Evaluation of the effects of biobased plasticizers on the thermal and mechanical properties of poly(vinyl chloride)

Blends were prepared of poly(vinyl chloride) (PVC) with four different plasticizers; esters of aconitic, citric, and phthalic acids; and other ingredients used in commercial flexible PVC products. The thermal and mechanical properties of the fresh products and of the products after 6 months of aging were measured. Young's modulus of the PVC blends was reduced about 10‐fold by an increase in the plasticizer level from 15 to 30 phr from the semirigid to the flexible range according to the ASTM classification, but a 40‐phr level was required for PVC to retain its flexibility beyond 6 months. At the 40‐phr level, tributyl aconitate performed better than diisononyl phthalate (DINP) or tributyl citrate, in terms of lowering Young's modulus, both in the fresh materials and those aged for 6 months. The effects of the four plasticizers on the glass‐transition temperature (T_g) were similar, with T_g close to ambient temperature at the 30‐ and 40‐phr levels in freshly prepared samples and at 40–60°C in those aged for 6 months. The thermal stability of the PVC plasticized with DINP was superior among the group. Overall, tributyl aconitate appeared to be a good candidate for use in consumer products where the alleged toxicity of DINP may be an issue. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1366–1373, 2006     

Novel polyurethane elastomer continuous carbon fiber composites: Preparation and characterization

Preparation and characterization of novel polyurethane (PUR)–carbon fiber (CF) composites are reported. The reinforcement of PUR elastomers was achieved using unidirectional continuous CFs with different coatings (uncoated and epoxy and polyester resin coatings) by applying molding for the preparation of PUR‐CF composites. Considerable reinforcement of PUR was attained even at relatively low CF content, e.g., maximum stress and Young's modulus of PUR‐CF composite at CF content 3% (m/m) were found to be 3–5 and 4–10 times higher than those of the PUR‐matrix, respectively. In addition, a linear relationship between the Young's modulus and the CF content was found as well as linear variation of maximum stress with the CF content was also observed. The adhesion of CF to the PUR‐matrix was strong in each case as concluded from the strain–stress and the scanning electron microscopy (SEM) investigations. However, the extent of reinforcement of PUR at a given CF content was found to depend greatly on the coatings of CF, and increased in the following order: epoxy resin < polyester resin < uncoated. The effect of the coating of CF on the reinforcement of PUR is also discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 287–292, 2007     

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     

Effects of poly(butylene succinate) and ultrafine wollastonite on the physical properties of plasticized poly(vinyl chloride)

In this study, diisononyl phthalate (DINP), a conventional plasticizer of poly(vinyl chloride) (PVC), was partially replaced by a polymeric plasticizer, poly(butylene succinate) (PBS), in order to reduce the leaching out of low‐molecular‐weight plasticizer from the plasticized PVC. Samples were prepared by melt mixing on a two‐roll mill followed by compression molding into a 3‐mm thick sheet. The DINP/PBS‐plasticized PVC provides a dose‐dependent increase in the tensile properties (tensile strength, Young's modulus, and elongation at break), tear strength, and thermal stability, as compared with the DINP‐plasticized PVC. According to the overall properties, PVC plasticized with 10/30 phr (parts by weight per hundred parts of resin) DINP/PBS was selected for preparing composites with varied loadings of an ultrafine wollastonite (particle size of 1,200 mesh). Their tensile properties, tear strength, thermal stability, and morphology were evaluated and compared with the 40 phr of DINP‐plasticized PVC composites. The results showed an increase in the Young's modulus and thermal stability but a decrease in the tensile strength, elongation at break, and tear strength of either 40 phr of DINP‐ or 10/30 phr of DINP/PBS‐plasticized PVC composites. Therefore, the products may be useful where the dimensional and thermal stability of the plasticized PVC are needed. J. VINYL ADDIT. TECHNOL. 21:220–227, 2015. © 2014 Society of Plastics Engineers     

Microstructural characterization of short glass fiber and PAN based carbon fiber reinforced nylon 6 polymer composites

