Preparation of a novel alloy composed of fluorene‐based polyester and polycarbonate and their properties for the optical uses

This paper is concerned with the structures and properties for fluorene‐based polyester‐polycarbonate (FBP/PC) alloys. Obtained alloys were characterized thermodynamically, optically, and viscoelastically, and the relationship between drawing behavior and molecular dynamics were also investigated. FBP/PC alloys showed transparent and a single glass transition temperature (Tg) for all compositions that indicated the complete compatibility in FBP/PC alloy systems. Tendency of the maximum draw ratios for alloy sheets was very similar to the profile of Tg versus FBP content. Maximum draw ratio was increased linearly with FBP content, demonstrating the intimate relationship between the large deformation and the molecular motion. A large amount of orientational birefringence occurred in PC sheet, but in the case of FBP/PC alloys and FBP, orientational birefringence was drastically decreased or not observed at all. This meant that positive birefringence of PC molecules was compensated by the absolutely smaller birefringence of FBP molecules. From a molecular mobility perspective, relaxation time (T2) for PC was smaller even at 200°C. However, for FBP and its alloys, T2 were much larger, showing the considerably enhanced molecular mobility in FBP or FBP/PC alloys. In this study, we could first reveal that the relationship between Tg and FBP content was very similar to the behaviors of birefringence (Δn)/draw ratio (λ) versus FBP content, T2 versus FBP content and 1/maximum draw ratio (λ_max) versus FBP content. Based on these results, we were able to propose a novel alloy with high refractive index, low orientational birefringence, and higher processability by alloying FBP with PC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility evolution of polycarbonate/polystyrene blends during compounding

The miscibility evolution of polycarbonate/polystyrene (PC/PS) blends during the compounding process in three blending methods of industrial relevance, namely melt blending, remelt blending in a twin‐screw extruder and third melt blending in an injection molding machine, was investigated by measuring their glass transition temperatures (T_g) and their specific heat increment (ΔC_p). Differential scanning calorimetry (DSC) was used to examine nine blend compositions. Shifts in glass transition temperature (T_g) of the two phases in melt‐mixed PC/PS blends suggest partial miscibility of one polymer in the other. The observed solubility strongly depends on blend composition and blending method. The T_g measurements showed maximum mutual solubility around 50/50 composition. The miscibility of PC/PS blended after the third stage (melt injection molding) was higher than that after the first stages (melt extrusion) and the second stages (remelt extrusion).     

Fine dispersion of carbon black in fluorene‐based resin

The dispersion ability of fluorene‐based epoxy resin (FBE), bisphenol A based epoxy resin (PBE), fluorene‐based polyester (FBP), and polycarbonate (PC) in carbon black (CB) was evaluated. CB/FBE composite had a lower L value (reflectance, blackness) than that of CB/PBE composite, for the same CB content. Aggregations of CB in CB/FBE composites were much smaller than those in CB/PBE composites. The strong interaction between fluorene with cardo structure and CB resulted in a fine dispersion of CB in FBE. FBP had much higher dispersion ability of CB than PC. CB (50 wt%) was dispersed into FBP compared with the 10 wt% of CB dispersed in PC by melt blending. The effect of CB on the mechanical properties of FBP was much higher than that on PC due to fine dispersion of CB in FBP. The effect of CB addition on the T_g of FBP was also higher than that of CB on the T_g of PC. Computational simulation indicates that most stable energy between fluorene with a cardo structure and graphite structure was smaller than the energy between bisphenol A and graphite. It was also shown that the minimum energy appeared when the fluorene structure was almost parallel to the graphite plane. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Effects of molecular weight on phase structure of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The phase structure of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends was studied in relation to the molecular weight. The samples were prepared by both solution blends, which showed two glass‐transition temperatures (T_g), and melt blends (MQ), which showed a single T_g, depending on the composition of the blends. The T_g of the MQ series was independent of the molecular weight of the homopolymer, although the degree of transesterification in the blends was affected by the molecular weight. The MQ series showed two exotherms during the heating process of a differential scanning calorimetry scan. The peak temperature and the heat flow of the exotherms were affected by the molecular weight of the homopolymers. The strain‐induced crystallization of the MQ series suggested the independent crystallization of PET and PEN. Based on the results, a microdomain structure of each homopolymer was suggested. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2428–2438, 2005     

