Determination of optimum blending conditions for poly(vinyl chloride)/epoxidized natural rubber blends

An attempt to resolve the difficulties normally faced in preparing PVC-dominant PVC/ENR blends with the Brabender plasticorder is discussed. As expected, it was found that the mechanical properties of PVC/ENR blends are greatly influenced by the mixing parameters, which are further reinforced with evidence from both dynamic mechanical analysis (DMA) and morphological studies. Both techniques showed the attainment of compatible 50/50/PVC/ENR blends, the former a single glass transition temperature (T_g) and the latter a single-phase system, albeit their inherent properties are dependent on the blending parameters. By utilizing the correlation between mixing temperature and rotor speed derived, good PVC/ENR blends can be easily procured. © 1993 John Wiley & Sons, Inc.     

Aspects of miscibility in poly(vinyl chloride)/epoxidized natural rubber blends. Part I: Mechanical and morphological properties

Miscibility in poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blends was studied by examining evidence from tensile, impact, and physical properties. The observation of synergism in tensile strength, percent elongation at break, hardness, and relative density has reaffirmed PVC/ENR blends as miscible systems. Studies of impact properties, however, revealed that the blends are microheterogeneous in nature. This could be attributed to the large sizes of polymer molecules involved and the microgel content of ENR-50. Results from Fourier transform infrared spectroscopy (FTIR) revealed that hydrogen bonding is extensively involved in PVC/ENR systems. This evidence unveiled the exact nature of the specific interactions responsible for miscibility and hence the enhanced mechanical properties of PVC/ENR blends.     

Mechanical Properties and Thermooxidative Aging of a Ternary Blend,Pvc/Enr/Nbr,Compared with the Binary Blends of Pvc

In the quest to improve the thermooxidative aging of the poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend, nitrile rubber (NBR) was incorporated into the blend to yield a ternary blend of PVC/ENR/NBR. A Brabender Plasticorder with a mixing attachment was used to perform the melt mixing at 150°C and 50 rpm followed by compression molding. The mechanical properties, dynamic mechanical properties, and thermooxidative aging behavior of the ternary blend were compared with those of the binary blends (i.e., PVC/ENR and PVC/NBR). It was found that the ternary blend exhibits mechanical properties which are superior to those of PVC/ENR. A single glass transition temperature (T _g) obtained from dynamic mechanical analysis coupled with synergism in the modulus and some other mechanical properties indicate that PVC, ENR, and NBR form a single phase (miscible system) in the ternary blend. Di-2-ethyl hexylphthalate (DOP) plasti-cizer improves the aging resistance of the blends generally, whereas the presence of CaCO₃ as a filler only imparts minor influences on the properties and aging resistance of the blends.     

Thermal and mechanical characterization of partially miscible blends of poly(ether ether ketone) and polyethersulfone

The miscibility behavior of poly(ether ether ketone) (PEEK) and polyethersulfone was studied by differential scanning calorimetry (glass transition temperature) and tensile properties: Young's modulus and ultimate tensile strength. A single glass transition temperature was observed over the entire composition range. The glass transition temperature of blends, however, did not follow any of the theoretical equations. Utracki and Jukes equation was used with K = 11 to fit the experimental data that indicate partial miscibility. Up to 30 wt % PEEK, the blends showed amorphous behavior with the glass transition temperature very close to that of polyethersulfone. Because of partial miscibility, blends showed mechanical compatibility. Both the modulus and strength increased significantly with an increasing concentration of PEEK in the blends, reaching a maximum around 40%. Electron microscopic results revealed phase separation but strong adhesion between the phases.     

