Bestimmung von Diffusionskoeffizienten nichtflüchtiger Additive in Polymerbeschichtungen mit Hilfe der inversen Mikro‐Raman‐Spektroskopie

In the scope of this work, the Fickian diffusion coefficient of a non‐volatile additive in the ternary system polymer/additive/solvent is determined by analysing the equalisation process of additive mass loading profiles in thin polymeric films by means of Inverse Micro Raman Spectroscopy (IMRS). The diffusion coefficients are obtained by fitting calculated to measured additive mass loading profiles. From the experiments presented in this work, for the first time the diffusion coefficient of the plasticizer triphenyl phosphate in polymeric solutions of methylene chloride and polyvinyl acetate could be determined over a wide range of additive and solvent mass loadings.     

Excess molar enthalpies of the ternary mixtures: Methyl tert‐butyl ether (or di‐isopropyl ether) + n‐octane + 2‐methylpentane at 293.15 K

Microcalorimetric measurements of excess molar enthalpies at 298.15 K are reported for the two ternary mixtures, methyl tert‐butyl ether (MTBE) or di‐isopropyl ether (DIPE) + n‐octane + 2‐methylpentane (2‐MP). The excess enthalpies for DIPE + 2‐MP are also reported. Smooth representations of the ternary enthalpies results are presented and used to construct constant excess molar enthalpy contours on Roozeboom diagrams. It is shown that good estimates of the ternary enthalpies can be obtained from the Liebermann and Fried model, using only the physical properties of the components and their binary mixtures.     

Non‐fickian three‐dimensional hindered moisture absorption in polymeric composites: Model development and validation

A new, three‐dimensional, anisotropic non‐Fickian diffusion model is developed to characterize moisture absorption in polymeric composites. The new hindered diffusion model extends the classical Fickian theory to include the effects of the interaction of diffusing molecules with the chemical and physical structure of polymeric composites. The numerical solution of the hindered diffusion model is obtained for a three‐dimensional, anisotropic domain by using a forward‐time, centered‐space finite difference technique. The moisture weight gain over time predicted by the model is shown to mimic a wide variety of anomalous absorption behavior, often exhibited by anisotropic composite laminates. The accuracy of the numerical solutions is verified by comparing the results to known analytical solutions of a one‐dimensional, “Langmuir‐type” diffusion model and for the limiting case of the three‐dimensional Fickian model. The utility of the proposed hindered diffusion model is demonstrated by accurately recovering the absorption behavior of three different material systems reported in literature. First, it is shown that the hindered diffusion model can accurately predict the moisture absorption data for unidirectional glass‐reinforced epoxy plates of varying dimensions exposed to a relative humidity of 80%. Second, the one‐dimensional version of the model is applied to experimental moisture absorption data for isotropic epoxy resin samples of different thicknesses. Anomalous effects due to sample thickness reported in the original article are accurately captured. Third, the proposed model is shown to be more accurate than a two‐stage diffusion model applied to moisture absorption data obtained from a woven 3‐ply carbon fiber reinforced bismaleimide composite. POLYM. COMPOS., 34:1144–1157, 2013. © 2013 Society of Plastics Engineers     

Prediction of diffusion in a ternary solvent–solvent–polymer blend by means of binary diffusion data: Comparison of experimental data and simulative results

Multicomponent diffusion of solvents in polymeric systems is not completely understood, despite many scientific contributions to the topic. Literature scarcely offers measurement data on diffusion for model validation in such systems. In this work, the ternary systems consisting of poly(vinyl acetate) and the solvents toluene and methanol was investigated experimentally and numerically. By means of inverse micro Raman spectroscopy (IMRS) concentration gradients in drying thin films have been measured. Initial composition of the samples has been varied systematically in order to detect mutual influence of the solvents' diffusive behavior. It was shown that the mobility of the different species is increased in the presence of other solvents as predicted by theory. This experimental data is provided for model validation. A new expression to calculate the diffusion coefficients in ternary mixtures is proposed which only requires binary data. This expression is tested by means of a model‐based simulation to predict the drying of ternary polymer solutions in terms of concentration profiles and residual solvent content. The results are in very good agreement with the experiments. Cross terms diffusion coefficients and thermodynamic factors were not found to be necessary for a satisfying prediction. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43899.     

