Rheological Investigation of Relaxation Behavior of Polycarbonate/Acrylonitrile-Butadiene-Styrene Blends.
ABSTRACT: The rheological properties of polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS) blends with various blend ratios are investigated at different temperatures to determine the shear dependent chain motions in a heterogeneous blend system. At low frequency levels under 0.1 rad/s, the viscosity of the material with a blend ratio of 3:7 (PC:ABS) is higher than that of pure ABS polymer. As the temperature increases, the viscosities of ABS-rich blends increase rather than decrease, whereas PC-rich blends exhibit decrease in viscosity. Results from the time sweep measurements indicate that ordered structures of PC and the formation and breakdown of internal network structures of ABS polymer occur simultaneously in the blend systems. Newly designed sequence test results show that the internal structures formed between PC and ABS polymers are dominant at low shear conditions for the blend ratio of 3:7 and effects of structural change and the presence of polybutadiene (PBD) become dominant at high shear conditions for pure ABS. The results of yield stress and relaxation time for PC/ABS blends support this phenomenon. The specimen with a blend ratio of 3:7 exhibited the highest value of yield stress at high temperature among others, which implies that the internal structure become stronger at higher temperature. The heterogeneity of ABS-rich blends increases whereas that of PC-rich blends decreases as temperature increases.
Project description:Morphology formation during compounding, as well as injection molding of blends containing 60 wt % polycarbonate (PC) and 40 wt % polybutadiene rubber-modified styrene-acrylonitrile copolymers (ABS), has been investigated by transmission electron microscopy (TEM). Profiles of the blend morphology have been recorded in injection-molded specimens and significant morphology gradients observed between their skin and core. A <10 µm thick surface layer with strongly dispersed and elongated nano-scale (streak-like) styrene acrylonitrile (SAN) phases and well-dispersed, isolated SAN-grafted polybutadiene rubber particles is followed by a 50-150 µm thick skin layer in which polymer morphology is characterized by lamellar SAN/ABS phases. Thickness of these lamellae increases with the distance from the specimen's surface. In the core of the specimens the SAN-grafted polybutadiene rubber particles are exclusively present within the SAN phases, which exhibit a much coarser and less oriented, dispersed morphology compared to the skin. The effects of the viscosity of the SAN in the PC/ABS blends on phase morphologies and correlations with fracture mechanics in tensile and impact tests were investigated, including scanning electron microscopy (SEM) assessment of the fracture surfaces. A model explaining the mechanisms of morphology formation during injection molding of PC/ABS blends is discussed.
Project description:The glycidyl-POSS (Polyhedral Oligomeric Silsesquioxanes, Polysilsesquioxane, POSS) (Gly-POSS) and trisilanolisooctyl-POSS (HO-POSS) were applied as functional additives influencing on the viscoelastic properties of the dynamic vulcanized PLA/ENR (poly(lactic acid)/epoxidized natural rubber) blends. The plasticizing effect of HO-POSS on PLA/ENR melt, leading to the decrease of complex viscosity at 160 °C, was observed. After the incorporation of Gly-POSS into PLA/ENR blends the complex viscosity increased confirming that the epoxy groups of Gly-POSS were able to react with the functional groups of ENR and the groups present at the end of PLA chains. The incorporation of Gly-POSS into 40:60 PLA/ENR blend provided significant enhancement of the storage shear modulus G' at 30 °C. Furthermore, the glass transition temperatures T<sub>g</sub> of ENR phase for PLA/ENR/Gly-POSS blends were shifted to higher values of temperature as compared with blends modified by HO-POSS. Strong reduction of the elongation at break E<sub>b</sub> for 40:60 PLA/ENR/Gly-POSS blend indicated that Gly-POSS particles acted as multifunctional cross-links reducing elasticity of the material. The modification of 40:60 PLA/ENR blend by HO-POSS molecules led to lower values of composting coefficient K<sub>C</sub> indicating stronger deterioration of the mechanical properties that resulted from more intense degradation processes occurring during disposal in soil.