Microstructural characterization of nylon 6/short glass fiber (SGF) and nylon 6/polyacrolonitrile based carbon fibers (PAN‐CFs) of 10 to 40 wt% has been performed by positron lifetime technique (PLT). The positron lifetime parameters viz., o‐Ps lifetime (τ₃), o‐Ps intensity (I₃), and fractional free volume (F_v) of nylon 6/SGF and nylon 6/PAN‐CF composites are correlated with the mechanical properties viz., tensile strength and Young's modulus. The F_v shows negative deviation with the reinforcement of 10 to 40 wt% of PAN‐CF and show positive deviation in nylon 6/SGF from the linear additivity relation. The negative deviation in nylon 6/PAN‐CF composite suggests the induced molecular packing due to the chemical interaction between the polymeric chains of nylon 6 and PAN‐CF. The positive deviation in nylon 6/SGF composite indicates the formation of interface between the polymeric chains of nylon 6 and SGF. The increased crystallinity of nylon 6/SGF and nylon 6/PAN‐CF composites shows the improved mechanical properties of the composites. The hydrodynamic interaction parameter (h), which shows more negative values in nylon 6/SGF than nylon 6/PAN‐CF composites. However, the extent of chemical interaction in nylon 6/SGF is less compare to nylon 6/PAN‐CF composites. This is evident from Fourier transform infrared spectrometry studies. POLYM. ENG. SCI., 58:1428–1437, 2018. © 2017 Society of Plastics Engineers     

On-Line Rheological Measurements and Mechanical Properties of Acrylonitrile-Butadiene-styrene/Corn Starch Composite

In this work, rheological and mechanical properties of acrylonitrile–butadiene–styrene/corn starch composites (ABS/starch) were studied. The composites were prepared using a laboratory-scale, single-screw extruder. Rheological properties were determined using the single-screw extruder, apparent shear rate (γ _a ), apparent shear stress (τ _a ), apparent viscosity (η _a ), non-Newtonian index (n), and flow activation energy at a constant shear rate (E _γ) and constant shear stress (E _τ). Mechanical properties in terms of tensile tests were performed using Testometric M350-10KN, stress at break, strain at break, and Young's modulus were determined. Rheological results showed that the composites are pseudo plastic in behavior, and the apparent viscosity of the composites increases with increasing starch content above the additive rule, which indicates a partial compatibility in the composite. It was also found that the flow activation energy of the composite increases with increasing starch content. The mechanical results showed that the strain at break of the composite decreases sharply by the presence of starch, whereas the Young's modulus increases with increasing starch content.     

Fusion,electrical conductivity,thermal, and mechanical properties of rigid poly(vinyl chloride) (PVC)/carbon black (CB) composites

Rigid and conductive poly(vinyl chloride) (PVC)/carbon black (CB) composites were prepared in a Haake torque rheometer. The results illustrate that the fusion torque of the PVC/CB composite is increased as the amount of CB is increased. Both the fusion percolation threshold and the fusion time of PVC/CB composites are decreased when the amount of CB is increased. Two major weight loss stages are observed in the TGA curve of PVC/CB composite. The first thermal degradation onset temperature (T_onset1) of PVC/CB composite is decreased as the amount of CB is increased. Both the first and second weight loss stages (ΔY₁ and ΔY₂) of PVC/CB composites are decreased as the amount of CB is increased. The surface resistivity of PVC/CB composite remains almost constant up to 6 parts per hundred unit weight of resin (phr) CB. When the amount of CB in PVC/CB composite is increased from 6 to 15 phr, the surface resistivity of PVC/CB composite is dramatically decreased from 10¹⁰ Ω/sq to 10⁴ Ω/sq. Because of the addition of CB, the rigidity of PVC/CB composite is increased and thus the mechanical properties, such as yield strength, tensile strength, and the Young's modulus, are improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

The Influence of Interfacial Adhesion on the Predicted Young's Modulus of Mica-Reinforced Nylon-6

Particle-filled polymer composites have become attractive because of their wide applications and low cost. Various factors influence the mechanical properties of thermoplastic composites. Of these, the aspect ratio of the reinforcement, interfacial adhesion, and binder content are the most important. Other than these, the particle size and particle size distribution of the reinforcement also influence the mechanical properties. In this paper, injection molded mica composites were investigated, using nylon-6 as a binder. Many models are available to predict the Young's modulus of the composites. A theoretical model for Young's modulus by Lewis and Nielsen was used to predict the Young's modulus of the composites. Tetra isopropyl titanate (TYZOR® TPT) was used to modify the adhesion between the reinforcement and the binder by mixing it with the reinforcement prior to compounding. It was found that Young's modulus was greater than the predicted values.     

