Toughening of poly(l-lactide) with poly(ε-caprolactone): Combined effects of matrix crystallization and impact modifier particle size

Enhancing matrix crystallization has been demonstrated to be an effective method to simultaneously improve the impact toughness and heat resistance of poly(l-lactide) (PLLA) modified with flexible polymers, such as poly(ε-caprolactone) (PCL). Unfortunately, increasing PLLA matrix crystallinity alone cannot guarantee the enhancement of impact toughness in most cases, so other structural parameters should be considered. In this work, taking PLLA/PCL (80/20) blend as an example, the combined roles of matrix crystallization and impact modifier particle size in the toughening have been investigated. PLLA matrix crystallinity was controlled by adding a highly effective nucleating agent and PCL particle size was tailored by varying processing conditions while maintaining constant interfacial adhesion. It is interesting to find that toughening is efficient only if matrix crystallinity and particle size are well matched. With the significant increase of matrix crystallinity, an evident decrease of optimum particle size for toughening PLLA has been identified for the first time. Therefore, suitable particle size is the precondition for highly crystalline matrix to work effectively in the toughening because only small particles (0.3–0.5 μm) are effective in trigger shear yielding mechanism of the matrix needed for good toughness, whereas relatively large particles (0.7–1.1 μm) are only capable of toughening amorphous matrix effectively by initiating multiple crazing of the matrix. Importantly, our findings can be used to well explain the reason for the different roles of matrix crystallization in the toughening of different PLLA blends reported in the literature. Furthermore, the heat resistance of the blend with a highly crystalline matrix is much better than that of the blend with an amorphous one as expected. This work could not only provide a new insight into the synergistic roles of matrix crystallization and modifier particle size in the toughening of PLLA but also set up a universal framework for designing high-performance PLLA products with both good impact toughness and high heat resistance.     

Vinyl‐addition type norbornene copolymers containing flexible spacers and sulfonated pendant groups for proton exchange membranes

Novel sulfonated poly(2‐butoxymethylenenorbornene‐co‐2‐(6‐phenoxy‐hexyloxymethylene)‐5‐norbornene [sP(BN/PhHN)] were prepared successfully through vinyl‐addition type polymerization and then sulfonated with concentrated sulfuric acid (98%) as sulfonating agent in a component solvent. The sP(BN/PhHN)‐40 with the maximal degree of sulfonation of 40% can be obtained by controlling the sulfonating reaction time from 8 to 20 h, and a proton conductivity of 3.35 × 10^?3 S/cm was achieved at 70°C. The methanol permeabilities of these membranes were in the range from 0.26 to 6.58 × 10^?7 cm²/s, which were remarkably lower than Nafion (2.36 × 10^?6 cm²/s). TEM analysis revealed that these side‐chain type membranes have a microphase separated structure composed of hydrophilic side‐chain domains and hydrophobic polynorbornene main chain domains. Sulfonated polynorbornene containing soft spacers displayed better properties, such as lower water uptake, high thermal properties, mechanical properties, and low methanol permeability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of novel hyperbranched polyimides end‐capped with metallophthalocyanines

A fluorinated hyperbranched polyimide (HBPI) is synthesized by using a triamine monomer, 1,3,5‐tris(2‐trifluoromethyl‐4‐aminophenoxy)benzene (TFAPOB) (B₃), as a “core” molecule, 4,4′‐oxydiphthalic anhydride (ODPA) as a A₂ monomer, and 4‐aminophthalonitrile as an end‐capping reagent. After that, a series of novel fluorinated hyperbranched polyimides end‐capped with metallophthalocyanines were prepared by the reactions of dicyanophenyl end‐capped hyperbranched polyimide with excessive amounts of 1,2‐dicyanobenzene and the corresponding metal salt in quinoline. The resulting polyimides containing metallophthalocyanine unites shows optical absorption in the visible region. The absorption bands of the polymers in chloroform solution are in the range of 665–701 nm. These polyimides show glass transition temperatures between 216 and 225°C, and the 5 wt % weight loss temperature of the polymers varied from 440 to 543°C under nitrogen. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Transferring noncharring polyolefins to charring polymers with the presence of Mo/Mg/Ni/O catalysts and the application in flame retardancy

This article presents a novel investigation on the Mo/Mg/Ni/O catalysts (Nmm‐cats) with which the noncharring polyolefins are basically transferred to the charring polymers under forced flaming conditions and the flame retardancy of polyolefins is improved dramatically. The results of model charring experiments show that when appropriate Mo/Mg/Ni molar ratio is adopted and only 3% Nmm‐cats is blended, the Nmm‐cats belong to high‐efficient charring catalysts that can deposit 56 and 64 wt % of volatile products in‐situ from linear low‐density polyethylene (LLDPE) and polypropylene (PP), respectively. The charring properties are characterized by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy; and the char‐forming mechanisms are analyzed by wide‐angle X‐ray diffraction experiment. The improvement in flammability properties for LLDPE and PP is demonstrated by using a cone calorimeter. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel Series of Low‐Firing Microwave Dielectric Ceramics: Ca5A4(VO4)6 (A2+ = Mg,Zn)

Using a conventional solid‐state reaction Ca₅A₄(VO₄)₆ (A²⁺ = Mg, Zn) ceramics were prepared and their microwave dielectric properties were investigated for the first time. X‐ray diffraction revealed the formation of pure‐phase ceramics with a cubic garnet structure for both samples. Two promising ceramics Ca₅Zn₄(VO₄)₆ and Ca₅Mg₄(VO₄)₆ sintered at 725°C and 800°C were found to possess good microwave dielectric properties: ε_r = 11.7 and 9.2, Q × f = 49 400 GHz (at 9.7 GHz) and 53 300 GHz (at 10.6 GHz), and τ_f = ?83 and ?50 ppm/°C, respectively.     

