Effects of Dynamic Crosslinking on Crystallization, Structure and Mechanical Property of Ethylene-Octene Elastomer/EPDM Blends

The dynamic crosslinking method has been widely used to prepare rubber/plastic blends with thermoplastic properties, and the rubber phase is crosslinked in these blends. Both polyolefin elastomer (POE) and ethylene-propylene-diene monomer rubber (EPDM) can be crosslinked, which is different from usual dynamic crosslinking components. In this paper, dynamic crosslinked POE/EPDM blends were prepared. For POE/EPDM blends without dynamic crosslinking, EPDM can play a nucleation role, leading to POE crystallizing at a higher temperature. After dynamic crosslinking, the crosslinking points hinder the mobility of POE chains, resulting in smaller crystals, but having too many crosslinking points suppresses POE crystallization. Synchrotron radiation studies show that phase separation occurs and phase regions form in non-crosslinked blends. After crosslinking, crosslinking points connecting EPDM and part of POE chains, enabling more POE to enter the EPDM phase and thus weakening phase separation, indicates that dynamic crosslinking improves the compatibility of POE/EPDM, also evidenced by a lower β conversion temperature and higher α conversion temperature than neat POE from dynamic mechanical analysis. Moreover, crosslinking networks hinder the crystal fragmentation during stretching and provide higher strength, resulting in 8.3% higher tensile strength of a 10 wt% EPDM blend than neat POE and almost the same elongation at break. Though excessive crosslinking points offer higher strength, they weaken the elongation at break.

Phase morphology, mechanical, and thermal properties of fiber-reinforced thermoplastic elastomer: Effects of blend composition and compatibilization

In this work, recycled high density polyethylene (rHDPE) was compounded with regenerated tire rubber (RR) (35–80 wt.%) and reinforced with recycled tire textile fiber (RTF) (20 wt.%) as a first step. The materials were compounded by melt extrusion, injection molded, and characterized in terms of morphological, mechanical, physical, and thermal properties. Although, replacement of the rubber phase with RTF compensated for tensile/flexural moduli losses of rHDPE/RR/RTF blends because of the more rigid nature of fibers increasing the composites stiffness, the impact strength substantially decreased. So, a new approach is proposed for impact modification by adding a blend of maleic anhydride grafted polyethylene (MAPE)/RR (70/30) into a fiber-reinforced rubberized composite. As in this case, a more homogeneous distribution of the fillers was observed due to better compatibility between MAPE, rHDPE, and RR. The tensile properties were improved as the elongation at break increased up to 173% because of better interfacial adhesion. Impact modification of the resulting thermoplastic elastomer (TPE) composites based on rHDPE/(RR/MAPE)/RTF was successfully performed (improved toughness by 60%) via encapsulation of the rubber phase by MAPE forming a thick/soft interphase decreasing interfacial stress concentration slowing down fracture. Finally, the thermal stability of rubberized fiber-reinforced TPE also revealed the positive effect of MAPE addition on molecular entanglements and strong bonding yielding lower weight loss, while the microstructure and crystallinity degree did not significantly change up to 60 wt.% RR/MAPE (70/30).

TPV: A New Insight on the Rubber Morphology and Mechanic/Elastic Properties

The objective of this work is to study the influence of the ratio between the elastomer (EPDM) phase and the thermoplastic phase (PP) in thermoplastic vulcanizates (TPVs) as well as the associated morphology of the compression set of the material. First, from a study of the literature, it is concluded that the rubber phase must be dispersed with a large distribution of the domain size in the thermoplastic phase in order to achieve a high concentration, i.e., a maximal packing fraction close to ~0.80. From this discussion, it is inferred that a certain degree of progress in the crosslinking reaction must be reached when the thermoplastic phase is melted during mixing in order to achieve dispersion of the elastomeric phase in the thermoplastic matrix under maximum stress. In terms of elasticity recovery which is measured from the compression set experiment, it is observed that the crosslinking agent nature (DCP or phenolic resin) has no influence in the case of a TPV compared with a pure crosslinked EPDM system. Then, the TPV morphology and the rubber phase concentration are the first order parameters in the compression set of TPVs. Finally, the addition of carbon black fillers leads to an improvement of the mechanical properties at break for the low PP concentration (20%). However, the localization of carbon black depends on the crosslinking chemistry nature. With radical chemistry by organic peroxide decomposition, carbon black is located at the interface of EPDM and PP acting as a compatibilizer.