Poly(vinyl chloride)/single wall carbon nanotubes composites: Investigation of mechanical and thermal characteristics

Composites of polyvinylchloride (PVC) with single wall carbon nanotubes (SWCNTs) were prepared by plastisol curing. Scanning electron microscopy (SEM) observations revealed that appropriate dispersion of the nanotubes was achieved. The mechanical properties showed that SWCNT improved the Young's modulus and tensile strength of the PVC. The composites have higher elongation at break and toughness as well. By comparing the mechanical properties of the composites, it is found that there is a critical SWCNT loading (about 1 wt%) below which the tensile properties increase with increasing nanofiller concentration. For the composites containing 0.25–0.75 wt% of SWCNT, this situation was observed, whereas for a sample with 1 wt% SWCNT, the mechanical properties decreased due to the agglomeration of the nanotubes. Thermogravimetric analysis indicated that the SWCNT increased T_5%, T_10%, T_50%, T_onset, and T_max and decreased weight loss in the degradation process of the PVC. In addition, by adding SWCNT to the polymer, residual mass at 600°C increased significantly. These results are advantages for the applications of the polymer in which high mechanical properties, including high tensile modulus and toughness, and good thermal properties are needed. J. VINYL ADDIT. TECHNOL., 22:128–133, 2016. © 2014 Society of Plastics Engineers     

Silica‐filled polypropylene composites: The effect of ethylene diamine dilaurate and maleic anhydride grafted polypropylene on mechanical properties,water absorption,morphology, and thermal properties

The effect of two compatibilizers, i.e. ethylene diamine dilaurate (EDD) and maleic anhydride grafted polypropylene (MAPP) on the mechanical properties, water absorption, morphology, and thermal properties of silica‐filled polypropylene (PP/Sil) composites were studied. The results show that the tensile, impact and flexural strengths (up to 2 php), Young's modulus, and elongation at break (Eb) increased with increasing EDD content. However, increasing MAPP content increases the tensile strength, Young's modulus, impact and flexural strengths, and water absorption resistance. At a similar compatibilizer content, EDD exhibits higher Eb, impact and flexural strengths but lowers tensile strength, Young's modulus, and water absorption resistance compared with MAPP. Scanning electron microscopy study of tensile fractured surfaces exhibits the evidence of better silica‐PP adhesion with MAPP and EDD compared with the similar composites but without compatibilizer. Fourier transform infra red spectra provide an evidence of interaction between EDD or MAPP with PP/Sil composites. Termogravimetry analysis results indicate that the addition of EDD or MAPP slightly increases the thermal stability of PP/Sil composites. Differential scanning calorimetry also indicates that PP/Sil composites with EDD or MAPP have higher heat fusion (ΔH_f(com)) and crystallinity (X_com) than similar composites but without compatibilizer. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Effects of the Treatment of Al(OH)3 by a Silane Coupling Agent on the Tensile Properties of PVC/Al(OH)3 Composite

The present work deals with the study of a composite based on poly(vinyl chloride) (PVC) and aluminum hydroxide (Al(OH)₃) which is treated with different concentrations of the silane coupling agent N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

The composites containing untreated Al(OH)₃ and those treated with the coupling agent were prepared by melt mixing using a two-roll mill.

Analysis of the treated filler by means of Fourier Transform Infrared spectroscopy (FTIR) showed the formation of oligoaminosilanes resulting from the condensation of the silane coupling agent.

The tensile properties of the PVC/Al(OH)₃ composite reflected the effect of the addition of the mineral filler and also the influence of the chemical treatment on the interfacial adhesion. The incorporation of aluminum hydroxide into PVC resulted in an increase of Young's modulus and the yield stress.

From the calculation of a parameter B which was used to quantify the state of adhesion between the polymeric matrix and the filler, it was concluded that the surface chemical treatment of the filler with the silane coupling agent leads to higher reinforcement as a result of the interfacial interactions developed between PVC and Al(OH)_3.     