Project description:In this work, the 70/30 and 30/70 w/w polycaprolactone (PCL)/polybutylene succinate (PBS) blends and their corresponding PCL/PBS/(polycarbonate (PC)/multiwalled carbon nanotubes (MWCNTs) masterbatch) nanocomposites were prepared in a twin-screw extruder. The nanocomposites contained 1.0 and 4.0 wt% MWCNTs. The blends showed a sea-island morphology typical of immiscible blends. For the nanocomposites, three phases were formed: (i) The matrix (either PCL- or PBS-rich phase depending on the composition), (ii) dispersed polymer droplets of small size (either PCL- or PBS-rich phase depending on the composition), and (iii) dispersed aggregates of tens of micron sizes identified as PC/MWCNTs masterbatch. Atomic force microscopy (AFM) results showed that although most MWCNTs were located in the PC dispersed phase, some of them migrated to the polymer matrix. This is due to the partial miscibility and intimate contact at the interfaces between blend components. Non-isothermal differential scanning calorimetry (DSC) scans for the PCL/PBS blends showed an increase in the crystallization temperature (Tc) of the PCL-rich phase indicating a nucleation effect caused by the PBS-rich phase. For the nanocomposites, there was a decrease in Tc values. This was attributed to a competition between two effects: (1) The partial miscibility of the PC-rich and the PCL-rich and PBS-rich phases, and (2) the nucleation effect of the MWCNTs. The decrease in Tc values indicated that miscibility was the dominating effect. Isothermal crystallization results showed that the nanocomposites crystallized slower than the neat blends and the homopolymers. The introduction of the masterbatch generally increased the thermal conductivity of the blend nanocomposites and affected the mechanical properties.
Project description:Electromagnetic interference (EMI), an unwanted phenomenon, often affects the reliability of precise electronic circuitry. To prevent this, an effective shielding is prerequisite to protect the electronic devices. In this study, an attempt was made to understand how processing of polymeric blend nanocomposites involving multiwalled carbon nanotubes (MWCNTs) affects the evolving interconnected network structure of MWCNTs and eventually their EMI shielding properties. Thereby, the overall blend morphology and especially the connectivity of the polycarbonate (PC) component, in which the MWCNTs tend to migrate, as well as the perfectness of their migration, and the state of nanotube dispersion are considered. For this purpose, blends of varying composition of PC and poly(methyl methacrylate) were chosen as a model system as they show a phase diagram with lower critical solution temperature type of characteristic. Such blends were processed in two different ways: solution mixing (from the homogeneous state) and melt mixing (in the biphasic state). In both the processes, MWCNTs (3 wt %) were mixed into the blends, and the evolved structures (after phase separation induced by annealing in solution-mixed blends) and the quenched structures (as the blends exit the extruder) were systematically studied using transmission electron microscopy (TEM). Both the set of blends were subjected to the same thermal history, however, under different conditions such as under quiescent conditions (in the case of solution mixing) and under shear (in the case of melt mixing). The electrical volume conductivity and the evolved morphologies of these blend nanocomposites were evaluated and correlated with the measured EMI shielding behavior. The results indicated that irrespective of the type of processing, the MWCNTs localized in the PC component; driven by thermodynamic factors and depending on the blend composition, sea-island, cocontinuous, and phase-inverted structures evolved. Interestingly, the better interconnected network structures of MWCNTs observed using TEM in the solution-mixed samples together with larger nanotube lengths resulted in higher EMI shielding properties (-27 dB at 18 GHz) even if slightly higher electrical volume conductivities were observed in melt-mixed samples. Moreover, the shielding was absorption-driven, facilitated by the dense network of MWCNTs in the PC component of the blends, at any given concentration of nanotubes. Taken together, this study highlights the effects of different blend nanocomposite preparation methods (solution and melt) and the developed morphology and nanotube network structure in MWCNT filled blend nanocomposites on the EMI shielding behavior.
