On the thermal degradation of poly(styrene sulfones). VII. Evaluations of poly(styrene sulfone) thermal stability using invariant kinetic parameters

The thermal degradation behavior of poly(styrene sulfone) was investigated by thermogravimetric analysis (TGA) measurement. This study described its thermal stability by applying the invariant kinetic parameter (IKP) method. The thermogravimetric and differential thermogravimetric analyses of different compositions of poly(styrene sulfones) were carried out over the temperature range 100–500°C under nitrogen. The kinetic parameters (preexponential factor and activation energy) of thermal decomposition of poly(styrene sulfone) can be obtained by dynamic measurement of TGA. The IKP method assumes that the kinetic parameters are independent of the experimental conditions. These parameters are computed without any hypothesis on the form of the kinetic degradation function. Invariant activation energies of the degradation of poly(styrene sulfone) show that the thermal stability decreases as the SO₂ content of poly(styrene sulfone) increases due to the thermal instability of the C? S bond. The relation equation, Ea_inv = 237.0 ? 290.5X_SO2, where X_SO2 is the molecular fraction of SO₂, was obtained to describe the effect of sulfur dioxide on the thermal stability of poly(styrene sulfone). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1698–1705, 2002     

Relationship between the composition of polycarbonate copolymers and the refractive index

With a polycarbonate (PC)–poly(methyl methacrylate) (PMMA) graft copolymer and a PC–poly(dimethyl siloxane) (PDMS) block copolymer, the relationship between the composition of PC copolymers and the refractive index (n_D) was investigated. According to the results, with a PMMA content of 38 wt %, the n_D value of the PC–PMMA graft copolymer was nearly the same as that of electrical (E) glass (n_D = 1.545), and with a PMMA content of 6 wt %, it was nearly the same as that of electrical corrosion resistance (ECR) glass (n_D = 1.579). However, with a PDMS content of 19 wt %, the n_D value of the PC–PDMS block copolymer was nearly the same as that of E glass, and with a PDMS content of 2 wt %, it was nearly the same as that of ECR glass. The combination of the PC–PDMS block copolymer and the glass fibers (GFs) of ECR glass led to haze values of 8 and 16% with GF contents of 10 and 20%, respectively. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 514–521, 2002; DOI 10.1002/app.2355     

Effect of Solvent Composition on Crystallization Process of Ascorbic Acid

The crystal growth kinetics of ascorbic acid in water and in the solvent systems water/ethanol, water/methanol, and water/propanol is determined by means of seeded isothermal batch crystallization experiments. The measurements are correlated by a power low equation of the form (G = k_g σⁿ). The composition of the solvent system is found to have a significant influence on the kinetic parameters of growth of ascorbic acid. An increase in growth rate in the presence of alcoholic solvents (20 wt %) is measured compared to experiments with pure water. The thermodynamic effect of the solvent on the growth kinetics is approached by the UNIFAC method. The kinetic effect of solvent composition is explained using the two‐step model. Both thermodynamic and kinetic analyses give the same result: The addition of alcoholic solvents (20 wt % ethanol, methanol, and propanol) to the ascorbic acid/water system slightly reduces the diffusion rate and significantly accelerates the surface integration process.     

Effect of doping polyacrylic acid with some dopants as studied by different techniques

The molecular weight of polyacrylic acid (PAA) was determined by a viscometric method using NaNO₃ as solvent at 30°C. The specific electric conductivities (σ) of PAA as well as PAA doped with carbon black (CB), chromium oxide (Cr₂O₃), and cupferron with different concentrations (from 0.25 to 1 wt %) were measured at a temperature range 360–400 K. IR spectra of some polymers were determined and it was shown that when PAA was doped with 0.5 wt % CB, a C? O? C band appeared at 775–875 cm^?1. The positron annihilation lifetime (PAL) spectra in PAA doped with the above‐mentioned dopants were measured as a function of their concentrations. It was observed that the short lifetime intensity I₁ decreased, whereas the intermediate lifetime intensity I₂, which is related to the conductivity of the material, increased with increasing the wt % of Cr₂O₃ and cupferron as well as at low concentrations of CB. These results are discussed in terms of the conducting island model. It was found that there were distinct positive relationships between σ and I₂. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 877–883, 2002; DOI 10.1002/app.10381     

Mechanical Properties and Degrading Behaviors of Aluminum Hypophosphite-Poly(Lactic Acid) (PLA) Nanocomposites