Studies on composites from wood and polypropylenes. II

Composites of polypropylene (PP) or maleic-anhydride-modified polypropylene (MPP) with refiner ground pulp (RGP) were prepared under various kneading conditions (mixing temperature, rate of rotation, and mixing time) and evaluated for their tensile strength (σ_max), break elongation (?_max), and Young's modulus (E). Particularly, for the rate of rotation, fiber length distribution and its fibrillation were investigated in connection with mechanical properties of the composites. Also evaluated in this study was the effect of modifiers of PP on the properties. Modified PP that can be grafted or can have affinity to RGP was proved to improve the tensile strength of the molded composites as the RGP content increases, while the strength was decreased for PP–RGP composite without a modifier. MPP was also evaluated as a compatibilizer for the PP–RGP composites, and a tremendous improvement of tensile strength was achieved with MPP addition of only 2.5%, indicating that MPP can act as a compatibilizer in its system. These lines of evidence is interpreted to be caused from the improvement of the adhesion between RGP and PP through localizing MPP at the interface of these two components.     

Mechanical Properties of PPS/PC/GF/Nano-CaCO3 Hybrid Composites

A kind of nanometer calcium carbonate (nano-CaCO₃) filled glass fibre-reinforced polyphenylene sulfide/polycarbonate (PPS/PC/GF) hybrid composites were fabricated with a twin-screw extruder in this paper, and the surface of the nanometer particles was pretreated with stearic acid in a high speed mixer before melt blending. The Young's modulus, tensile strength, tensile elongation at break, flexural modulus and strength of these hybrid composites were measured at room temperature by using a universal materials testing machine, to identify the influence of the nano-CaCO₃ content on the mechanical properties of these hybrid composites. It was found that there were relatively evident reinforcing and toughening effects of the nano-CaCO₃ on the PPS/PC/GF hybrid composites. The Young's modulus, tensile strength, flexural strengt and elongation at break of these composites increased nonlinearly with an addition of the nano-CaCO₃ weigh fraction (φ _f ) when φ _f was less than 6%, and they reached the maximum at φ _f of 6%, and then decreased; while the flexural modulus increased as φ _f was less than 4%, and then decreased.     

A rheological and morphological study of treated PVC

This article reports a rheological and morphological study of poly(vinyl chloride) (PVC) that was subjected to a treatment capable of decreasing the simultaneous mass transfers occurring between liquid food (or simulant) and PVC packaging. The storage modulus (G′), loss modulus (G″), and the loss angle (tan δ), have been used to determine the glass transition temperature using a Rheometric Scientific Dynamic Analyzer. Young's modulus was measured on a dynamometer, and a morphological characterization was carried out with an optical microscope. The obtained results show that treated PVC behaves like a composite material, which is in agreement with a previously established model. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3497–3502, 2003     

Experimental assessment of the thermodynamic theory of the compositional variation of Tg: PVC systems

The glass-transition temperatures (T_g's) and specific heats (C_p) of poly(vinyl chloride) (PVC) and PVC plasticized with 5–120 phr di(2-ethylhexyl) adipate (DOA) and tri(2-ethylhexyl) trimellitate (TOTM) have been determined by differential scanning calorimetry (DSC). Measured T_g's were compared to predictions by the Couchman and Karasz (C–K) thermodynamic theory, three related empirical equations, and a new equation obtained from the C–K relation by assuming the product T_gΔC_p to be constant. It was found that the T_g's of the PVC/TOTM mixtures are adequately predicted only by the C–K and the derivative relation. The T_g's of the PVC/DOA mixtures follow a sigmoidal or cusp-like dependence on plasticizer composition as has been observed for some other PVC/plasticizer mixtures. In this case, the approximation afforded by the C–K or derivative equations is still superior to the empirical models over a wide composition range. Dynamic mechanical analysis of the PVC/DOA mixtures suggests that the DSC transitions may consist of two overlapping phase transitions. The reported sigmoidal composition dependence of the DSC T_g's may therefore result from the measured T_g's being weighted towards the temperature corresponding to the predominant dynamic mechanical transition (i.e., the high T_g phase at low plasticizer concentrations and the low T_g phase at high plasticizer concentrations). In such cases of partial phase separation, the C–K or the derivative equation may be used to estimate the composition of the two phases at each overall plasticizer concentration.     

