Phase behavior and morphology of poly(phenylene ether)/epoxy blends

The miscibility of diglycidyl ether of bisphenol-A (DGEBA) based epoxies with a series of poly(2,6-dimethyl-1,4-phenylene ether) (PPE) resins was measured and the effects of PPE molecular weight, end-capped or grafted functionality, and blend composition were explored. Interpretation of phase behavior was aided by the use of the Flory-Huggins theory. Miscibility behavior in the unreacted blends was found to correlate with trends in phase separation during the curing reaction. The cured morphologies of these blend systems were also studied. The compatibilization effect of PPE-epoxy copolymer formation was found to play a dominant role in determining the final size of the dispersed phase, while temperature control of reaction and mass transfer kinetics were identified as a possible means of further affecting the cured morphology.     

Miscibility,phase behavior,and mechanical properties of ternary blends of poly(vinyl chloride)/polystyrene/chlorinated polyethylene-graft-polystyrene

The effectiveness of chlorinated polyethylene-graft-polystyrene (CPE-g-PS) as a polymeric compatibilizer for immiscible poly(vinyl chloride)/polystyrene (PVC/PS) blends was investigated. The miscibility, phase behavior, and mechanical properties were studied using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), Izod impact tests, tensile tests, and scanning electron microscopy (SEM). DSC and DMA studies showed that PVC is immiscible with chlorinated polyethylene (CPE) in CPE-g-PS, whereas the PS homopolymer is miscible with PS in CPE-g-PS. The PVC/PS/CPE-g-PS ternary blends exhibit a three-phase structure: PVC phase, CPE phase, and PS phase that consisted of a PS homopolymer and PS in CPE-g-PS. The mechanical properties showed that CPE-g-PS interacts well with both PVC and PS and can be used as a polymeric compatibilizer for PVC/PS blends. CPE-g-PS can also be used as an impact modifier for both PVC and PS. SEM observations confirmed, after the addition of CPE-g-PS, improvement of the interfacial adhesion between the phases of the PVC/PS blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 995–1003, 1998     

Phase behavior of poly(ε-caprolactone)/ poly (vinylidene fluoride) blends

The miscibility of blends of poly (ε-caprolactone) (PCL)/poly(vinylidene fluoride) (PVDF) was studied by measuring the cloud point, melting point depression and crystallization kinetics. Lower critical solution temperature (LCST) behavior was observed at PCL-rich compositions, whilst it was not observed at high compositions of PVDF. However it is possible that an LCST could exist below the melting point of PVDF. From analysis of the melting point depression, the Flory interaction parameter x₁₂, was calculated from the Nishi-Wang equation and the value was found to be-1.5. The crystallization rate of PCL increased with increasing amount of PVDF in the blend. The spinodal curve for PCL/PVDF blends was simulated by using the lattice-fluid theory.     

Influence of compositional gradient on the phase behavior of ternary symmetric homopolymer-copolymer blends: A Monte Carlo study

The formation of bicontinuous microemulsions (BUEs) in ternary symmetric blends including two immiscible homopolymers A and B as well as a linear gradient copolymer G is verified by Monte Carlo simulations. Four phase diagrams as a function of segregation strength and blend composition are constructed to show the effects of compositional gradient. Compared with the blends of A/B/diblock copolymers, the BUE phase occupies a broader region in the phase diagram of the A/B/G blends and is replaced by the three-phase coexistence phases of A + B + L or A + B + D at a much lower chain length ratio. Moreover, the lamellar phase is formed at a higher value of segregation strength, has a shorter periodic length and lower orientational order, and spans a narrower range of the phase diagram. A “counteraction effect” is proposed to explain those discrepancies caused by gradient copolymers.     

Phase behavior of blends of poly(2,6-dimethyl-1,4-phenylene oxide)/polystyrene/poly(o-chlorostyrene-co-p-chlorostyrene) copolymer

The phase behavior of ternary blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), polystyrene (PS) and a 50/50 mole % statistical copolymer of o-chlorostyrene and p-chlorostyrene [p(oClS-pClS)] has been investigated by differential scanning calorimetry (DSC) and analyzed in terms of a Flory-Huggins mean-field segmental interaction parameter treatment. Both PS/PPO and PPO/p(oClS-pClS) binary blends exhibit single glass transition temperatures over the full composition range whereas the PS/p(oClS-pClS) system displays a substantial immiscibilty window which extends into the ternary phase diagram. In principle, ternary systems provide enhanced opportunities relative to binary systems for evaluating segmental interaction parameters χ_ijs from experimental data because of the high sensitivity of phase boundary locations to these parameters and to component molecular weights. In this system the effect of these parameters on the phase boundary was studied experimentally and compared to calculated values.     