Melt elasticity behavior and extrudate characteristics of rigid poly(vinyl chloride)/epoxidized natural rubber miscible blends

A study on the melt elasticity behavior and extrudate characteristics of melts of rigid poly(vinyl chloride), PVC, and rigid poly(vinyl chloride)/epoxidized natural rubber (ENR) miscible blends were conducted. Extrusion studies were carried out in a capillary rheometer and examinations of the surface characteristics of the extrudate were made by taking photomicrographs in a scanning electron microscope. The anomalous behavior in the die swell ratio of rigid PVC arising from the particle agglomerates continued in its blends up to 50 wt% composition of ENR. Temperature independence for high ENR blends was noted for the principal normal stress difference and elastic shear modulus, when shear stress was held constant. Recoverable shear strain and die swell ratio behaved identically in terms of blend composition and processing temperature. Factors which control the extrudate distortion and melt fracture of the melts of rigid PVC/ENR systems were fusion of particle agglomerates and strength of melts. Diamond cavitations were typical of the extrudate surface of PVC melts as those of the fracture surface of the tensile failure of PVC. Conditions to obtain a smooth extrudate surface of rigid PVC melts in blends with ENR have been found to be the low ENR content, low shear rate, or stress and high processing temperature.     

Miscibility and thermooxidative degradation of poly(vinyl chloride)/biodegradable aliphatic–aromatic copolyester blends

The miscibility of poly(vinyl chloride) (PVC) and a biodegradable aliphatic–aromatic copolyester (AAC) was investigated by differential scanning calorimetry. The thermooxidative degradation of the blends was investigated thermogravimetrically. The blends were prepared by dissolution in 1,2‐dichloroethane and precipitation with methanol. The investigated blends were completely miscible with the glass‐transition temperatures best predicted by the Fox equation. Fourier transform infrared analysis showed that the interactions responsible for miscibility were the hydrogen bonds between the blend components. The thermooxidative stability of the PVC/AAC blends was improved compared to that of pure PVC. Furthermore, when AAC was added, the dehydrochlorination rate of PVC decreased, and the maximum rate shifted to a higher temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2158–2163, 2006     

Internal mixer studies of poly(vinyl chloride)/epoxidized natural rubber blends

Blends of polyvinyl chloride/epoxidized natural rubber (PVC/ENR) blends were studied. Their rheological properties were studied with a Brabrender Plasticorder. It was found that the rheological properties of any PVC/ENR blends are governed by their blending conditions. To ensure homogenous PVC/ENR blends, adequate and suitable blending conditions must be utilized. PVC thermoplastics phases enhances rigidity while ENR rubbery phases imparts flexibility and processability to the blends. With premixing, Ba/Cd/Zn-based PVC stabilizer is effective in stabilizing the PVC/ENR blends. Their properties are further enhanced by the addition of curatives.     

Modification of PVC/ENR blends by electron beam irradiation

The effects of electron irradiation, with doses ranging from 20 to 100 kGy on the physical properties of poly(vinyl chloride)/epoxidised natural rubber blends (PVC/ENR50 blends) were investigated. The enhancement in tensile strength, elongation at break, hardness, and aging properties of the blends have confirmed the positive effect of irradiation on the blends. Crosslinking of the ENR50 phase proved to play a major role in the improvement of mechanical properties of blends. The results also revealed that at any blend composition the enhancement in properties depends on the irradiation dose which controls the degree of radiation-induced crosslinking. The single glass transition temperature obtained confirms that the blends remain miscible upon irradiation.     

Molecular dynamics and dissipative particle dynamics simulations for the miscibility of poly(ethylene oxide)/poly(vinyl chloride) blends

The miscibility of poly(ethylene oxide) (PEO)/poly(vinyl chloride) (PVC) blends are investigated by atomistic molecular dynamics and mesoscale dissipative dynamics simulations. The specific volumes of three PEO/PVC blends (with weight ratio at 70/30, 50/50 and 30/70) as well as pure PEO and PVC are examined as a function of temperature. The glass transition temperatures are estimated to be 251, 268, 280, 313 and 350 K for pure PEO, PEO/PVC 70/30, 50/50, 30/70 and pure PVC. Among different energy contributions, the torsion and van der Waals energies exhibit pronounced kinks versus temperature. The Flory-Huggins parameters determined from the cohesive energy densities and the radial distribution functions of the inter-molecular atoms suggest that PEO/PVC 70/30 and 30/70 blends are more miscible than 50/50 blend. This is further supported by the morphologies of PEO/PVC blends, in which the 50/50 blend exhibits segregated domains implying a weak phase separation. Hydrogen bonds are found to form between O atoms of PEO and H atoms of PVC, with a larger degree in PEO/PVC 70/30 and 30/70 blends than in 50/50 blend. The addition of PVC into PEO suppresses the mobility of PEO chains, which is consistent with the experiment observation of decreased crystallization rate as well as crystallization temperature of PEO.     