Low‐Temperature Sintering and Microwave Dielectric Properties of (Mg0.95Zn0.05)2(Ti0.8Sn0.2)O4–(Ca0.8Sr0.2)TiO3 Composite Ceramics

0.9(Mg_0.95Zn_0.05)₂(Ti_0.8Sn_0.2)O₄–0.1(Ca_0.8Sr_0.2)TiO₃ (MZTS–CST) ceramics were prepared by a conventional solid‐state route. The MZTS–CST ceramics sintered at 1325°C exhibited ε_r = 18.2, Q × f = 49 120 GHz (at 8.1 GHz), and τ_f = 15 ppm/°C. The effects of LiF–Fe₂O₃–V₂O₅ (LFV) addition on the sinterability, phase composition, microstructure, and microwave dielectric properties of MZTS–CST were investigated. Eutectic liquid phases 0.12CaF₂/0.28MgF₂/0.6LiF and MgV₂O₆ were developed, which lowered the sintering temperature of MZTS–CST ceramics from 1325°C to 950°C. X‐ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS) analysis revealed that MZTS and CST coexisted in the sintered ceramics. Secondary phase Ca₅Mg₄(VO₄)₆ as well as residual liquid phase affected the microwave dielectric properties of MZTS–CST composite ceramics. Typically, the MZTS–CST–5.3LFV composite ceramics sintered at 950°C showed excellent microwave dielectric properties: ε_r = 16.3, Q × f = 30 790 GHz (at 8.3 GHz), and τ_f = ?10 ppm/°C.     

Composition Inhomogeneity due to Alkaline Volatilization in Li‐Modified (K,Na)NbO3 Lead‐Free Piezoceramics

Alkaline volatilization during sintering in (K, Na)NbO₃ (KNN)‐based lead‐free piezoceramics is a problem that causes non‐stoichiometry and hence affects the phase structures and properties. This work investigated the depth‐dependent distributions of alkaline elements in Li‐modified KNN ceramics using X‐ray photoelectron spectroscopy and Raman spectroscopy. It was found that Li evaporated more severely than Na and K, consequently almost no Li elements remained on the as‐sintered surface, while its content became stable at the depth over 55 μm from the outmost surface. In addition, X‐ray diffraction results suggested the phase structure might show discrepancy at the pellet surface and the interior part due to the textured surface grains.     

Fluorescent‐tagged maleic anhydride‐allylpolyethoxy carboxylate copolymer as an environmentally benign inhibitor for calcium phosphate in industrial cooling systems

Allyloxy polyethoxy ether (APEG) and succinic anhydride were used to prepare allyloxy polyethoxy carboxylate (APEL). 8‐hydroxy‐1,3,6‐pyrene trisulfonic acid trisodium salt (PY) was reacted with allyl chloride to produce fluorescent monomer 8‐allyloxy‐1,3,6‐pyrene trisulfonic acid trisodium salt (PA). APEL and PA were copolymerized with maleic anhydride (MA) to synthesize PA tagged no phosphate and nitrogen‐free calcium phosphate inhibitor POLY(MA–APEL–PA). Structures of PA, APEG, APEL, and POLY(MA–APEL–PA) were carried out by FTIR and ¹H‐NMR. Different MA : APEL mole ratios were employed for the manufacture of POLY(MA–APEL–PA) to study the effect of mole ratio on performance of POLY(MA–APEL–PA). Relationship between POLY(MA–APEL–PA)'s fluorescent intensity and its dosage was studied. The results indicate that capability of POLY(MA–APEL–PA) is heavily depended on the mole ratio of MA : APEL. Correlation coefficient r of POLY(MA–APEL–PA)'s fluorescent intensity and its dosage is 0.9999, and detection limit of POLY(MA–APEL–PA) is 0.86 mg/L. POLY(MA–APEL–PA) can be used to accurately measure polymer consumption on line besides providing excellent calcium phosphate inhibition. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

A VUV Photoionization Aerosol Time-of-Flight Mass Spectrometer with a RF-Powered VUV Lamp for Laboratory-Based Organic Aerosol Measurements

A vacuum ultraviolet (VUV) photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) has been developed for real-time, quantitative chemical analysis of organic particles in laboratory environments. A nozzle of ～ 0.12 mm orifice combined with an aerodynamic lens assembly and a three stage differential pumping system is used to sample particles at atmospheric pressure. The particles are vaporized on a thermal heater, and then the nascent vapor is photoionized by light generated with a RF-powered VUV lamp. A 0.41 V/cm electric field is used to drive the ions from the ionization region into the ion extraction region where a positive electric pulse repels the ions into a reflectron mass spectrometer. The mass resolution of the spectrometer is ～ 350 and the detection limit is ～ 400 μ m ³ . The signal intensities observed are linear with the mass concentration of aerosols. Oleic acid particles are well quantified with an uncertainty of 15% in mass concentrations ranging from 3.9 mg/m ³ to 392 mg/m ³ . The VUV-ATOFMS has substantial potential for the use in laboratory investigations on organic aerosol chemistry.