Project description:Microfibrillar and droplet morphology of polypropylene (PP) phase dispersed in polypropylene (PS) was fabricated by using melt-extrusion. This morphology was obtained by introducing isotactic PP (20 wt.%) with different viscosity in the PS matrix (80 wt.%). Furthermore, the rheological properties of the blend investigated as a function of the viscosity ratio K. The variations in blend morphology were related to crystallization, melting properties, and viscoelasticity. The blends with K >> 1 develop a fine morphology with PP microfibrils along the flow direction, while diameters of the dispersed PP droplets gradually increase with lower values of K = 1, or K << 1. Crystallinity of the prepared blends significantly decreases compared to neat PP, while the microfibrillar morphology induces homogeneous crystallization with small crystallites. This is reflected in a decrease of the crystallization temperature, small loss in the crystallinity, and lower melting temperature of the PS80/PP20 blend compared to neat PP. The storage moduli, loss moduli, and complex viscosity are highest for the microfibrillar morphology that presents retarded relaxation. The rheological properties are dominated by the dispersed phase (K > 1), or matrix (K < 1). The variation in blend properties with microfibrillar morphology can be clearly distinguished from heterogeneous blends containing PP droplets, providing an efficient tool to create a binary blend with unique properties.
Project description:We present a comprehensive experimental rheological dataset for purified entangled ring polystyrenes and their blends with linear chains in nonlinear shear and elongation. In particular, data for shear stress growth coefficient, steady-state shear viscosity, and first and second normal stress differences are obtained and discussed as functions of shear rate as well as molecular parameters (molar mass, blend composition and decreasing molar mass of linear component in blend). Over the extended parameter range investigated, rings do not exhibit clear transient undershoot in shear, in contrast to their linear counterparts and ring-linear blends. For the latter, the size of the undershoot and respective strain appear to increase with shear rate. Universal scaling of strain at overshoot and fractional overshoot (ratio of maximum to steady-state shear stress growth coefficient) indicates subtle differences in the shear-rate dependence between rings and linear polymers or their blends. The shear thinning behaviour of pure rings yields a slope nearly identical to predictions (-4/7) of a recent shear slit model and molecular dynamics simulations. Data for the second normal stress difference are reported for rings and ring-linear blends. While <i>N</i> <sub><i>2</i></sub> is negative and its absolute value stays below that of <i>N</i> <sub><i>1</i></sub> , as for linear polymers, the ratio <i>-N</i> <sub><i>2</i></sub> <i>/N</i> <sub><i>1</i></sub> is unambiguously larger for rings compared to linear polymer solutions with the same number of entanglements (almost by factor of two), in agreement with recent non-equilibrium molecular dynamics simulations. Further, -<i>N</i> <sub><i>2</i></sub> exhibits slightly weaker shear rate dependence compared to <i>N</i> <sub><i>1</i></sub> at high rates, and the respective power-law exponents can be rationalized in view of the slit model (3/7) and simulations (0.6), although further work is needed to unravel the molecular original of the observed behaviour. The comparison of shear and elongational stress growth coefficients for blends reflects the effect of ring-linear threading which leads to significant viscosity enhancement in elongation. Along the same lines, the elongational stress is much larger than the first normal stress in shear, and their ratio is much larger for rings and ring-linear blends compared to linear polymers. This conforms the interlocking scenario of rings and their important role in mechanically reinforcing linear matrices.
Project description:Fabrication of partially biobased poly(trimethylene terephthalate) (PTT) elastomeric blends was done via melt processing. Both natural rubber (NR) and epoxidized NR (ENR) were investigated as impact modifiers at 40 wt % loading to avoid lowering the overall biobased content of the blend system below that of the PTT alone (35% renewable content), along with maleated polybutadiene rubber (MR) and dicumyl peroxide (DCP) as reactive compatibilizers. The compatibility of the blend components was investigated using contact angle, rheometry, and scanning electron microscopy (SEM). The interfacial tensions and work of adhesions indicated that ENR was more miscible than NR in the PTT blend system, which was corroborated by the higher shear viscosity of the ENR blends and strong shear thinning behavior. Additionally, the predictive modeling of viscosity ratios on the elastomer-thermoplastic morphology was found to match the SEM micrographs with the dispersed elastomeric phase within the PTT matrix. The SEM images of the blends also establish that both the compatibilizers reduced the rubber inclusions size, though DCP hampered the impact performance as compared to the MR. In the presence of the MR, there was an increased cross-linking and observed variation in the Fourier transform infrared peaks demonstrating chemical interactions between the maleic anhydride groups with the PTT that allowed for the impact strength to reach 137 J·m<sup>-1</sup> or 4.5 times that of the neat PTT, with the modulus of toughness increased by 82% and an elongation at yield of 50% because of the flexibility and amorphous nature of the rubber constituent.