Modification of PET in high‐speed melt spinning by blending with PEN

Blends of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) were melt spun using a high‐speed winding process in a single‐screw extruder combined with a spinning setup. The filaments had a single T_m and T_g, which indicates excellent compatibility in both the amorphous and crystalline phases. Birefringence and wide angle X‐ray measurements indicated that compounding PEN into PET suppresses stress‐induced orientation and decreases the stressinduced crystallization in the filaments. Adding PEN to PET relaxes the formation of skin‐core structures for as‐spun fibers and reduces the occurrence of broken filaments. Although the addition of PEN reduced crystallinity, it did not affect the tenacity and the shrinkage of the compounded filaments. The elongation of the fibers could be reduced by 30% to 40%, eliminating the need for a further drawing. These results are attributed to PEN's rigid backbone. Adding PEN to PET improves PETs spinnability during high‐speed spinning.     

Single-Phase blends of polycarbonate and poly(phenyl methacrylate)

Miscibility studies on blends of polycarbonate (PC) and poly(phenyl methacrylate) (PPMA) were undertaken by means of differential scanning calorimetry (DSC), dynamic mechanical, and dielectric relaxation methods. PC and PPMA were mixed by dissolving in tetrahydrofuran (THE) and subsequently coprecipitated in methanol. DSC studies showed a single glass transition (T_g) that shifts systematically with composition. These T_gs are reproducible in repeated DSC heating cycles, suggesting true miscibility of the pair. The dry PC and PPMA pellets were melt mixed in a Mini-Mixer/Molder. The extrudates were compression molded. These melt-mixed PC/PPMA blends exhibited glass like transparency and also showed a single T_g in the DSC scans. The true miscibility of PC and PPMA was further confirmed by dynamic mechnaical and dielectric relaxation methods. The net birefringence has been reduced substantially because of the opposite sign of the itrinsic birefringence of PC and PPMA molecules. At the 12/88 PC/PPMA, the birefringence remains zero at all draw ratios, indicating the achievement of birefringence free polymer alloys.     

Effect of low‐temperature annealing on dimensional stability of poly(ethylene 2,6‐naphthalene dicarboxylate) fibers melt‐spun at high speed

To investigate structural factors, necessary to obtain a valuable industrial fiber possessing excellent thermomechanical properties, poly(ethylene 2,6‐naphthalene dicarboxylate) (PEN) fibers were produced by high‐speed melt‐spinning to a take‐up speed of 8 km/min, followed by low‐temperature annealing between the glass‐transition temperature (T_g) and exothermic cold crystallization temperature (T_{c cold}), where little transition of crystalline phase, as well as little thermal degradation, takes place. Their thermomechanical behavior, as well as structural variations, were investigated through differential scanning calorimetry, Rheovibron, thermomechanical analysis (TMA), and tensile testing. Two types of the α‐ and α′‐dispersions were observed at near T_g and at a temperature 50–60°C higher than T_g, respectively. The dispersions were affected by rearranged structures, which are generated by developing an inhomogeneous taut structure with rigidity of aromatic segment and aliphatic segment. The α‐dispersion seemed to reflect an inhomogeneous taut structure by the less nearly arranged segments. Consequently, at intermediate take‐up speeds between 2 and 6 km/min the inhomogeneous taut structure may be partially formed, but the homogeneously ordered structure may be enlarged as the take‐up speed and annealing temperature increased. Thermal shrinkage increased above the α‐dispersion temperature, which suggested that the onset point of dimensional change in PEN fibers was attributed to α‐dispersion. In the case of annealed fibers, the start of length change coincided with the respective annealing temperatures, which indicated that dimensional stability could be gained from restraining the inhomogeneous taut structure in the amorphous region without the transition of crystalline phase by annealing between T_g and T_{c cold}. Therefore, to obtain dimensional stability in PEN fibers, it is supposed that the inhomogeneous taut structure exhibited by the α‐dispersion should be controlled. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 212–218, 2005     