Crystallization behavior and mechanical properties of poly(ethylene oxide)/poly(L‐lactide)/poly(vinyl acetate) blends

Poly(vinyl acetate) (PVAc) was added to the crystalline blends of poly(ethylene oxide) (PEO) and poly(L ‐lactide) (PLLA) (40/60) of higher molecular weights, whereas diblock and triblock poly(ethylene glycol)–poly(L ‐lactide) copolymers were added to the same blend of moderate molecular weights. The crystallization rate of PLLA of the blend containing PVAc was reduced, as evidenced by X‐ray diffraction measurement. A ringed spherulite morphology of PLLA was observed in the PEO/PLLA/PVAc blend, attributed to the presence of twisted lamellae, and the morphology was affected by the amount of PVAc. A steady increase in the elongation at break in the solution blend with an increase in the PVAc content was observed. The melting behavior of PLLA and PEO in the PEO/PLLA/block copolymer blends was not greatly affected by the block copolymer, and the average size of the dispersed PEO domain was not significantly changed by the block copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3618–3626, 2001     

Phase behavior of semicrystalline polymer blends

The phase behavior of the semicrystalline polymer blend composed of isotactic polypropylene (iPP) and linear low density polyethylene (PE) was studied using small angle X-ray scattering (SAXS) and optical microscopy (OM). Based on the random phase approximation, the iPP/PE interaction parameter, χ, was obtained, and used to construct the iPP/PE phase diagram. The χ values reported in this study are lower than the χ values for deuterium-labeled moieties, measured by small angle neutron scattering (SANS). The predicted phase diagram has upper critical solution temperature (UCST) behavior with a critical temperature of 143 °C for the molecular weights used in this study. OM was used to locate cloud points and the results are consistent with the predicted phase diagram. Since iPP melts above the critical point, care was taken to distinguish phase separation from iPP crystallization by studying the kinetics of iPP crystallization, and the iPP crystallization was discerned from dewetting. In PE-rich blends, the iPP crystallization was suppressed and no dewetting was observed.     

聚乳酸/聚乙二醇共混物的结晶与降解行为

针对聚乳酸（PLLA）亲水性差、降解周期长的问题,利用与亲水性高分子聚乙二醇（PEG）共混的方法对其进行改性。采用转矩流变仪制备了不同组成的PLLA/PEG共混物颗粒,系统研究了PLLA/PEG共混物的结晶和熔融、亲水性和在酸碱介质中的降解行为。结果表明,PEG的加入增强了共混物中PLLA的结晶能力,提高了PLLA在降温过程中的熔融结晶温度。PLLA/PEG共混物在等温结晶中表现出比纯PLLA更快的结晶速度。通过改变PLLA/PEG共混物的组成,可调控材料的表面亲水性和降解速率。随着PEG含量的增多,PLLA/PEG共混物的表面接触角降低。PLLA与PLLA/PEG共混物均可在水溶液中降解,共混物的降解速率高于纯PLLA,随着PEG含量的升高和降解液中酸碱浓度的提高,PLLA/PEG共混物的降解速率加快。     

Phase distribution and separation in poly(2-acetoxyethyl methacrylate)/polystyrene latex interpenetrating polymer networks

A series of latex interpenetrating polymer networks (LIPNs) were prepared via two-stage soap-free emulsion polymerization of styrene on cross-linked poly(2-acetoxyethyl methacrylate) (PAEMA) seed latexes, using potassium persulfate as initiator. It was found that a compositional gradient was present when PAEMA seeds cross-linked either lightly or highly were used. The polystyrene (PS) phase is localized near the particle center in the former case, while it is segregated near the surface in the latter case. A uniform distribution of PS phase in LIPN was formed, if moderately cross-linked PAEMA seed was used. All the LIPNs appeared to be microphase-separated, and increase of cross-linking degree in seed latexes decreased the PS-rich domain size. The results were explained by the particle growth mechanism that involved the formation of surface-active oligomeric radicals in water phase, adsorption of the radicals onto monomer-swollen particle/water interface, and chain propagation in the interface with subsequent phase migration dominated by the competitive effects of thermodynamics and kinetics.     