Project description:This article contains water vapor sorption data obtained on amorphous blends of octenyl succinic acid-modified (denoted as hydrophobically modified starch; HMS) and sucrose (S) in the anhydrous weight HMS/S ratios between 100/0 and 27/75. The water vapor sorption data was obtained gravimetrically. The amorphous state of the blends was confirmed by X-ray diffraction. The glass transition temperatures of the phase-separated blends are listed; the blends show phase separation into a sucrose-rich phase and a HMS-rich phase, the composition of which varies with the blend ratios. The sucrose-rich phase is characterized by a glass transition temperature <i>T</i> <sub>g,lower</sub> that is 40 to 90?K lower than the glass transition temperature <i>T</i> <sub>g,upper</sub> of the HMS-rich phase.
Project description:In this study, nanocomposites were prepared by melt blending poly(butylene succinate) (PBS) with a polycarbonate (PC)/multi-wall carbon nanotubes (MWCNTs) masterbatch, in a twin-screw extruder. The nanocomposites contained 0.5, 1.0, 2.0, and 4.0 wt% MWCNTs. Differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) results indicate that the blends are partially miscible, hence they form two phases (i.e., PC-rich and PBS-rich phases). The PC-rich phase contained a small amount of PBS chains that acted as a plasticizer and enabled crystallization of the PC component. In the PBS-rich phase, the amount of the PC chains present gave rise to increases in the glass transition temperature of the PBS phase. The presence of two phases was supported by scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis, where most MWCNTs aggregated in the PC-rich phase (especially at the high MWCNTs content of 4 wt%) and a small amount of MWCNTs were able to diffuse to the PBS-rich phase. Standard DSC scans showed that the MWCNTs nucleation effects saturated at 0.5 wt% MWCNT content on the PBS-rich phase, above this content a negative nucleation effect was observed. Isothermal crystallization results indicated that with 0.5 wt% MWCNTs the crystallization rate was accelerated, but further increases in MWCNTs loading (and also in PC content) resulted in progressive decreases in crystallization rate. The results are explained by increased MWCNTs aggregation and reduced diffusion rates of PBS chains, as the masterbatch content in the blends increased.
Project description:P(<i>N</i>-phenylmaleimide-alt-styrene) (P(NPMI-alt-St)) and P(<i>N</i>-(4-carboxyphenyl)maleimide-alt-styrene) (P(CPMI-alt-St)) were designed and synthesized via free radical copolymerization. Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (¹H NMR and <sup>13</sup>C NMR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC) were used to confirm the structure of P(NPMI-alt-St) and P(CPMI-alt-St). Next, the effect of P(CPMI-alt-St) on the heat deflection temperature (<i>HDT</i>) of nylon 6 was studied. In comparison to the PA6/P(NPMI-alt-St) blend, with the addition of 10 wt %, the <i>HDT</i> value of the PA6/P(CPMI-alt-St) blend increased by 15.7 °C, and the glass transition temperature (<i>T</i>g) by Dynamic mechanical analysis (DMA) increased 2.3 °C. According to the analysis of DMA, dynamic viscosity, and the SEM of PA6 and its blends, P(CPMI-alt-St) promoted its compatibility with PA6, and promoted the storage modulus and dynamic viscosity of the blends. Thus, the introduction of 4-carboxyl can significantly improve the effect of P(CPMI-alt-St) on the heat resistance modification of nylon 6.