Soap‐free emulsion copolymerization of perfluoroalkyl acrylates in the presence of a reactive surfactant

Soap‐free emulsion copolymerization of perfluoroalkyl acrylate (FA)/methyl methacrylate (MMA)/n‐butyl acrylate (n‐BA) was carried out in the presence of sodium 2‐acrylamide‐2‐methyl propanesulfonate (AMPSNa) as a reactive surfactant and potassium persulfate (KPS) as an initiator. An analysis of the effects of concentration of AMPSNa, KPS, FA as well as polymerization temperature on the kinetic features (rate of polymerization) and colloidal characteristics (mean particle diameter, particle disperse index, particle numbers, and surface charge density) was followed. NMR, FTIR, AFM, and fluorine‐selective electrode analysis were used to characterize the composition and morphology of the FA copolymers. Both AFM analysis and contact angle measurements strongly implied that the fluorinated segments migrated to the outmost surface and created films with lower surface energy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2438–2444, 2007     

Effects of Y2O3 and ZrO2 on the Densification of Si3N4-Zr(Y)O2 Composites

The effects of ZrO₂ and Y₂O₃ on the densification of hotpressed Si₃N₄-Zr(Y)O₂ composites have been studied. High density could not be obtained by the addition of pure or 3-mol%-Y₂O₃-doped ZrO₂ in this composite; however, nearly full density (>97%) could be obtained in Si₃N₄ using 6- and 8-mol%-Y₂O₃-doped ZrO₂. It is concluded that Y₂O₃ diffusing out from the added Zr(Y)O₂ promoted the densification and that ZrO₂ also had some role in the formation of an oxynitride glass.     

Synthesis of copolymers of tert‐butyl vinyl ether with maleic and citraconic anhydrides

In the present study, the effects of charge‐transfer complex formation and intramolecular fragmentation (side‐chain lactonization) in radical copolymerization of tert‐butyl vinyl ether (t‐BVE) with anhydrides of maleic (MA) and citraconic (CA) acids and the structure–thermal behavior relationships of the resulting copolymers were examined using the ¹H‐NMR, FTIR, DSC, and TGA analysis methods. It was shown that copolymerization under the chosen conditions proceeded through intramolecular fragmentation with the formation of γ‐lactone units. Side‐chain fragmentation of t‐BVE–MA and t‐BVE–CA copolymers also was confirmed by TGA and DSC analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2455–2463, 2006 2006     

C3S在NaOH和水中早期水化的ESCA研究

用ＥＳＣＡ研究了Ｃ３Ｓ在水中和ＮａＯＨ溶液中水化１－１０ｍｉｎ试样的表面组成;用等离子发射光谱仪测定了Ｃ３Ｓ早期水化液相中的组成,结果表明：Ｃ３Ｓ早期水化表面组成ｎ（Ｃａ）／ｎ（Ｓｉ）〉３,或ｎ（Ｃａ＋Ｎａ）／ｎ（Ｓｉ）〉３,形成一富Ｃａ层,初步认为Ｃ３Ｓ在ＮａＯＨ溶液中水化,Ｃａ＾３＋溶出受阻而Ｓｉ＾４＋溶出加快：Ｎａ在水化早期进入双电层和表面组成中,实验表明,欲采用ＥＳＣＡ技术测定Ｃ３Ｓ早期水     

Exploring single electrode reactions in polymer electrolyte fuel cells

Utilising a pseudo-reference electrode in polymer electrolyte fuel cells allows for the separation of anodic and cathodic contributions to the entire cell impedance. Modelling the impedance responses by using equivalent circuits inhibits the investigation of kinetic parameters of the basic electrochemical reactions, which take place at single electrode-electrolyte interfaces. Therefore, we evaluate single electrode impedance measurements by a kinetic model, which is based on specific reaction pathways, either for the oxygen reduction reaction (ORR) or the hydrogen oxidation reaction (HOR). As a consequence, it is possible to obtain kinetic parameters for the specific reaction of interest. Furthermore, the information gained from the single electrode impedance measurements and the kinetic model can give insight into single reactions steps. In particular, the ORR has to include a chemical step in the reaction pathway.     

