC. The original amorphous sample exhibited an exothermic peak at about 100°C (exothermic peak I), an exothermic peak just below the melting point (exothermic peak II), and an endothermic peak when it was melted. Exothermic peak I was caused by cold crystallization. When the melting points of PLLA samples, heat-treated in various ways, were plotted as a function of annealing temperature, there was discontinuity at about 120°C. From analyses of wide-angle X-ray diffraction patterns, it was found that when amorphous PLLA was crystallized at a temperature below 120°C, crystallites of the β-form formed, and when annealed at a temperature above 120°C, crystallites of the α-form grew. Thus, exothermic peak I was attributed to cold crystallization of the β-form, and peak II was caused by the phase transition of the β-form to a more stable form.     

Improved Dispersion of Carbon Nanoparticles Modified by Poly(Sodium 4-Styrenesulfonate) and Its Influence on the Properties of Natural Rubber Latex

A novel strategy of radical polymerization of sodium 4-styrenesulfonate on the surface of carbon black (CB) in the solid state was developed to prepare hydrophilic carbon nanoparticles (PNASS-CB). A high performance natural rubber latex (NRL)/PNASS-CB composite was produced by the latex compounding technique. Scanning electron microscope shows considerable improvement in the dispersion of PNASS-CB in rubber matrix. The lower degree of filler–filler networks and the stronger filler–rubber interaction of PNASS-CB in rubber matrix were confirmed by dynamic mechanical thermal analysis. Rheometric properties of NRL/PNASS-CB, like scorch time and optimum cure time, decreased. Tensile strength, tear strength, and elongation at break increased due to stronger interaction between the PNASS-CB and rubber matrix. Dynamic mechanical properties of the modified carbon nanoparticles further corroborated a significant contribution from the better dispersion and efficient load transfer of PNASS-CB on the static and dynamic mechanical properties of composites.     

Miscibility and Isothermal Crystallization Behavior of Poly (Butylene Succinate-co-Adipate) (PBSA)/Poly (Trimethylene Carbonate) (PTMC) Blends

Poly(butylene succinate-co-adipate) (PBSA)/poly (trimethylene carbonate) (PTMC) blend samples with different weight ratios were prepared by solution blending. The morphologies after isothermal crystallization and in the melt were observed by optical microscopy (OM). Differential scanning calorimetry (DSC) was used to characterize the isothermal crystallization kinetics and melting behaviors. According to the OM image before and after melting, it was found that the blends formed heterogenous morphologies. When the PTMC content was low (20%), PBSA formed the continuous phase, while when the PTMC contents was high (40%), PBSA formed the dispersed phase. The glass transition temperatures (T_g) of the blends were determined by DSC and the differences of the T_g values were smaller than the difference between those of pure PBSA and PTMC. In addition, the equilibrium melting points were depressed in the blends. According to these results, the PBSA/PTMC blends were determined as being partially miscible blends. The crystallization kinetics was investigated according to the Avrami equation. It was found that the incorporation of PTMC did not change the crystallization mechanism of PBSA. However, the crystallization rate decreased with the increase of PTMC contents. The change of crystallization kinetics is related with the existences of amorphous PTMC, the partial miscibility between PLLA and PTMC, and the changes of phase structures.     

Rheological Behavior of Blends of Poly(Phenylene Sulfide) with a Thermotropic Liquid Crystalline Aromatic Poly(Ether Ester)

A new type of thermotropic liquid crystalline aromatic poly(ether ester) (PEE) was prepared from 1,3-bis(4′-carboxyphenoxy)benzene, 1,4-diacetoxybenzene, and p-acetoxybenzoic acid through a melt transesterification process. The rheological behavior of blends of poly(phenylene sulfide) (PPS) with PEE was studied using a high-pressure capillary rheometer with the shear rate range of 50 s^?1 to 3000 s^?1. The results show that according to the range of shear rate, the flow curves of PEE/PPS blends can be divided into three zones: a first shear-thinning zone (n < 1, “n” represents non-Newtonian indexes), a shear-thickening zone (n > 1), and a second shear-thinning zone (n < 1), and the former two zones are more obvious with the increase of PEE content or elevated temperature. In the second shear-thinning zone, the PPS melt is close to a Newtonian fluid at high temperature and high shear rate; meanwhile the non-Newtonian behavior of the PPS melt at high temperature is enhanced with the addition of PEE. The apparent viscosity of PPS melts sharply dropped after adding PEE, especially at relatively low temperature and low shear rate. The curve of apparent viscosity vs. shear rate starts to flatten out after adding PEE, suggesting that the addition of PEE lowers the sensitivity of PPS to shear rate. As the content of PEE increases, the activation energy of the viscous flow, ΔE_η, of PPS decreases, which means that adding PEE weakens the temperature sensitivity of the apparent viscosity of the PPS melt. It can clearly be seen that the addition of PEE is beneficial to the processing of PPS.     

Isothermal Crystallization and Melting Behavior of Composites Composed of Poly(L-lactic Acid) and Poly(glycolic Acid) Fibers

Several composites of poly (L-lactic acid) (PLLA) with poly (glycolic acid) (PGA) fibers were prepared. The isothermal crystallization kinetics and melting behavior of PLLA and all of the composites were characterized by using differential scanning calorimetry. The experimental data were processed by using the Avrami equation. The relative parameters, such as the Avrami exponent and half-time crystallization, revealed that PGA fibers had positive effects on the crystallization of PLLA, but these effects had only a minimal dependence on the PGA fiber content. Moreover, at low isothermal crystallization temperatures (85°C～110°C), recrystallization during the heating scan was observed, which could lower the melting point of the samples to a certain extent.     

