Influence of charge density on rheological properties and dehydration dynamics of weakly charged poly(N-isopropylacrylamide) during phase transition

It is well-known that introduction of charged groups to poly(N-isopropylacrylamide) (PNIPAM) raises its phase transition temperature. However, the influence of charged groups on structural evolution and dehydration dynamics of weakly charged PNIPAM during phase transition still lacks systematic investigation. In the current study, armed with rheometer and two-dimensional Fourier transform infrared spectrometer (2D-FTIR), we investigated on mesoscopic and microscopic scales the phase transition of sodium poly(N-isopropylacrylamide-co-2-acrylamido-2-methylpropanesulfonate), abbreviated as poly(NIPAM-co-NaAMPS), with charge density of 1–10%. At ambient temperature, scaling exponent of poly(NIPAM-co-NaAMPS) varies from that of neutral polymer to polyelectrolytes as charge density increases. Above phase transition temperature, mesoscopic structure of poly(NIPAM-co-NaAMPS) varies from network of physical gel to viscoelastic liquid containing branched aggregates with increase of charge density, indicating increasing hindrance to intra/inter-chain association due to electrostatic repulsion. On a molecular level, poly(NIPAM-co-NaAMPS) exhibits distinctive microdynamic sequence of dehydration during phase transition, in contrast to neutral PNIPAM. In particular, sulfonate groups decouple the cooperative dehydration of alkyl and carbonyl groups, resulting in their distinctive phase transition temperature as well as temperature range. In analogy to hydration of proteins, it is proposed that the microdynamic sequence, implying the hydration stability of each group, is closely related to the density of hydration layer as well as influence of electrostatic field generated by charged groups. For poly(NIPAM-co-AMPS) with charge density of 3%, there still remains 72.3% of hydrogen bonds between carbonyl group and water at 60 °C, meanwhile a highly hydrated network forms with network strands 1–2 times as long as the copolymer chain length.     

Effects of mesoporous silica particles on the emulsion polymerization of methyl methacrylate

Rod‐like and spherical mesoporous SBA‐15 silica particles were synthesized as pure silicas and surface modified by organosilane coupling agents firstly, and then the effects of these mesoporous materials on the critical micelle concentration (CMC) of sodium dodecylsulfate (SDS), the stabilities of batch and semi‐continuous MMA emulsion polymerizations, and the molecular weights and molecular weight distributions of the polymer products were studied. The incorporation of both unmodified and silane‐modified forms of the mesoporous silica particles in the polymerization reaction increased the CMC of SDS. The presence of the unmodified mesoporous silica in the polymerization process led to instability in the batch emulsion polymerization process, as indicated by the formation of increased amounts of coagulum, and a decrease in the molecular weight of the polymer product. However, in comparison to the polymer formed in the absence of particle additives the molecular weight of the PMMA polymer increased with the amount of emulsifier and the addition of silane‐modified SBA‐15 particles, suggesting the growth of the polymer chains is facilitated at least in part by reaction in the pores of the particles. The improvement in molecular weight indicates that semi‐continuous MMA emulsion polymerization is best suited for the preparation of PMMA–mesoporous silica composites. POLYM. ENG. SCI., 54:2746–2752, 2014. © 2013 Society of Plastics Engineers     

Thermal analysis and non‐isothermal kinetics of poly(ethylene glycol) with different molecular weight

This study focuses on comprehensively investigating polyethylene glycol (PEG) with different molecular weight. Thermal properties of the PEGs were investigated by differential scanning calorimetry (DSC), as well as gradual melting and freezing tests with thermocouples. Results show that the degree of PEG crystallization increased with the increasing of the molecular weight of polymers. The temperatures of pure PEG 1000 and PEG 1000‐PEG 600 blends ranged from 20 to 50°C. The apparent activation energy of pure PEG1000 was 300 kJ/mol, whereas that of the PEG blend was 239 kJ/mol. During the crystallization process, Avrami index n ranged from 5 to 3 and half‐crystallization time t_1/2 decreased with the acceleration of the crystallization rate R. This difference was due to the increase in polydispersity of the PEG system and decrease in the degree of crystallization. POLYM. ENG. SCI., 54:2872–2876, 2014. © 2014 Society of Plastics Engineers     