Physico-mechanical properties and automotive fuel resistance of EPDM/ENR blends containing hybrid fillers

This research aimed to investigate the effect of blend ratios on cure characteristics, mechanical and dynamic properties, morphology and automotive fuel resistance of ethylene-propylene diene rubber (EPDM) and epoxidized natural rubber (ENR) blends containing carbon black and calcium carbonate hybrid filler. The composition of EPDM/ENR blends varied were 100/0, 70/30, 50/50, 30/70 and 0/100 %wt/wt. All ingredients used for preparing each blended compound, except for the curatives, were mixed in a kneader. Thereafter, the compound was further mixed with curatives on a two-roll mill and then were vulcanized together with shaped by compression molding before determining cure characteristics, mechanical properties, morphology and weight swelling ratio in three automotive fuels; gasohol-91, diesel and engine oils. The results indicated that Mooney viscosity and cure time of EPDM/ENR blends tended to decrease with increasing ENR content, while cure rate index and crosslink density increased. Tensile strength of all EPDM/ENR blends is lower than that of the individual EPDM and ENR. This is attributed to the incompatibility between nonpolar and polar nature of EPDM and ENR, respectively, supporting by the glass transition temperature form dynamic mechanical thermal analysis (DMTA) and scanning electron micrographs (SEM). Owing to the differences in polarity of automotive fuels and rubbers, weight swelling of EPDM/ENR vulcanizates decreased in diesel and engine oils, but increased in gasohol-91 with increasing in ENR content.     

A Viscometric Study of the Miscibility Behaviour of Poly(N-Vinyl Pyrrolidone) Blends

The miscibility behaviour of blends of poly(N-vinyl pyrrolidone) (PVP) with poly(vinyl chloride) (PVC), poly(vinyl acetate) (PVAc) and vinyl chloride–vinyl acetate (VCVAc) copolymer has been investigated on the basis of a viscometric approach. PVP is found to be miscible with PVC over the entire composition range, as is evident from the high values observed for the intrinsic viscosity of transfer. This is further supported by the single glass transition temperature observed in differential scanning calorimetry studies of the blend films. Blends of PVP with VCVAc copolymer exhibit microphase separation which is shown clearly in the scanning electron micrographs of the films. PVAc/PVP blends show interaction only at low PVAc contents, but in general are immiscible. © of SCI.     

Free volume microprobe studies on poly(methyl methacrylate)/poly(vinyl chloride) and poly(vinyl chloride)/polystyrene blends

Blends of Poly(methyl methacrylate) (PMMA)/Poly(vinyl chloride) (PVC) and Poly(vinyl chloride) (PVC)/Polystyrene (PS) of different compositions were prepared by solution casting technique. The blends were characterized using Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), and Positron Lifetime Spectroscopy. DSC data were found to be inadequate to describe whether PMMA/PVC blends are miscible or not, possibly because of the small gap in their glass transition temperatures. On the other hand, PVC/PS blends were clearly found to be immiscible by DSC. FTIR results for PMMA/PVC indicate the possible interactions between the carbonyl group of PMMA and α‐hydrogen of PVC. Free volume data derived from Positron lifetime measurements showed that the PMMA/PVC blends to be miscible in low PVC concentration domain. For the first time, the authors have evaluated the hydrodynamic interaction parameter α, advocated by Wolf and Schnell, Polymer, 42, 8599 (2001), to take into account the friction between the component molecules using the free volume data. This parameter (α) has a high value (?57) at 10 wt% of PVC, which could be taken to read miscibility for PMMA/PVC blends to be high. In the case of PVC/PS blends, the positron results fully support the DSC data to conclude the blends to be immiscible throughout the range of concentration. As expected, the hydrodynamic interaction parameter α does not show any change throughout the concentration in PVC/PS blends, further supporting the idea that α is another suitable parameter in the miscibility study of polymer blends. POLYM. ENG. SCI., 46:1231–1241, 2006. © 2006 Society of Plastics Engineers     