Multiwalled carbon nanotubes‐based polypropylene composites: Influence of interfacial interaction on the crystallization behavior of polypropylene

Composites of polypropylene (PP) and multi‐walled carbon nanotubes (MWCNTs) were prepared via melt‐mixing utilizing Li‐salt of 6‐amino heaxanoic acid (Li‐AHA) modified MWCNTs in the presence of a compatibilizer (polypropylene‐g‐maleic anhydride; PP‐g‐MA). Improved interaction between the anhydride group of PP‐g‐MA and the amine functionality of Li‐AHA was confirmed via FTIR and Raman spectroscopic analysis. A higher glass transition temperature (T_g) of the PP phase has been observed in these composites as compared to pristine MWCNTs‐based composites. The crystallization temperature (T_c) of the PP phase was increased as a function of pristine MWCNTs concentration in PP/MWCNTs composites indicating hetero‐nucleating action of MWCNTs. However, T_c value was decreased in the presence of Li‐AHA modified MWCNTs indicating the adsorbed Li‐AHA on the MWCNTs surface. Moreover, T_c value was higher in the presence of Li‐AHA modified MWCNTs with PP‐g‐MA as compared to that of without PP‐g‐MA, suggesting the desorbed Li‐AHA from the MWCNTs surface due to melt‐interfacial reaction. Further, MWCNTs were extracted by hot vacuum filtration technique from PP/MWCNTs composites containing Li‐AHA and PP‐g‐MA. The isothermal crystallization kinetics showed a variation in crystallization behavior of the PP phase in the corresponding composites as compared to the “extracted MWCNTs.” POLYM. ENG. SCI., 57:183–196, 2017. © 2016 Society of Plastics Engineers     

Intrinsic birefringence of amorphous poly(bisphenol-A carbonate)

The birefringence of uniaxially oriented poly(bisphenol-A carbonate) (PC) samples stretched over a wide range of temperatures has been measured accurately with a combination of the compensator and the wedge methods. The Hermans' orientation function of anisotropic PC was calculated from the measured dichroic ratio of the infrared absorption band at 1364 cm^-1. Measurements using differential scanning calorimetry, X-ray diffraction, or infrared spectroscopy indicated no stress-induced crystallinity in stretched amorphous PC. At each state having a defined molecular orientation, samples stretched below the glass transition temperature (T_g) always exhibited excess birefringence and slightly higher density. This phenomenon is attributed to bond distortion during stretching, a result of the suppression of large-scale segmental motions of polymer chains below the T_g. The birefringence of samples stretched above the T_g arises exclusively from the orientation effect as a result of greater chain mobility. These measured birefringence values are proportional to Hermans' orientation functions, yielding a linear relationship which allows precise determination of the intrinsic birefringence of amorphous PC as 0.192 ± 0.006.     

Polymer blends of poly(ethylene‐2,6‐naphthalate) with polystyrene compatibilized by styrene‐glycidyl methacrylate copolymers. I. Rheology,morphology, and mechanical properties