Conductive-filler-filled poly(ϵ-caprolactone)/poly(vinyl butyral) blends. I. Crystallization behavior and morphology

The crystallization behavior and morphology of poly(ϵ-caprolactone) (PCL)/poly(vinyl butyral) (PVB) blends containing carbon black (CB) were studied as functions of PVB and CB content. The presence of CB had no influence on the primary nucleation of PCL crystals or the spherulitic growth rate. They were only influenced by the blend ratio of PVB. The growth rates of spherulites were unchanged throughout the crystallization process, regardless of the CB content. The results indicate that the concentration of PCL at the front of growing spherulite remains constant during crystallization. The distribution of CB in the spherulites was observed using atomic force microscopy to explain these results. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 797–802, 1997     

顺酐化聚苯乙烯对PVC/SEBS共混物的增容作用

以顺酐化聚苯乙烯(PS-g-MAH)为增容剂,研究了苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)对聚氯乙烯(PVC)的共混增韧改性,讨论了该共混物在常温、低温下的力学性能及动态力学性能。结果表明,PS-g-MAH能明显改善SEBS与PVC的相容性,使PVC/SEBS共混物中分散相颗粒尺寸明显减小,分布更均匀,共混物的玻璃化转变温度内移,常温和低温下缺口冲击强度增大。当PVC/PS-g-MAH/SEBS(质量比)为75/6/25时,共混物的常温缺口冲击强度为50.6 kJ/m2,低温(-20℃)缺口冲击强度为29.8 kJ/m2。     

Spherulite morphology and crystallization behavior of poly(trimethylene terephthalate)/poly(ether imide) blends

The spherulite morphology and crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(ether imide) (PEI) blends were investigated with optical microscopy (OM), small-angle light scattering (SALS), and small-angle X-ray scattering (SAXS). Thermal analysis showed that PTT and PEI were miscible in the melt over the entire composition range. The addition of PEI depressed the overall crystallization rate of PTT and affected the texture of spherulites but did not alter the mechanism of crystal growth. When a 50/50 blend was melt-crystallized at 180 °C, the highly birefringent spherulite appeared at the early stage of crystallization (t < 20 min). After longer times, the spherulite of a second form was developed, which exhibited lower birefringence. The SALS results suggested that the observed birefringence change along the radial direction of the spherulite was mainly due to an increase in the orientation fluctuation of the growing crystals as the radius of spherulite increased. The lamellar morphological parameters were evaluated by a one-dimensional correlation function analysis. The amorphous layer thickness showed little dependence on the PEI concentration, indicating that the noncrystallizable PEI component resided primarily in the interfibrillar regions of the growing spherulites.     

Crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The crystallization kinetics of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were investigated by DSC as functions of crystallization temperature, blend composition, and PET and PEN source. Isothermal crystallization kinetics were evaluated in terms of the Avrami equation. The Avrami exponent (n) is different for PET, PEN, and the blends, indicating different crystallization mechanisms occurring in blends than those in pure PET and PEN. Activation energies of crystallization were calculated from the rate constants, using an Arrhenius‐type expression. Regime theory was used to elucidate the crystallization course of PET/PEN blends as well as that of unblended PET and PEN. The transition from regime II to regime III was clearly observed for each blend sample as the crystallization temperature was decreased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 23–37, 2001     

Compatibilization of polyethylene/poly(propylene)/polystyrene blends

The compatibilization of mixtures of polyolefins or of polyolefins with polystyrene using either liquid polybutadiene (l-PB)/organic peroxide or styrene-butadiene-styrene (SBS) block copolymers was investigated. Tensile impact strength was chosen as a measure of compatibility. Binary blends LDPE/high-impact polystyrene (HIPS) and LDPE/poly(propylene) (PP) as well as LDPE/HDPE/PP/HIPS blends were prepared by blending in the chamber of a Brabender Plasticorder. Composition of the blends corresponds to real commingled plastic waste. It was found that l-PB-based compatibilizer enhanced the impact strength of LDPE/HIPS blends with LDPE contents higher than 60 wt.-% only. Also SBS copolymer enhanced the impact strength of LDPE/PP blends with LDPE contents higher than 40 wt.-%. Both the compatibilizers substantially increased the toughness of LDPE/HDPE/PP/HIPS blends with composition similar to the municipal plastic waste.     