The flame retardancy of poly(lactic acid) (PLA)/aluminum hypophosphite (AHP, phosphorous content = 41.87 wt.%) nanocomposites (PLA/(AHP-x), x = 15%, 20%, 25%; and x denotes the weight percentage content of AHP) was greatly enhanced by melt blending of AHP into PLA through twin-screw extruder and injection-molding process. The UL 94 V-0 flammability rating can be reached for PLA/(AHP-20%) with the LOI value over 28.8. The well dispersion of the AHP in PLA/(AHP-x) was investigated by FT-IR spectra under the line mapping model. Based on TGA results under a non-isothermal condition, the thermal degradation kinetics of PLA/(AHP-x) composites were studied by Kissinger’s, Ozawa’s and Flynn-Wall-Ozawa’s (FWO’s) methods. And those thermal degradation dynamic analyses showed lower activation energy (E_K or E_O) (from 155 to 122 kJ·mol^–1) corresponded to higher content of AHP (from 15 to 25 wt.%) for PLA/(AHP-x) nanocomposites. Kissinger’s, FWO’s and Coast-Redfern’s methods were used to discriminate the kinetic models and kinetic parameters for the thermal degradation of PLA/(AHP-x), which suggested conversion function G (α) = [-ln(1-α)]^2/3 or G (α) = α for the investigated process. The flame retardant PLA nanocomposites obtained in this study will become safety environment-friendly potential candidates in household and automobile engineering with high performance.     

Rheological characterization of cellulose solutions in N‐methyl morpholine N‐oxide monohydrate

Three different modes of rheological properties were measured on 11 and 13 wt % solutions of cellulose in N‐methyl morpholine N‐oxide (NMMO) monohydrate, in which concentration range lyocell fibers of much reduced fibrillation are preferably produced. The dynamic rheological responses revealed that the Cox–Merz rule did not hold for these cellulose solutions. Both cellulose solutions showed a shear thinning behavior over the shear rate measured at 85, 95, 105, and 115°C. However, 13 wt % solution gave rise to yield behavior at 85ºC. The power law index ranged from 0.36 to 0.58. First normal stress difference (N₁) was increased with lowering temperature and with increasing concentration as expected. Plotting N₁ vs shear stress (τ_ω) gave almost a master curve independent of temperature and concentration, whose slope was about 0.93 for both cellulose solutions over the shear rate range observed (τ_ω > 500 Pa). In addition, the cellulose solutions gave high values of recoverable shear strain (S_R), ranging from 60 to 100. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 216–222, 2002     

Crystallization of poly(butylene terephthalate)/poly(ethylene octene) blends: Nonisothermal crystallization

Poly(ethylene octene) (POE), maleic anhydride grafted poly(ethylene octene) (mPOE), and a mixture of POE and mPOE were added to poly(butylene terephthalate) (PBT) to prepare PBT/POE (20 wt % POE), PBT/mPOE (20 wt % mPOE), and PBT/mPOE/POE (10 wt % mPOE and 10 wt % POE) blends with an extruder. The melting behavior of neat PBT and its blends nonisothermally crystallized from the melt was investigated with differential scanning calorimetry (DSC). Subsequent DSC scans exhibited two melting endotherms (T_mI and T_mII). T_mI was attributed to the melting of the crystals grown by normal primary crystallization, and T_mII was due to the melting of the more perfect crystals after reorganization during the DSC heating scan. The better dispersed second phases and higher cooling rate made the crystals that grew in normal primary crystallization less perfect and relatively prone to be organized during the DSC scan. The effects of POE and mPOE on the nonisothermal crystallization process were delineated by kinetic models. The dispersed phase hindered the crystallization; however, the well‐ dispersed phases of an even smaller size enhanced crystallization because of the higher nucleation density. The nucleation parameter, estimated from the modified Lauritzen–Hoffman equation, showed the same results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of chemical cellulose from ascidian tunic and their regenerated cellulose fibers

Chemical cellulose (dissolving pulp) was prepared from ascidian tunic by modified paper‐pulp process (prehydrolysis with acidic aqueous solution of H₂SO₄, digestion with alkali aqueous solution of NaOH/Na₂S, bleaching with aqueous NaOCl solution, and washing with acetone/water). The α‐ cellulose content and the degree of polymerization (DPw) of the chemical cellulose was about 98 wt % and 918, respectively. The Japanese Industrial Standard (JIS) whiteness of the chemical cellulose was about 98%. From the X‐ray diffraction patterns and ¹³C‐NMR spectrum, it was found that the chemical cellulose obtained here has cellulose Iβ crystal structure. A new regenerated cellulose fiber was prepared from the chemical cellulose by dry–wet spinning using N‐methylmorpholine‐ N‐oxide (NMMO)/water (87/13 wt %) as solvent. The new regenerated cellulose fiber prepared in this study has a higher ratio of wet‐to‐dry strength (<0.97) than commercially regenerated cellulose fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1634–1643, 2002.     