The compatibilization of blends of poly(ethylene‐2,6‐naphthalate) (PEN) with polystyrene (PS), through the styrene‐glycidyl methacrylate copolymers (SG) containing various glycidyl methacrylate (GMA) contents, was investigated in this study. SG copolymers are able to react with PEN terminal groups during melt blending, resulting in the formation of desirable SG‐g‐PEN copolymers in the blend. These in situ formed copolymers tend to reside along the interface preferentially as the result of interfacial reaction and thus function as effective compatibilizers in PEN/PS blends. The compatibilized blends exhibit higher viscosity, finer phase domain, and improved mechanical properties. It is found that the degree of grafting of the in situ formed SG‐g‐PEN copolymer has to be considered as well. In blends compatibilized with the SG copolymer containing higher GMA content, heavily grafted copolymers would be produced. The length of the styrene segment in these heavily grafted copolymers would be too short to penetrate deep enough into the PS phase to form effective entanglements, resulting in the lower compatibilization efficiency in PEN/PS blends. Consequently, the in situ formation of SG‐g‐PEN copolymers with an optimal degree of grafting is the key to achieving the best performance for the eventually produced PEN/PS blends through SG copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 967–975, 2003     

Microstructural modifications in uniaxially hot‐drawn polycyclohexylene terephthalate films

Semi‐aromatic thermoplastic polycyclohexylene terephthalate (PCT), initially wholly amorphous, was uniaxially drawn to study microstructural modifications as the appearance of the strain‐induced (S.I.) crystalline phase. Polyethylene terephthalate (PET) and poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) (PETG) are considered as reference materials in this work. In polycyclohexylene terephthalate (PCT) the presence of a saturated ring (which is not quite as rigid as the aromatic ring) modifies the characteristics of both thermal and S.I. crystallization. Samples with various draw ratios (drawing of PCT films is performed at T > T_g) were analyzed by Modulated Differential Scanning Calorimetry, wide angle X‐ray scattering, and birefringence measurements. In drawn PCT films, an S.I. crystalline phase appears continuously with the draw ratio and reaches 35%. For this polymer and for the highest draw ratio, the “true” amorphous fraction practically disappears. The material is composed only of the S.I. crystalline phase and the “rigid” amorphous phase. Polym. Eng. Sci. 44:509–517, 2004. © 2004 Society of Plastics Engineers.     

Role of 2‐hydroxyethyl end group on the thermal degradation of poly(ethylene terephthalate) and reactive melt mixing of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends

In an attempt to minimize the acetaldehyde formation at the processing temperatures (280–300°C) and the outer–inner transesterification reactions in the poly (ethylene terephthalate) (PET)–poly(ethylene naphthalate) (PEN) melt‐mixed blends, the hydroxyl chain ends of PET were capped using benzoyl chloride. The thermal characterization of the melt‐mixed PET–PEN blends at 300°C, as well as that of the corresponding homopolymers, was performed. Degradations were carried out under dynamic heating and isothermal conditions in both flowing nitrogen and static air atmosphere. The initial decomposition temperatures (T_i) were determined to draw useful information about the overall thermal stability of the studied compounds. Also, the glass transition temperature (T_g) was determined by finding data, indicating that the end‐capped copolymers showed a higher degradation stability compared to the unmodified PET and, when blended with PEN, seemed to be efficient in slowing the kinetic of transesterification leading to, for a finite time, the formation of block copolymers, as determined by ¹H‐NMR analysis. This is strong and direct evidence that the end‐capping of the ? OH chain ends influences the mechanism and the kinetic of transesterification. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Polylactide/nano‐ and micro‐scale silica composite films. II. Melting behavior and cold crystallization

Nonisothermal crystallization of polylactide (PLA)/silica composites prepared by (i) directly blending the PLA with nanoscale colloidal silica sol and by (ii) a sol–gel process are studied by differential scanning calorimeter (DSC) at various heating rates. Samples quenched from the molten state exhibited two melting endotherms (T_ml and T_mh) due to melt‐recrystallization during the DSC scans. Lower heating rate and the presence of silica particles generate a lower peak intensity ratio of T_ml /T_mh. The nonisothermal crystallization kinetics is analyzed by modified Avrami model, Ozawa model, and Liu‐Mo models. The modified Avrami and Liu‐Mo models successfully described the nonisothermal cold crystallization processes, but Ozawa is inapplicable. The nucleation constant (K_g) is calculated by modified Lauritzen‐Hoffman equation and the activation energy by Augis‐Bennett, Kissinger, and Takhor models. These calculated parameters indicate consistently that the nanoscale silica particles seem to form more heterogeneous nucleation to increase crystallization, but microscale one form hindrance to retard crystallization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Laser annealing of polyetheretherketone (PEEK)