Investigations on CaF2:Nd Microcrystal‐Glass Composites with High Transmittance and Long Fluorescence Lifetime

A kind of novel CaF₂:Nd microcrystal‐glass composites with high transmittance and long fluorescence lifetime were prepared by a two‐step melt‐quenching technique. Based on Mie theory, a theoretical estimate of the scattering losses was suggested for the microcrystal‐glass composites. By matching dispersion curve of the glass matrix and CaF₂ microcrystal in the range of UV–Vis‐NIR, the transmittance can reach 83%. The effects of CaF₂:Nd microcrystals/glass ratio on structure and optical properties were investigated. The composite sample‐doped 30 wt% CaF₂:Nd nano/microcrystals exhibits long fluorescence lifetime of 518 μs at 1051 nm.     

Dielectric Relaxor Evolution and Frequency‐Insensitive Giant Strains in (Bi0.5Na0.5)TiO3‐Modified Bi(Mg0.5Ti0.5)O3–PbTiO3 Ferroelectric Ceramics

The 0.45Bi(Mg_0.5Ti_0.5)O₃–(0.55 ? x)PbTiO₃–x(Bi_0.5Na_0.5)TiO₃ (BMT–PT–xBNT) ternary solid solution ceramics were prepared via a conventional solid‐state reaction method; the evolution of dielectric relaxor behavior and the electrostrain features were investigated. The XRD and dielectric measurements showed that all studied compositions own a single pseudocubic perovskite structure and undergo a diffuse‐to‐relaxor phase transition owing to the evolution of the domain from a frozen state to a dynamic state. The formation of the above dielectric relaxor behavior was further confirmed by a couple of measurements such as polarization loops, polarization current density curves, as well as bipolar strain loops. A large strain value of ~0.41% at a driving field of 7 kV/mm (normalized strain d₃₃* of ~590 pm/V) was obtained at room temperature for the composition with x = 0.32, which is located near the boundary between ergodic and nonergodic relaxor. Moreover, this electric field‐induced large strain was found to own a frequency‐insensitive characteristic.     

Physicochemical Properties Improvement of Soy Protein Using Divalent Ions During a Two-Step Fractionation Process

This study proposed a two-step fractionation (TSF) method with the addition of divalent ions to produce a soy protein with lower contents of lipophilic proteins and polar lipids (less-LP SPI). Flavor volatiles profiles and some functional properties of less-LP SPI were compared with soy protein prepared from conventional acid precipitated methods (APP). Protein composition and thermal behavior analysis indicated that less-LP SPI prepared with the addition of 10 mM Ca²⁺ during TSF process contained less lipophilic proteins and less denatured proteins. Gas chromatography–mass spectrometry analysis showed that the flavor volatiles content of less-LP SPI was significantly lower than that of APP (p < 0.05). The emulsifying stability of less-LP SPI was improved in comparison to that of APP (p < 0.05), as indicated by a less significant change in the creaming index and particle size (after 14 and 30 days of storage) of the emulsion prepared with the former than with the latter. Less-LP SPI had a similar or slightly lower water solubility compared to APP, but it possessed a higher protein content and a lower lipid level. These improvements in the properties of less-LP SPI might be due to the removal of lipophilic proteins and polar lipids by the divalent ions during the TSF process.     

The Competitive and Combining Effects of Grain Boundary and Fe/Mo Antisite Defects on the Low‐Field Magnetoresistance in Sr2FeMoO6

Sr₂FeMoO₆ ceramics with different Fe/Mo antisite defect (ASD) concentrations and grain‐boundary (GB) properties were prepared. The competitive and combining effects of GB and Fe/Mo ASD on the transport and magnetoresistance were discussed. The GB properties, that is, intergrain coupling strength, positively related with resistivity value, is extremely sensitive to the total flux of reducing gas, in general, lower total gas flux leads to larger resistivity, thus stronger intergrain coupling strength, and then the contributions of GB effect to low‐field magnetoresistance (LFMR) increase appreciably regardless of the amount of ASD. In detail, when ASD concentration is less than 26%, LFMR is dominantly controlled by the GB effect. However, the suppressed ASD effect on LFMR behavior comes to play when the ASD content is larger than or equal to 26%, where the GB and ASD effects contribute together to the LFMR.     