Disproportionation of toluene on ZSM5 washcoated monoliths

ZSM5 washcoated monoliths with zeolite loading ranging from 10 to 60 wt % were prepared, characterized, and examined for disproportionation of toluene. Toluene conversion increased with temperature and W/F_Ao but decreased with washcoat thickness. The selectivity of the most desirable isomer (p‐xylene) increased with a decrease in temperature, W/F_Ao and washcoat thickness. The high selectivity to p‐xylene indicates that the initially formed para isomer is easily removed from the zeolite pores in the thin washcoat to the bulk gas phase preventing further isomerization of the primary product. A reaction scheme has been proposed for this reaction and the kinetic parameters determined for the 10 wt % ZSM5 monolith. A one‐dimensional reactor model was developed to predict the performance of the reactor for disproportionation of toluene. The model equations were coupled with a module to calculate the concentration profile in the washcoat by considering the effect of diffusion and reaction. © 2011 American Institute of Chemical Engineers AIChE J, 00: 000–000, 2011     

Macroporous poly(N-isopropylacrylamide) networks

Summary Effects of the gel preparation temperature T _prep and the initial monomer concentration c on the swelling and the porosity properties of poly(N-isopropylacrylamide) (PNIPA) networks are described. PNIPA networks were prepared by free-radical crosslinking copolymerization of N-isopropylacrylamide and N,N'-methylene(bis)acrylamide (BAAm) in aqueous solutions. The crosslinker (BAAm) concentration in the initial monomer mixture was kept constant at 30 wt %. It was shown that macroporous PNIPA networks with a stable porous structure can be prepared at T _prep = 22.5°C and at an initial monomer concentration c > 5 w/v %. The PNIPA networks contain pores of about 0.1 μm in radius, corresponding to the interstices between the microspheres. The experimental data also show collapse of the porous structure in PNIPA networks formed at higher temperatures. Received: 30 January 2002 / Revised version: 16 May 2002 / Accepted: 1 June 2002     

Influence of degree of deacetylation on critical concentration of chitosan/dichloroacetic acid liquid‐crystalline solution

We prepared chitosans with various degrees of deacetylation (DDAs) by mixing completely deacetylated chitosan and acetic anhydride at room temperature without serious degradation and O‐substitution. We obtained a standard curve to measure DDA by plotting the IR absorbance ratio of A₁₅₆₀/A₂₈₈₀ against the known DDAs (from 1–100%) of 10 specimens. The effect of DDA on the critical concentration (C*) of chitosan/dichloroacetic acid solutions required to form mesophase was investigated by optical methods. A maximum C* value of 23 wt % appeared at a relative medium DDA (～20%). The effect was explained by the disordering of chains with medium composition ratios of the copolymer of glucosamine and N‐acetyl glucosamine. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1204–1208, 2002     

Kinetic role of C/Zr ratio in the reaction process,combustion behavior,and synthetic product of 70 wt.% (xC–Zr)–30 wt.% Cu

The kinetic role of C/Zr ratio in the reaction processes, combustion behaviors, and synthesized products of 70 wt.% (xC–Zr)–30 wt.% Cu was investigated. Results indicated that ZrC particles were produced by the replacement reaction between carbon atoms and Zr–Cu melt. With an increase in C/Zr ratio, more carbon atoms combined with the zirconium atoms in Zr–Cu liquid. As a result, the formation rate of massive ZrC enhanced, which shortened the ignition time of combustion reaction. On the other hand, the quantity, the lattice parameter, and the x value of synthetic ZrC_x increased, while the byproduct Cu_yZr_x compounds decreased. These effects contributed to an increase in the burning temperature and ZrC_x particle size. Moreover, it is also revealed that the formation of ZrC_x is a multistep process, which leads to an inhomogeneous distribution of the particle size. Results from this work offer a theoretical reference for the kinetic research of combustion synthesis and related techniques, and provide a valuable guide to the in situ synthesis of composite materials containing ZrC.     