Preparation of Self-healing Natural Rubber/Polycaprolactone (NR/PCL) Blends

Abstract

The preparation of self-healing polymers for use following mechanical failure using commercial, bio-based polymers without complex synthesis and expensive healing reagents has been very rare. In this study two commercial, bio-based polymers, natural rubber (NR) and polycaprolactone (PCL), were melt-blended to form NR/PCL blends. To increase the healing efficiency via supramolecular hydrogen bonding interactions, various amounts of acrylic acid were grafted onto the PCL. The results showed that the healing efficiency of the blends in the self-healing test at 80°Cwas higher than for blends at 60?°C due to higher molecular mobility/diffusion resulting from the molecular motions above the melting temperature of PCL which was near 55?°C in all cases. The highest healing efficiency, 62.8%, was attained for the NR/PCL-g-4AA (40/60) blend containing 4 phr PCL of AA. In addition, with the application of the shape memory-assisted self-healing (SMASH) mechanism, the healing efficiency increased further, up to 79.9%. The high shape recovery ratio (>90%) helped the crack to close faster when the sample was heated to trigger the shape memory process, leading to the increased healing efficiency in comparison with the sample without the shape memory process triggered by heating. To the best of the authors’ knowledge, there have been no similar works in the preparation of self-healing, bio-based polymer blends through the current approach so far. We suggest the synergistic effects of both the physical and chemical processes applied to commercial, bio-based polymers provide the chance of expanding the applications of these green polymers with additional functionality.     

The Effect of Epoxidized Natural Rubber and Two Kinds of Organoclay upon Molecular Interaction,Structure and Mechanical Properties of (Styrene-Butadiene Rubber/Acrylonitrile-Butadiene Rubber/Organoclay) Nanocomposites

Epoxidized natural rubber (ENR50) and two different kinds of organoclay (C30B and C15A) were used in blends of styrene-butadiene rubber (SBR) and acrylonitrile butadiene rubber (NBR) and their effects upon interaction between phases, morphology, and mechanical properties of the blends were investigated. The compounds were characterized by means of Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and differential scanning calorimetry (DSC). The obtained results showed formation of hydrogen bonding between the compounds ingredients due to incorporation of C30B, especially in presence of ENR. AFM and FE-SEM analysis revealed good dispersion of the nanoparticles in the polymer matrix upon addition of ENR as well as better dispersion of C30B than C15A in the NBR phase. XRD results showed a greater expansion of the silicate layers by simultaneous use of organoclay and ENR Incorporation of organoclay alone or in combination with ENR in the blends caused shifting of the SBR T_g toward the NBR T_g. The tensile properties of the blends showed improvement by using nanoparticles in the presence of ENR.     

Preparation and Properties of Natural Rubber (NR)/Polycaprolactone (PCL) Bio-Based Shape Memory Polymer Blends

Shape memory NR/PCL bio-based blends, where NR served as the reversible phase and PCL served as the switching phase, were prepared using a melt blending process. Peroxide, besides its role as a cross-linking agent to NR, was used to enhance the compatibility between NR and PCL, which was confirmed via Fourier transform infrared spectra and scanning electron microscopy analyses. With increasing peroxide content, the tensile strength increased steadily with decreasing PCL contents, up to 12.3 ± 0.8 MPa for the NR/PCL (70/30) blend at 2 phr peroxide. The shape fixing ratio decreased slightly with increasing peroxide content, especially for high NR content. The values of the shape recovery ratio were high, up to 100%, regardless of PCL content. The recovery stress was found to reach its maximum value around 60°C. In order to consider both fixing ratio (R_f) and recovery ratio (R_r) together, an additional denotation of shape memory index, R_fR_r, coupling both ratios by the product of the fixing ratio and recovery ratio, is proposed. The shape memory index (R_fR_r) reached values close to 100%, at the NR/PCL composition of 50/50 and 70/30; in particular, the highest value was for the 50/50 case regardless of peroxide concentration. The shape recovery ratio and fixing ratio remained largely unchanged even after 30 cycles of deformation and recovery processes for a typical NR/PCL/DCP (30/70/0.5) blend which, thus, outperformed all known shape memory blends in the literature.     

Long-Time Exudation of Plasticizer from Swollen Rubber Vulcanizates: (I) Diffusivity during Swelling

This series of two papers attempt to obtain appropriate estimates of diffusivity during extensive swelling/exudation of plasticizer in vulcanized rubbers and make clearer the difference in their behaviors in terms of diffusivity and time taken to reach equilibrium. Therefore, two mutually consistent kinetic models for extensive absorption/desorption are presented first. A particular treatment of the models is an incorporation of characteristic parameters into the theoretical diffusion coefficient, based on the Flory–Rehner theory. In this first paper, using the model for swelling (or absorption), we confirm that it can provide realistic diffusion coefficients by analyzing experimental data on the swelling of several standard rubber vulcanizates immersed in plasticizer (i.e., dioctyl phthalate), taken from the literature. In the second paper, the counterpart for exudation will provide both diffusivities during extensive exudation and time periods taken to reach equilibrium using the corresponding data. The results have a great difference from those of the swelling case, with the cause being explained.     

Long-Time Exudation of Plasticizer from Swollen Rubber Vulcanizates: (II) Diffusivity during Exudation

In the first paper in this series, two mutually consistent kinetic models were put forth to evaluate concentration-dependent diffusion coefficients of plasticizer during the extensive swelling and exudation processes of several typical rubber vulcanizates containing it. According to the model for swelling, the diffusivities were estimated using experimental data taken from the literature. In this paper the counterpart for exudation is applied to the exudation data of the same systems and diffusivities and exudation times taken to reach equilibrium are both estimated. The predicted results are compared with those of the swelling case. The results of both cases are used to account for the remarkable difference between the swelling/exudation behaviors and the lengthy exudation time as compared with the corresponding swelling time.