On the dynamic state of plasticized poly(vinyl chloride)

The spin probe technique is suggested to be suitable for the study of polymer-plasticizer interactions. In this work it was found that the rotational relaxation time (τ) of probe radicals in plasticized poly(vinyl chloride) (PVC) diminishes strongly when the amount of plasticizer is increased. A linear correlation between τ and Young's modulus (G) was observed. This indicated that the microstate considerably influences the mechanical behaviour of the gel. The translational diffusion constant of plasticizer molecules at 25°C was calculated to change from 0.2 times; 10^-8 cm²/s (PVC weight fraction 0.83) to 4.6 times; 10^-8 cm²/s, (PVC weight fraction 0.20). These values indicate a high degree of freedom for lateral motion of plasticizer molecules in gels.     

Transition-metal coordination for complexing poly-(vinyl chloride)–polyurethane blends

Binary blends of poly(vinyl chloride) (PVC) and polyether polyurethane (PU) containing divalent transition metal (Zn²⁺) have been prepared by solution blending. The physical and mechanical properties of the blends are studied utilizing differential scanning calorimetry (DSC), thermogravimetry (TG), and tensile testing. The DSC results showed a high degree of molecular mixing of the two polymers. The glass transition temperatures (T_g) of the blends exhibited one major T_g whose position on the temperature scale is raised with increasing levels of PVC. The blends yielded stress–strain behavior similar to reinforced elastomers at low PVC, but at high PVC contents, they exhibited increased elongation. The latter materials showed well-developed yield points, stress whitening, and necking. Cold drawing was exhibited by the materials under tension. The tensile strength and Young's modulus were enhanced as the PVC content was increased.     

Mechanical studies on poly(vinylidene fluoride) based polymer electrolytes

The mechanical strength of the poly(vinylidene fluoride) (PVDF) based polymer electrolyte deteriorates with increasing salt content. For a salt concentration of 2 wt% the Young's modulus is 10^?5 Pa. The Young's modulus reduces by 60% when the salt concentration increases five‐fold. The decrease in mechanical strength of the polymer electrolyte by the incorporation of the salt is attributed to the intramolecular interaction between the chains of the polymer and the salt. The mechanical strength of the polymer electrolyte was also analyzed for different plasticizer content. The plasticizer used was ethylene carbonate (EC). The Young's modulus of the plasticized polymer electrolyte decreased with increased in EC content, but the elongation of the material and the energy at break increased with EC content, showing increased flexibility.     

Modified syndiotactic polypropene: Poly(propene-co-octene) and blends with atactic oligopropene

Propene and 1-octene were copolymerized with the syndiospecific homogeneous metallocene catalyst Me₂C(Cp)(Flu)ZrCl₂/MAO. Large amounts of octene were incorporated randomly. While catalyst activity was not affected markedly by low octene content, molecular weight, crystallinity, Young's modulus, and glass transition temperature were reduced with increasing octene content. Blends of atactic oligopropene with syndiotactic polypropene and poly(propene-co-octene) were prepared from toluene solution and compared with a reactor blend prepared with a hybrid catalyst containing a mixture of syndiospecific Me₂C(Cp)(Flu)ZrCl₂/MAO and non-specific Cp₂ZrCl₂/MAO. Atactic oligopropene acted as plasticizer reducing Young's modulus and glass transition temperature of the blends.     

In situ Reaction Synthesis and Mechanical Properties of TaC–TaSi2 Composites

TaC–TaSi₂ composites were fabricated at 1700°C by an in situ reaction/hot pressing method using Ta, Si, and graphite as initial materials. TaSi₂ content was 0–100 vol%. The microstructure and mechanical properties of the composites were investigated. It was found that the relative densities of composites were above 97.5% when the volume content of TaSi₂ was above 10%. The TaC/10 vol% TaSi₂ composite presented the highest flexural strength of 376 MPa. When the TaSi₂ content was 30–50 vol%, the composites showed the highest fracture toughness of about 4.3 MP·am^1/2. In addition, the composites could retain high Young's modulus up to at least 1525°C.