Changes in the crystalline morphology and thermal behavior of amorphous poly(etheretherketone) (PEEK) films have been effected by irradiation with a continuous wave CO₂ laser. At high laser scan rate and power, PEEK films melt and requench into amorphous transparent films. At a scanning velocity of 14 μm/s and incident intensities ≥ 4.8 W/cm² and a Gaussian beam radius of 1.63 mm, PEEK films crystallize “completely” above T_g on laser annealing. Irradiation of PEEK films on a quartz substrate reduces the cooling rate, allowing slower and more perfect recrystallization. Similar changes are effected by reducing the laser scan velocity or by increasing the laser power. Depending on the experimental conditions, laser induced recrystallization may occur on annealing above T_g or on cooling from the melt.     

Influence of carbon nanotubes with different functional groups on the morphology and properties of PPO/PA6 blends

Carbon nanotubes with different functional groups were prepared and then incorporated into the poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6) blend via melt blending. The influence of different carbon nanotubes on the morphology and properties of the blend was studied. The results show that addition of pristine CNTs, CNTs‐OH, CNTs‐NH₂ leads to the evolution of the phase structure of PPO/PA6 (mass ratio: 60/40) blend from sea‐island to cocontinuous, whereas incorporation of CNTs‐COOH does not change the blend morphology due to serious aggregation of the carbon nanotubes. Incorporating different CNTs into PPO/PA6 blend increases the tensile modulus and storage modulus of the blends, whereas decreases slightly the tensile strength. At the same time, the glass transition temperatures (T_g) of PA6 and PPO are enhanced. ΔT_g, the gap between the T_g of PA6 and PPO, decreases with the addition of carbon nanotubes due to the stronger interaction of carbon nanotubes with PA6 than PPO. A similar tendency was found in the storage modulus (G′) and complex viscosity (η*) of the composites. The dispersion state of different carbon nanotubes and their interaction with polymer components are different, which causes the different confinement effect to the macromolecular chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure and properties of polypropylene/hydrotalcite nanocomposites

This article presents the study of the modification of the particle/matrix interface region and its effects on the structure and dynamic mechanical behavior of polypropylene (PP)/hydrotalcite nanocomposites prepared by melt extrusion. The interface modification was promoted by combinying the organophillization of the hydrotalcite particles with blending the PP with a maleic anhydride‐grafted‐PP (PP‐g‐MAH) or a maleic anhydride‐grafted‐poly(styrene‐co‐ethylenebutylene‐co‐styrene) (SEBS‐g‐MAH). Sodium dodecyl sulphate was used to promote the organophillization of the hydrotalcite particles. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) showed a partially exfoliated hydrotalcite structure, with an increasing exfoliation being achieved by adding a compatibilizer and organo‐modifying the particles. Values of the Young's modulus (E), storage modulus (E′), maximum tensile strength (σ_max), neck propagation strength (σ_neck), and elongation at break (ε_b) were found to depend both on the nature of the particle matrix interface as well as on the type of compatibilizer. Also, nanocomposites prepared with the organophillized particles showed lower T_g and loss factor values. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Morphology and texture development of uniaxially stretched poly(ethylene naphthalene‐2,6‐dicarboxylate)