Preparation of Human Milk Fat Substitutes from Lard by Lipase‐Catalyzed Interesterification Based on Triacylglycerol profiles

Human milk fat substitutes (HMFSs) with triacylglycerol profiles highly similar to those of human milk fat (HMF) were prepared from lard by physical blending followed by enzymatic interesterification. Based on the fatty acid profiles of HMF, different vegetable and single‐cell oils were selected and added to the lard. Blend ratios were calculated based on established physical blending models. The blended oils were then enzymatically interesterified using a 1,3‐regiospecific lipase, Lipozyme RM IM (RML from Rhizomucor miehei immobilized on Duolite ES562; Novozymes A/S, Bagsværd, Denmark), to approximate HMF triacylglycerol (TAG) profiles, particularly with respect to the distribution of palmitic acid in the sn?2 position. The optimized blending ratios were determined to be: lard:sunflower oil:canola oil:palm kernel oil:palm oil:algal oil:microbial oil = 1.00:0.10:0.50:0.13:0.12:0.02:0.02. The optimized reaction conditions were determined to be: enzyme load of 11 wt%, temperature of 60 °C, water content of 3.5 wt%, and reaction time of 3 hours. The resulting product was evaluated for total and sn?2 fatty acids, polyunsaturated fatty acids, and TAG composition. A high degree of similarity was obtained, indicating the great potential of the product as a fat alternative for use in infant formulas.     

Hexafunctional poly(propylene glycol) based hydrogels for the removal of heavy metal ions

Two types of degradable poly(propylene glycol) (PPG) hydrogels that are suitable for the absorption of heavy metals have been presented. The PPG‐O‐P(O)Cl₂ fragments obtained by treating hexafunctional PPG with phosphorous oxychloride (POCl₃) react with 1,3‐propanediamine (PDA; Gel‐1 ) or PDA together with 1,2‐ethanedithiol ( Gel‐2 ), to yield cross‐linked and water‐swellable hydrogels in a one‐pot method. This protocol for the fabrication of PPG hydrogels exhibits promising advantages over prior methods including a short reaction time, mass‐production, easy separation, and high yield. A series of heavy metal ions were employed to test the adsorptive properties of the hydrogels. Gel‐2 shows better adsorption capacity than Gel‐1 for all the metal ions and the metal ions adsorption efficiency of the two types of hydrogels is in the order of Fe(III) > Pb(II) > Cd(II) > Zn(II) > Cu(II) > Ni(II) > Co(II) > Hg(II). The amounts of metal ions adsorbed increases with metal ion concentration and hydrogel dosage, but decreases with temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40610.     

Preparation of a chitosan‐based flame‐retardant synergist and its application in flame‐retardant polypropylene

A novel flame‐retardant synergist, chitosan/urea compound based phosphonic acid melamine salt (HUMCS), was synthesized and characterized by Fourier transform infrared spectroscopy and ³¹P‐NMR. Subsequently, HUMCS was added to a fire‐retardant polypropylene (PP) compound containing an intumescent flame‐retardant (IFR) system to improve its flame‐retardant properties. The PP/IFR/HUMCS composites were characterized by limiting oxygen index (LOI) tests, vertical burning tests (UL‐94 tests), microscale combustion calorimetry tests, and thermogravimetric analysis to study the combustion behavior and thermal stability. The addition of 3 wt % HUMCS increased the LOI from 31.4 to 33.0. The addition of HUMCS at a low additive amount reduced the peak heat‐release rate, total heat release, and heat‐release capacity obviously. Furthermore, scanning electron micrographs of char residues revealed that HUMCS could prevent the IFR–PP composites from forming a dense and compact multicell char, which could effectively protect the substrate material from combusting. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40845.