Phase behavior and properties of poly(methyl methacrylate)/poly(vinyl acetate) blends prepared via in situ polymerization

Polymer blends composed of poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) were prepared via radical-initiated polymerization of methyl methacrylate (MMA) in the presence of PVAc. Differential scanning calorimetry and dynamic mechanical analysis were employed to investigate the miscibility and phase behavior of the blends. The PMMA/PVAc blends of in situ polymerization were found to be phase separated and exhibited a two-phase structure, although some chain transferring reaction between the components occurred. The phase separation resulted from the solvent effect of MMA during the in situ polymerization, which was confirmed by the investigation of phase behavior based on solution cast blending. Solubility analysis of the polymerized blends indicated that some chain transferring reaction between the components occurred during the polymerization. An abrupt increase in gel content from 21.2 to 72.4 wt % was observed when the inclusion of PVAc increased from 30 to 40 wt %, and the gel component consisted of the component polymers as shown by infrared spectroscopy studies. The thermogravimetric analysis study indicated that the inclusion of a small amount of PVAc gives rise to a marked stabilization effect on the thermal stability. The PMMA/PVAc blends exhibited increased notched impact properties with the inclusion of 5 wt % PVAc. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 675–684, 1998     

Poly(butylene terephthalate)/poly(ethylene glycol) blends with compatibilizers

Polymer blend systems offer a versatile approach for tailoring the properties of polymer materials for specific applications. In this study, we investigated the compatibility of polybutylene terephthalate (PBT) and poly(ethylene glycol) (PEG) blends processed using a twin-screw extruder, with the aim of enhancing their compatibility. Phthalic anhydride (PAn) and phthalic acid (PAc) were used as potential compatibilizers at different concentrations to improve interfacial interactions between PBT and PEG. Blend morphologies were characterized using scanning electron microscopy, which revealed improved interfacial compatibility and reduced phase separation with the incorporation of small amounts of PAn and PAc. Differential scanning calorimetry analysis indicated changes in the melting temperature (T_m) and glass transition temperature (T_g) of the blends owing to the compatibilizing effects of PAn and PAc. Dynamic mechanical analysis further corroborated the influence of the compatibilizers on the T_g and viscoelastic behavior. Thermogravimetric analysis demonstrated enhanced thermal stability with the addition of either PAn or PAc. Rheological measurements indicated an increase in complex viscosity with increasing compatibilizer content, indicating improved compatibility. The degradation point (T_d) of PBT/PEG blend increased from 158 to 200 and 319°C with the incorporation of 5 phr PAn and 2 phr PAc, respectively. Mechanical properties, including tensile strength, Young's modulus, and Izod impact strength, were evaluated. For instance, the tensile strength of PBT/PEG blend was enhanced from 43.5 to 48.7 and 49.7 MPa by incorporating 5 phr PAn and 2 phr PAc, respectively. However, the impact strength of PBT/PEG blend increased from 3.0 to 4.3 and 4.2 kJ/m² with the addition of 1 phr PAn and 1 phr PAc, respectively. The findings demonstrated that adding 5 phr PAn or 2 phr PAc to the PBT/PEG blends was advantageous, achieving a harmony of performance benefits and compromises. Rheological observations contributed significantly to the mechanical and thermal properties. Overall, the study highlights the significance of utilizing PAn and PAc as effective compatibilizers for enhancing the properties of PBT/PEG blends, making them potential candidates for various applications.     

Three-parameter (3P) weibull distribution for characterization of strength of ceramics showing R-Curve behavior

Strength distribution of advanced ceramics is commonly characterized by two-Parameter (2P) Weibull distribution. However, deviation of strength distribution from 2P-Weibull distribution may occur in ceramics due to various mechanisms. R-curve behavior is one of these mechanisms where increase of fracture resistance with the extension of crack occurs. In such cases, 2P-Weibull distribution may not be the best fitting distribution function based on the goodness-of-fitness tests. This article examines the effectiveness of three-parameter (3P) Weibull distribution function for fitting the strength variation due to R-curve effect by using experimental and virtual strength data. The effect of Weibull parameters, degree of increase in crack resistance and number of samples on effectiveness of fitting via 3P-Weibull distribution is investigated. It is reported that 3P-Weibull distribution function fits the strength distribution better than 2P-Weibull distribution function for materials showing R-curve behavior when the crack resistance curve is steep and Weibull modulus is high. Furthermore, it is shown that at least 100 samples should be used for a reliable estimate when the material exhibits R-curve behavior.     