Effect of electron‐beam irradiation on poly(vinyl chloride)/epoxidized natural rubber blend: dynamic mechanical analysis

The irradiation‐induced crosslinking in 50/50 poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend was investigated by means of dynamic mechanical analysis. The influence of trimethylolpropane triacrylate on the irradiation‐induced crosslinking of PVC/ENR blends was also studied. The enhancement in storage modulus and T_g with irradiation dose indicated the formation of irradiation‐induced crosslinks. This is further supported by the decrease in tan δ_max and loss modulus peak. The compatibility of the blend was found to be improved upon irradiation. The Fox model was used to provide a further insight into the irradiation‐induced compatibility in the blend. Scanning electron microscopy studies on the cryofracture surface morphology of the blends as well as the homopolymer have been undertaken in order to gain more evidence on the irradiation‐induced crosslinking. © 2001 Society of Chemical Industry     

Compatibilization of poly(lactic acid)/epoxidized natural rubber blend with maleic anhydride

The objective of this work was to determine the compatibilization effect of different concentrations of maleic anhydride (MA) in poly(lactic acid) blended with epoxidized natural rubber (PLA/ENR). ENR-grafted MA [ENR-g-MA] was synthesized using four concentrations of MA: 0.15, 0.30, 0.45, and 0.60 phr. Using an internal mixer, binary (PLA/ENR, PLA/ENR-g-MA) and ternary (PLA/ENR/ENR-g-MA) polymer blends were prepared with a constant rubber content of 10 wt %. ENR impaired the mechanical properties of PLA, perhaps due to the relatively large size of the rubber particles. The compatibilization effect of MA was evaluated from the results of impact strength testing. ENR-g-MA was a toughening agent for PLA when the concentration of MA was in the range of 0.30–0.60 phr. MA increased miscibility between PLA and ENR. This effect was indicated in the blends by reductions in rubber particle size, the glass transition temperature of PLA, and the α-transition temperatures of PLA and ENR. In the binary polymer blends, the MA concentration in ENR-g-MA that produced the optimal mechanical properties of PLA was 0.60 phr. In the ternary blends, mechanical properties of PLA did not improve at any concentration of MA in ENR-g-MA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48297.     

Rheological properties of poly(vinyl chloride)/epoxidized natural rubber blends. Part I: Composition dependence and the effect of compounding conditions

Epoxidized natural rubber is a recently commercialized modified form of natural rubber. This paper is part of our continuing effort to study the responses of this new material to melt mixing and other shaping processes. The Shimadzu capillary rheometer was used to evaluate the composition dependence of miscibility of polyvinyl chloride/epoxidized natural rubber blends (PVC/ENR blends). The rheometer was also used to evaluate the effect of compounding parameters on the rheological properties of the blends. The results confirmed PVC/ENR blends as miscible systems that show a synergism in apparent shear viscosity highlighted by the positive deviation from the logarithmic additivity rule. These results based on capillary rheometry are also in very good agreement with our earlier attempt to predict optimum mixing from torque rheometry by using the Brabender Plastogram as an indicator.     

DSC studies of poly(vinyl chloride)/poly(ε-caprolactone)/poly(ε-caprolactone)-b-poly(dimethylsiloxane) blends

Poly(vinyl chloride)/poly(ε-caprolactone)/poly(ε-caprolactone)-b-poly(dimethylsiloxane) [PVC/PCL/(PCL-b-PDMS)] blends were prepared by solvent casting from tetrahydrofuran. The content of PVC was kept constant (60 wt%); the PCL and PCL-b-PDMS contents were varied by replacing different amounts of PCL [0–20 wt% from the PVC/PCL (60/40) blend] with PCL-b-PDMS copolymer having different molecular weights of the PCL blocks. The thermal properties of prepared blends were investigated by differential scanning calorimetry in order to analyse miscibility (through glass transition temperature) and crystallinity. Differential scanning calorimetry analyses show that the PVC/PCL/PCL-b-PDMS blends are multi-phase materials which contain a PVC plasticized with PCL phase, a block copolymer PCL-b-PDMS phase (with crystalline and amorphous PCL and PDMS domains) and a PCL phase (preponderantly crystalline).     