One‐step synthesis and ring‐opening polymerization of novel macrocyclic(arylene multisulfide) oligomers

A series of macrocyclic(arylene multisulfide) oligomers were synthesized under high dilution conditions by reacting diphenyl ether/diphenyl/diphenyl disulfide/diphenyl methane with dichloro disulfide in the presence of a trace amount of iron powder by a one‐step reaction. From MALDI‐TOF mass spectra, it was established that the repeating units of the cyclization ranged from two to seven and the unit of macrocyclic(arylene multisulfide) oligomers had one to seven sulfur atoms. The macrocyclic oligomers readily underwent ring‐opening polymerization in the melt, resulting in linear, high molecular weight polymultisulfides. DSC thermograms demonstrated that the four polymultisulfides, derived from the macrocyclic(arylene multisulfide) oligomers, are amorphous in nature. The macrocyclic(arylene multisulfide) oligomers and polymers were analyzed by MALDI‐TOF‐MS, IR, HPLC, NMR, DSC, and TGA methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 735–741, 2004     

Biobased thermosets from the free‐radical copolymerization of conjugated linseed oil

New polymeric thermosets were prepared through the bulk free‐radical copolymerization of 100% conjugated linseed oil, acrylonitrile, and divinylbenzene. Under the appropriate reaction conditions and with the appropriate curing sequence, 61–96 wt % of the oil was incorporated into the crosslinked thermosets. The resulting yellow, transparent thermosets varied from being soft and flexible to being hard and brittle. Dynamic mechanical analysis and thermogravimetric analysis showed that these thermosets had good mechanical properties and thermal stability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 979–985, 2007     

Gas Hold‐Up in Stirred Tank Reactors in the Presence of Inorganic Electrolytes

Gas hold‐up (?_G) in air‐aqueous electrolyte solutions in stirred tank reactors (STR) is correlated using a relative gas dispersion parameter, N/N_cd and a surface tension factor (STF), (c/z)(dδ/dc)². For electrolyte concentration below transition concentration (c_t) a single correlation in the form of ?_G = f(N/N_cd, vvm, STF) shows good agreement with gas hold‐up data over a wide range of system and operating conditions. Above ct no effect of STF on gas hold‐up is observed and the correlation obtained is of the form ?_G = f(N/N_cd, vvm). Data available in the literature on large STR show good fit with the proposed correlation.     

Effect of Co2+, Ni2+, Cu2+, or Zn2+ on properties of polyaniline nanoparticles

Uniform polyaniline (PANI) nanoparticles with typical sizes of about 50 nm were electropolymerized on indium tin oxide surfaces in the presence of Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺. According to shaping theory, we first suggest the reason forming PANI spherical particles. Their conductivity, UV‐vis spectra, FTIR spectra, X‐ray diffraction, and thermogravimetric analysis were investigated. The conductivities and crystallinity of PANI doped with these ions are higher than those of PANI doped with HCl (PANI/HCl). Both UV‐vis absorption spectra and FTIR spectra indicate the interactions between Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ and PANI chains. TG analysis also shows that the thermal stability of PANI doped by Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ is lower than that of PANI/HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Comparative effects of cobalt carboxylates on the thermo‐oxidative degradation of LDPE films

This article reports the effect of three cobalt carboxylates—cobalt stearate (CoSt₃), cobalt palmitate (CoPal₃), and cobalt laurate (CoLau₃)—on the thermo‐oxidative degradation of low‐density polyethylene (LDPE) films prepared by sheeting process. The carboxylates were blended with LDPE in the concentration range of 0.05–0.2% (w/w). The degradation was monitored by techniques such as FTIR spectroscopy, change in the mechanical properties (tensile strength and elongation at break), viscometry, surface electron microscopy, melt flow index measurements, and apparent density measurements. Studies indicate that films containing these additives are highly susceptible to thermo‐oxidative degradation. Oxygen containing functionalities such as carbonyl and vinyl species are generated on the surface of polyethylene because of thermo‐oxidation, as indicated by FTIR studies. This oxidative process is accelerated in the presence of cobalt carboxylates. The degradation of LDPE was found to increase proportionally with concentration as well as with increasing chain length of the cobalt carboxylate, and follow the order CoSt₃ > CoPal₃ > CoLau₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3758–3765, 2007