The texture development of PEN films with different semicrystalline morphologies have been studied by X‐ray diffraction. These different structures have been obtained by uniaxially stretching PEN amorphous films at 100 and 160°C (below and above T_g) at different drawing ratios. Samples have also been characterized by DSC to determine the crystallinity ratios, the crystallization, and melting temperatures. To define the orientation of crystallites in the oriented samples, pole figures have been constructed, as a function of temperature and drawing ratio (DR) in the range 1.5–4. In the range from DR = 2 to 4 the orientation is clearly uniplanar‐axial. At T_draw = 100°C the crystallinity shown by DSC analysis is higher than the sample stretched at 160°C. The orientation is also higher when samples are stretched at 100°C. The naphthalene rings mainly stay in the plane of the film with a lower fraction perpendicular to the plane of the film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 395–401, 2007     

ELIMINATING FLOW INDUCED BIREFRINGENCE AND MINIMIZING THERMALLY INDUCED RESIDUAL STRESSES IN INJECTION MOLDED PARTS*

Eliminating flow-induced birefringence and stresses and reducing thermally induced stresses in the injection molded parts have been studied using rapid thermal response (RTR) molding technique. In the RTR molding, mold surface temperature can be rapidly raised above T _g in the filling stage, while the normal injection molding cycle time is still maintained. Therefore, the melt can fill the cavity at temperatures above T _g, which enables the flow-induced stresses to relax completely in a short time after filling and before vitrification. Residual stresses and birefringence in a RTR molded strip specimen are compared with the conventional molded parts by applying layer removal method and retardation measurement. For the material (Monsanto® Lustrex Polystyrene) and process conditions chosen, the birefringence level decreased as the RTR temperature approached and exceeded the glass transition temperature until it almost disappeared at a RTR temperature of 180°C. Reduction of magnitude and shift of peak location were observed in the gapwise stress profile for RTR molded specimen.

     

In situ AFM study of near‐surface crystallization in PET and PEN

The surface crystallization behavior of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6‐naphthalate) (PEN) spin‐coated thin films was compared by means of atomic force microscopy (AFM) with an in situ heating stage. As the films were heated up stepwise, characteristic surface crystals appeared at a crystallization temperature (T_c) in the near‐surface region which is about 15 °C under the bulk T_c, and were replaced by bulk crystals when the temperature was increased to the bulk T_c. In the case of films whose thickness is less than 70 nm (PET) and 60 nm (PEN), significant increases in the bulk T_c were observed. Scanning force microscopy (SFM) force‐distance curve measurements showed that the glass transition temperature (T_g) of the near‐surface region of PET and PEN were 22.0 and 26.6 °C below their bulk T_g (obtained by DSC). After the onset of surface crystallization, edge‐on and flat‐on crystals appeared at the free surface of PET and PEN thin films, whose morphologies are very different to those of the bulk crystals. Although the same general behavior was observed for both polyesters, there are significant differences both the influence of the surface and substrate on the transition temperatures, and in morphology of the surface crystals. These phenomena are discussed in terms of the differences in the mobility of polymer chains near the surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44269.     

Strong orientation correlation and optical anisotropy in blend of cellulose ester and poly(ethylene 2,6‐naphthalate) oligomer

Molecular orientation of two aromatic additives in cellulose acetate propionate (CAP) matrix was investigated from orientation birefringence data and an intermolecular orientation correlation represented by nematic interaction (NI) was evaluated. Poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) oligomers with low molecular weight (ca. 400 g mol^?1) were used as the additives. The NI strengths of CAP‐PET and CAP‐PEN were determined to be 0.28 ± 0.05 and 0.96 ± 0.15, respectively. In particular, compared with other polymer/polymer and polymer/small additive blends, the NI value in CAP/PEN blend is much stronger and represents the perfect orientation correlation. The strong orientation correlation is possibly due to the rigid naphtalate structure in PEN. Contrary, a relation between birefringence and orientation function for CAP in bulk and blend showed the same trend, suggesting that the orientation behavior of CAP determines the orientation birefringence. As two ester groups in CAP are responsible for birefringence, the alignment of the ester groups is affected by only the main chain orientation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40570.