Thermodynamics of mixing of poly(vinyl chloride) and poly(ethylene-co-vinyl acetate)

The miscibility of poly(vinyl chloride) (PVC) and an ethylene-vinyl acetate copolymer with 85 wt[percnt] of vinyl acetate units (EVA85) has been studied by measuring the glass transition temperature and the enthalpy of mixing of several mixtures covering the whole composition range. An accurate thermal characterization as regards the specific heat of the two polymers and their blends has also been obtained. The enthalpy of mixing has been found negative for all the mixtures, indicating that specific interactions are involved between the polar groups of the two components. Particular attention has been paid also to the excess specific heat, which comes out positive for the PVC-rich blends and with a small negative value in a narrow region at high contents of EVA85. This finding is in agreement with negative and positive deviations that are observed for the glass transition temperature. Modelistic considerations about the type of interactions and the organization between PVC and EVA85 in the blends are proposed.     

Enhancement of PVC/ENR blend properties by poly(methyl acrylate) grafted oil palm empty fruit bunch fiber

Effect of oil palm empty fruit bunch (OPEFB) fiber and poly(methyl acrylate) grafted OPEFB on several mechanical properties of poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blends were studied. The composites were prepared by mixing the fiber and the PVC/ENR blends using HAKEE Rheomixer at the rotor speed of 50 rpm, mixing temperature 150°C, and mixing period of 20 min. The fiber loadings were varied from 0 to 30% and the effect of fiber content in the composites on their ultimate tensile strength (UTS), Young's modulus, elongation at break, flexural modulus, hardness, and impact strength were determined. An increasing trend was observed in the Young's modulus, flexural modulus, and hardness with the addition of grafted and ungrafted fiber to the PVC/ENR blends. However the impact strength, UTS, and elongation at break of the composites were found to decrease with the increase in fiber loading. An increase in elongation at break and UTS and decrease in the flexural and Young's modulus was observed with the addition of PMA‐g‐OPEFB fiber compared to ungrafted fiber. This observation indicates that grafting of PMA onto OPEFB impart some flexibility to the blend. The morphology of cryogenically fractured and tensile fracture surfaces of the composites, examined by a scanning electron microscope shows that the adhesion between the fiber and the matrix is improved upon grafting of the OPEFB fiber. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Processing,Tensile, and Thermal Studies of Poly(Vinyl Chloride)/Epoxidized Natural Rubber/Kenaf Core Powder Composites with Benzoyl Chloride Treatment

The kenaf core powder (KCP) has been treated with benzoyl chloride (BC) in poly(vinyl chloride)(PVC)/epoxidized natural rubber (ENR)/KCP composites. The presence of BC grafted on KCP was evident by infrared analysis. PVC/ENR/KCP samples were prepared using Haake Polydrive with the temperature of 140°C and KCP loading of 5, 10, 15, and 20?phr. The processing, tensile and thermal properties of the composites were investigated. The enhancement of tensile properties showed that the treatment improved the interfacial adhesion between KCP with PVC/ENR matrix. Higher glass transition temperature and higher thermal stability after treatment with BC support the enhancement of the composites’ tensile properties.     

Morphology,mechanical and viscoelastic properties of nitrile rubber/epoxidized natural rubber blends

A new class of blend membranes from blends of nitrile rubber (NBR) and epoxidized natural rubber (ENR) has been prepared and their morphology, miscibility, mechanical, and viscoelastic properties have been studied. The ebonite method was used to study the blend morphology of the membranes. The morphology of the blends indicated a two‐phase structure in which the minor phase is dispersed as domains in the major continuous phase. The performance of NBR/ENR blend membranes has been studied from the mechanical measurements. The viscoelastic behavior of the blends has been analyzed from the dynamic mechanical data. An attempt was made to relate the viscoelastic behavior with the morphology of the blends. Various composite models have been used to predict the experimental viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by theoretical group contribution analysis. The homogeneity of the system was further evaluated by Cole–Cole analysis. Finally, a master curve for the modulus of the blend was generated by applying the time–temperature superposition principle. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1561–1573, 2005