Enhanced Morphology-Dependent Tensile Property and Breakdown Strength of Impact Polypropylene Copolymer for Cable Insulation

The decrease in electrical properties caused by the toughening of polypropylene (PP) is a difficult problem for the modification of PP used for cable insulation. In this research, an isotactic PP, a cross-linked polyethylene (XLPE) and two impact PP copolymers (IPCs) with an ethylene–propylene rubber phase content of 15 and 30% were prepared to assess the possibility of IPCs to be used as cable insulating material. The tensile properties and breakdown strength were evaluated, meanwhile, the rubber phase content dependence of the crystalline structure, morphology and trap distribution were also investigated. Results show that IPCs with a 15% rubber phase content (IPC15) can achieve the simultaneous improvement of elongation at break and breakdown strength compared with isotactic PP, which can be attributed to the special crystalline structure. According to the results of differential scanning calorimetry (DSC) and FTIR, it is proposed that the lamella thickness of IPC15 is maximal and some ethylene segments exist in PP crystals of IPC15 as crystalline structure defects, which is responsible for this enhanced breakdown strength. The morphology results reveal that rubber microspheres are found to coexist with spherulites, which can promote the relative sliding among lamellas under external force and further results in the increase in the elongation at break.

Versatile Polypropylene Copolymers from a Pilot-Scale Spheripol II Process

Polypropylene (PP) is one of the most widely used polymers. In this paper, three types of PPs including random PP, impact PP, and impact PP with high clarity, were prepared through a 75 kg/h pilot-scale Spheripol II process. The three produced PPs were produced by the selection or combination the two loops and gas phase reactor and controlling the comonomer and hydrogen concentrations. The three prepared PPs then were pelleted with the clarified nucleating agent NX 8000 and tested for mechanical, thermal, and optical properties. Their molecular structures and rubber phase size were also investigated by GPC, 13C NMR, temperature rising elution fractionation (TREF), XRD, SEM analysis, etc. The results showed that the random PP (PP-1) and the impact PP with high clarity (PP-3) obtained excellent optical transparency with a haze of 12.5% and 13.5% due to their small rubber phase size (roughly ≤ 100 nm), while the impact PP (PP-2) obtained bad transparency with a haze of 98.8% due to the large rubber phase size (about 1 μm) caused by the poor thermal compatibility with the PP matrix. The rubber phase content and ethylene/propylene sequence distributions of the three PPs varied much and resulted in different impact strengths and stiffness properties. PP-2 had a high impact strength of 14.5 kJ/m2 due to the rubber phase generated in the gas phase reactor. Except for the optical transparency, PP-3 gained stiffness and toughness, with 914 MPa of flexural modulus and 25.1 kJ/m2 of impact strength due to the unique molecular structure of its rubber phase.

Development of Polypropylene-based Thermoplastic Elastomers with Crumb Rubber by Dynamic Vulcanization: A Potential Route for Rubber Recycling

In our current paper the preparation and properties of thermoplastic elastomer produced by dynamic vulcanization is presented and discussed. We dynamically vulcanized natural and styrene butadiene rubber (NR/SBR) phase by continuous extrusion. Dispersion and in-situ vulcanization of the rubber phase occurred simultaneously in a co-rotating twin screw extruder. We used a random polypropylene copolymer (rPP) as the thermoplastic matrix and untreated crumb rubber (CR) to partially substitute the neat fresh rubber in order to check whether this is a potential recycling route for waste rubber products. We studied the effect of various rubber formulations, various processing conditions (screw speed and configuration) and various CR particle size distributions by characterizing the mechanical performance of the thermoplastic dynamic vulcanizates (TDVs) with tensile and hardness tests and their morphology by evaluating SEM micrographs taken from the fracture surfaces of the tensile specimens. The results showed that increasing screw speed and more high-shear elements in the screw setup led to a finer dispersion of the rubber phase, resulting in improved mechanical properties. The ultimate tensile properties of the best TDVs reached 20.5 MPa in tensile strength and 550 % in strain at break. However, partial replacement of the fresh rubber with untreated CR caused a significant deterioration in mechanical properties, due to poor adhesion between the CR particles and the matrix and rubber. This suggests that some kind of pre-treatment (e.g. by microwave or other devulcanization techniques) is necessary to enhance the surface activity of the CR particles.