A kinetic model for ammonia selective catalytic reduction over Cu-ZSM-5

Kinetic modeling, in combination with flow reactor experiments, was used in this study for simulating NH₃ selective catalytic reduction (SCR) of NO_x over Cu-ZSM-5. First the mass-transfer in the wash-coat was examined experimentally, by using two monoliths: one with 11 wt.% wash-coat and the other sample with 23 wt.% wash-coat. When the ratio between the total flow rate and the wash-coat amount was kept constant similar results for NO_x conversion and NH₃ slip were obtained, indicating no significant mass-transfer limitations in the wash-coat layer. A broad range of experimental conditions was used when developing the model: ammonia temperature programmed desorption (TPD), NH₃ oxidation, NO oxidation, and NH₃ SCR experiments with different NO-to-NO₂ ratios. 5% water was used in all experiments, since water affects the amount of ammonia stored and also the activity of the catalyst. The kinetic model contains seven reaction steps including these for: ammonia adsorption and desorption, NH₃ oxidation, NO oxidation, standard SCR (NO + O₂ + NH₃), rapid SCR (NO + NO₂ + NH₃), NO₂ SCR (NO₂ + NH₃) and N₂O formation. The model describes all experiments well. The kinetic parameters and 95% linearized confidence regions are given in the paper. The model was validated with six experiments not included in the kinetic parameter estimation. The ammonia concentration was varied from 200 up to 800 ppm using NO only as a NO_x source in the first experiment and 50% NO and 50% NO₂ in the second experiment. The model was also validated with transient experiments at 175 and 350 °C where the NO and NH₃ concentrations were varied stepwise with a duration of 2 min for each step. In addition, two short transient experiments were simulated where the NO₂ and NO levels as well as NO₂-to-NO_x ratio were varied. The model could describe all validation experiments very well.     

Influence of electron donors on the initial stage of cyclopolymerization of 1,5‐hexadiene with MgCl2‐supported Ziegler catalysts analyzed by temperature rising elution fractionation

Additive effects of donors on the initial polymerization of 1,5‐hexadiene with the MgCl₂‐supported Ziegler catalysts were investigated by using the stopped‐flow method, temperature rising elution fractionation (TREF) analysis, and kinetic study. The cyclopolymerization of 1,5‐hexadiene proceeded within an extremely short period (≤ 0.2 s) and yielded a unique poly(methylene‐1,3‐cyclopentane). cis ring content and cis–cis unit in meso dyad of the resulting polymer were increased by the addition of electron donors. The influence of internal and external donors was examined by the estimation of kinetic parameters and TREF analysis. Because the addition of the internal donor caused an obvious change in one of the kinetic parameters and the microstructure, an isospecific active site was considered to be formed by the addition of the internal donor. In the case of the external donor, the additive effects on the stereospecificity were weaker than those of the internal donor. It was expected from TREF measurements that the external donor modified an aspecific active site into a lower isospecific active site. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2976–2983, 2002; DOI 10.1002/app.2326     

Guaiacol HDO on La-modified Pt/Al2O3: Influence of rare-earth loading

The stability of the catalyst used in hydrodeoxygenation (HDO) of biomass-derived oils needs improvement. La has been applied in delaying Al₂O₃ phase-change under reaction conditions. Lanthanum (0.5–8 wt.%)-γ-alumina was studied as Pt (1 wt.%) carrier aimed at guaiacol (GUA) HDO. Materials characterization included N₂ physisorption, X-ray diffraction (XRD), thermal analysis, FTIR, UV–vis, and TPR. Solids pore size (~8–10 nm) was suitable for GUA (kinetic diameter~0.668 nm) hydrotreating. Mixed carriers were amorphous (XRD), suggesting well-dispersed La domains; meanwhile, carbonates/bicarbonates were formed (from CO₂) due to the basic surface properties of modified supports (FTIR). That could impart catalyst stability by inhibiting coking through the passivation of Lewis acidity on Al₂O₃. Pt reducibility increased with La loading in various formulations. However, that was not reflected in enhanced GUA HDO (T = 488 K and P = 3.2 MPa, batch reactor), presumably due to the strong metal–support interaction (SMSI), where LaO_x covered the metallic Pt particle surface. GUA HDO on various catalysts was approximated by pseudo-first-order kinetics (integral regime, k), where deviations were observed as La loading increased, presumably by an SMSI state that could affect the rate-determining step of the reaction mechanism. Basic sites provided by rare-earth could contribute to altering HDO reaction pathways as well. At 1 wt.% rare-earth, GUA HDO was maximized (k~25% higher than that on Pt/Al₂O₃), with that material also exhibiting similar deoxygenation (85%–90% at total GUA conversion) to the latter Pt over pristine alumina. Conversely, both parameters significantly diminished over the catalyst of the highest La content. Materials at low rare-earth concentrations deserve further studies focused on catalyst stability under HDO conditions.     