Novel miscible poly(ethylene sebacate)/poly(4-vinyl phenol) blends: Miscibility, melting behavior and crystallization study

High molecular weight samples of the novel biodegradable polyester poly(ethylene sebacate) (PESeb) were synthesized. Miscible poly(ethylene sebacate)/poly(4-vinyl phenol) semicrystalline/amorphous blends were prepared by applying the solvent casting method. Miscibility was proved by the single composition dependent glass transition temperature over the entire composition range observed in DSC traces of the quenched blend samples and also by the melting point depression. The Flory-Huggins interaction parameter was found to be x₁₂ = −1.3. Also, FTIR spectra supported the hypothesis of intermolecular interactions due to hydrogen bonding. The crystallization of PESeb in blends was studied. As expected, isothermal crystallization rates decreased in the blends with increasing the PVPh content. The Lauritzen-Hoffman analysis was tested. The values of nucleation constant K_g did not show any substantial variation. The non-isothermal crystallization of the blends was also tested. It was found that the crystallization is retarded in the case of blends, compared to the neat PESeb.     

Miscibility and phase behavior of poly(D,L-lactide)/poly(p-vinylphenol) blends

The miscibility of poly(D ,L -lactide) (PDLLA) and poly(p-vinylphenol) (PVPh) blends has been studied by differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). Phase separation was observed in blends over a wide composition range. A PDLLA-rich phase was found to coexist with an almost pure PVPh phase. The quenched blend samples showed two glass transitions (T_gs), except for a blend with a low PVPh content. However, the T_g value of the PDLLA-rich phase showed a gradual increase with increasing PVPh content. No evidence of interassociation (hydrogen bond formation) between PDLLA and PVPh was found by FTIR. The phase behavior of the blends was simulated using an association model. The results suggested that the equilibrium constant of interassociation between PDLLA and PVPh was small. The phase compositions of the two separated phases were calculated using Fox, Gordon-Taylor, and Couchman equations. The amount of PVPh in the PDLLA-rich phase increased with increasing PVPh content in the blend. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 811–816, 1998     

Preparation of polystyrene/poly(methyl methacrylate) blends by compressed fluid antisolvent technique

Submicron polystyrene (PS)/poly(methyl methacrylate) (PMMA) blends were generated by the precipitation with a compressed antisolvent (PCA) technique. The generation of PS/PMMA blends was carried out by spraying a solution containing PS and PMMA into a precipitator. The blends without coalescence were observed to only be generated when both vapor and liquid CO₂ existed in the precipitator combined with appropriate total polymer concentration in solution, molecular weights (Mws) of PS and PMMA, mass ratio of PS to PMMA, flow rates of CO₂ and polymer solution, and liquid CO₂ level in the precipitator. Two Mws of PS, 144,000 and 44,000, and two Mws of PMMA, 85,000 and 36,000, were used in this study. It was found that the blends could be easier to generate using a higher PS Mw, a lower PMMA Mw, and a higher mass ratio of PS to PMMA. Toluene with a solubility parameter smaller than that of tetrahydrofuran (THF) was found to be the more appropriate solvent for generating spherical PS/PMMA submicron blends. The SEM and TEM images show that the spherical PS/PMMA core/shell blends could be generated at a temperature of 298 K, a pressure of 6.41 MPa, a liquid CO₂ level of 1/2 of the precipitator, a CO₂ flow rate of 2000 mL/min, a solution flow rate of 5 or 10 mL/min, and a total polymer concentration of 0.72 wt% for a PS Mw of 144,000, a PMMA Mw of 36,000, and a PS/PMMA mass ratio of 9/1. Individual and spherical PS and PMMA particles or spherical PS particles partially covered by a PMMA films, however, were generated when the liquid CO₂ level was of 1/8 or lower in the precipitator. A possible mechanism for the formation of core-shell blend was proposed.