Toughened High-Flow Polypropylene with Polyolefin-Based Elastomers

Polyolefin is the most widely used and versatile commodity polymer. In this work, three types of polyolefin-based elastomers (PBEs) were adopted to toughen a high-flow polypropylene to improve its overall performance. The chain microstructures of these PBEs, including ethylene/1-octene (E/O) random copolymer from Dow Chemical′s polyolefin elastomer (POE), olefin block copolymers (OBCs) of E/O from Dow, and ethylene/propylene random copolymer from ExxonMobil’s propylene-based elastomer, were elucidated by GPC, 13C NMR, TREF, and DSC techniques. The mechanical, thermal and optical properties, and morphology analysis of the PP/PBE blends were also studied to investigate the toughening mechanism of these PBEs. The results showed that all three types of PBEs can effectively improve the Izod impact strength of the PP/PBE blends by the addition of the rubber compositions, at the cost of the stiffness. PBE-1 and PBE-2 were found to have a great stiffness–toughness balance with about 1700 MPa of flexural modulus, about 110 °C of HDT and 3.6 kJ/m2 of impact strength on the prepared PP/PBE blends by forming separated rubber phase and refined spherulite crystals. As a result, the OBC with alternating hard and soft segments could achieve a similar toughening effect as the E/P random copolymer. Surprisingly, no obvious rubber phase separation was observed in the PP/PBE-4 blend, which might be due to the good compatibility of the E/P random chains with the isotactic PP; therefore, the PP/PBE blend obtains great toughness performance and optical transparency with the highest Izod impact strength of 4.2 kJ/m2 and excellent transparency.

RESEARCH ON PRODUCING TEMPERATURE INDUCED COLOR CHANGE IN FUCTIONAL RUBBER COMPOUNDS

Today, the rubber is used not only in technology products but also in household products. In this study, thermolchromic rubber exhibiting the available color changing property with the ambient temperature alteration is fabricated. The effects of thermochromic pigment content and silica filler on the mechanical properties and color-changing durability of the rubber compound are investigated. The results show that the introduction of thermolchromic pigment of 1 wt.% into the rubber phase does not adversely affect the mechanical property, while creating the novel color-changing property of the rubber compond. Furthermore, the color-changing durability of the rubber compound maintains after more than 100 cycles, while the original color does not change compared to before the durable test.

Thermoplastic Dynamic Vulcanizates with In Situ Synthesized Segmented Polyurethane Matrix

The aim of this paper was the detailed investigation of the properties of one-shot bulk polymerized thermoplastic polyurethanes (TPUs) produced with different processing temperatures and the properties of thermoplastic dynamic vulcanizates (TDVs) made by utilizing such in situ synthetized TPUs as their matrix polymer. We combined TPUs and conventional crosslinked rubbers in order to create TDVs by dynamic vulcanization in an internal mixer. The rubber phase was based on three different rubber types: acrylonitrile butadiene rubber (NBR), carboxylated acrylonitrile butadiene rubber (XNBR), and epoxidized natural rubber (ENR). Our goal was to investigate the effect of different processing conditions and material combinations on the properties of the resulting TDVs with the opportunity of improving the interfacial connection between the two phases by chemically bonding the crosslinked rubber phase to the TPU matrix. Therefore, the matrix TPU was synthesized in situ during compounding from diisocyanate, diol, and polyol in parallel with the dynamic vulcanization of the rubber mixture. The mechanical properties were examined by tensile and dynamical mechanical analysis (DMTA) tests. The morphology of the resulting TDVs was studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM) and the thermal properties by differential scanning calorimetry (DSC). Based on these results, the initial temperature of 125 °C is the most suitable for the production of TDVs. Based on the atomic force micrographs, it can be assumed that phase separation occurred in the TPU matrix and we managed to evenly distribute the rubber phase in the TDVs. However, based on the SEM images, these dispersed rubber particles tended to agglomerate and form a quasi-continuous secondary phase where rubber particles were held together by secondary forces (dipole–dipole and hydrogen bonding) and can be broken up reversibly by heat and/or shear. In terms of mechanical properties, the TDVs we produced are on a par with commercially available TDVs with similar hardness.