Toughening of vinylester–urethane hybrid resins through functionalized polymers

Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (K_c) and energy (G_c) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (T_g) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and T_g. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392     

Small angle neutron scattering study of structural aspects of nonionic surfactants (Tween 20 and Tween 80) in the presence of polyethylene glycols and triblock polymers

Small angle neutron scattering (SANS) technique has been used to study the micellar behavior of nonionic surfactants, Tween 20 and Tween 80 with additives like polyethylene glycols (PEG with molecular mass 400, 6000, and 15,000) and triblock polymers (TBPs) of varying composition. Surfactant‐additive interactions have been explained on the basis of parameters like aggregation number (N_agg), core radius (R_c), hard sphere radius (R_hs), volume fraction (ϕ) and axial ratio (b/a). The SANS analysis indicate the reduction in values of N_agg of Tween on addition of PEG additive. Shape of Tweens (3 wt %) micelles in the presence of PEG (10 wt %) is found to oblate ellipsoidal. Similarly, the shape of Tween (3 wt %) micelles is oblate ellipsoidal at low concentration of TBPs (1 wt %); however, they become spherical as the concentration of TBP increases to 10 wt %. The shape of micelles of pure TBPs also comes out to be spherical. Results reflects that at low concentration of TBP shape is controlled by surfactant (Tween 20 and Tween 80) while at high concentration of TBP shape of mixed micelle is controlled by TBP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Physical properties of lyocell fibers spun from different solution‐dope phases

The hydration number (n) of NMMO hydrates has a significant effect on the rheological properties and phase of the cellulose solutions in the hydrates. The physical properties of the lyocell fibers spun from the cellulose solutions in NMMO hydrates with different values of n were investigated relative to the phase of the solution dope. NMMO hydrate with n = 1.1 could not fully dissolve cellulose, resulting in a heterogeneous solution. NMMO hydrate with n = 0.72 produced a mesophase solution that exhibited a good spinnability. When NMMO hydrates with n = 0.72 and 1.0 were used, the lyocell fiber spun from 15 wt % solution dope gave higher tensile strength than that spun from 12 wt % solution dope. NMMO hydrate with n = 1.0 produced a lyocell fiber whose tensile strength was slightly affected by spin–draw ratio but the tensile strength of the lyocell fiber prepared from NMMO hydrate with n = 0.72 was monotonically increased with increasing spin–draw ratio. Further, the latter gave higher birefringence. The lyocell fiber spun from 15 wt % solution in NMMO hydrate with n = 0.72 produced finely fibrillated structures. When treated with sonic wave the lyocell fiber prepared from 15 wt % cellulose (DP_w 940) solution in NMMO hydrate with n = 0.72 yielded the most serious fibrillation on the fiber surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 981–989, 2002     

Delivery of bupivacaine included in poly(acrylamide‐co‐monomethyl itaconate) hydrogels as a function of the pH swelling medium

Copolymeric hydrogels of poly(acrylamide‐co‐monomethyl itaconate) (A/MMI) crosslinked with N,N′‐methylenbisacrylamide (NBA) were synthesized as devices for the controlled release of bupivacaine (Bp). Two compositions of the copolymer, 60A/40MMI and 75A/25MMI, were studied. A local anesthetic was included in the feed mixture of polymerization (2–8 mg Bp/tablet) and by immersion of the copolymeric tablets in an aqueous solution of the drug. A very large amount of Bp (36–38 mg Bp/tablet) was included in the gels by sorption due to interactions between the drug and the side groups of the hydrogels. Swelling and drug release were in accordance with the second Fick's law at the first stages of the processes. The swelling behavior of these copolymers depended on the pH of the medium. The equilibrium swelling degree (W_∞) was larger at pH 7.5 (W_∞ ≈ 90 wt %) than at pH 1.5 (W_∞ ≈ 52–64 wt %) due to the ionization of the side groups of the copolymer. Release of the drug also depended on the pH of the swelling medium; at pH 7.5, about 60% of the included drug was released, and at pH 1.5, about 80% was released. Bp release was controlled by the comonomer composition of the gels, their drug‐load, and the pH of the swelling medium. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 327–334, 2002