混合电解质溶液在多孔颗粒内扩散的数学模型

建立了混合电解质溶液在多孔颗粒内扩散的数学模型,并由此计算了交互扩散效应的大小;讨论了单一扩散系数的菲克定律描述电解质混合物扩散的适用性;用模型处理了HCl-KCl-H_2O体系的实验数据,得出了有效主扩散系数和有效交互扩散系数.     

Dispersion polymerization of n‐butyl acrylate

The dispersion polymerization of n‐butyl acrylate (BA) was investigated using alcohol/water mixtures as the dispersion medium, 4,4′ ‐azobis‐(4‐cyanopentanoic acid) as the initiator, and polyvinylpyrrolidone (PVP) as the stabilizer. The effects of polymerization parameters, such as the alcohol/water ratio in the medium and the type and concentration of the polymeric stabilizer, on the resulting particle size and size distribution were studied. The final particle size and the stability of the dispersion system were found to be greatly influenced by the type of alcohol used in the mixture; that is, methanol or ethanol, even though the apparent solubility parameters are almost the same for the two types of mixtures. Poly(butyl acrylate) particles with controlled size and size distribution (monodisperse), and gel content were successfully prepared in a 90/10 methanol/water medium. It was found that the particle size decreased with increasing initiator concentration. This is the opposite of what was previously reported in the dispersion polymerizations of styrene and methyl methacrylate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2692–2709, 2002     

Study on swelling behavior of poly(sodium acrylate‐co‐2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid)/attapulgite macroporous superabsorbent composite

A fast swelling sulfonic acid macroporous superabsorbent composite is prepared by copolymerization of partially neutralized acrylic acid, 2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid, and attapulgite. The effects of pH values, ions, and their concentration on swelling behavior of sample are investigated. The results show that the swelling behavior of sample is affected by pH value. The supercase Π diffusion is observed in all NaCl solutions with different pH value. An overshooting effect appears in all solutions containing multivalent cations. This phenomenon may be attributed to the reorganization of the gel structure due to the formation of complex compound between cation and polymer network. A quantitative kinetics model proposed by Díez‐Peña is used to interprete it and the theoretical curves are in good agreement with the experimental data. For anions, it shows little effect on swelling process, and supercase Π diffusion is also observed no matter which kind of anion exists in swelling medium. POLYM. ENG. SCI., 55:681–687, 2015. © 2014 Society of Plastics Engineers     

Swelling and drug release profile of poly(2‐ethyl‐2‐oxazoline)‐based hydrogels prepared by gamma radiation‐induced copolymerization

Poly(2‐ethyl‐2‐oxazoline) and acrylic acid were copolymerized in different compositions using γ‐rays‐induced polymerization and cross‐linking to obtain a series of pH‐sensitive hydrogels. The preparation parameters that may affect the copolymerization process such as the feed solution composition and irradiation dose were optimized. Swelling characteristics of the obtained polymeric hydrogels were evaluated. The results show the significant effects of the hydrogel composition, soaking time, and pH on the swelling equilibrium. The diffusion parameters obtained at pH 1 and 7 show the possibility of using the prepared hydrogels in the field of colon‐specific drug delivery systems. Ibuprofen as a model drug was loaded into (poly(2‐ethyl‐2‐oxazoline)/acrylic acid) copolymer hydrogel to investigate their drug release behavior at different pH values. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

In situ thermal polymerization of an ionic liquid monomer for quasi‐solid‐state dye‐sensitized solar cells

In situ thermal polymerization of a model ionic liquid monomer and ionic liquids mixture to form gel electrolytes is developed for quasi‐solid‐state dye‐sensitized solar cells (Q‐DSSCs). The chemical structures and thermal property of the monomers and polymer are investigated in detail. The effect of iodine concentration on the conductivity and triiodide diffusion of the gel electrolytes is also investigated in detail. The conductivity and triiodide diffusion of the gel electrolytes increase with the increasing I₂ concentration, while excessive I₂ contents will decrease the electrical performances. Based on the in situ thermal polymeric gel electrolytes for Q‐DSSCs, highest power conversion efficiency of 5.01% has been obtained. The superior long‐term stability of fabricated DSSCs indicates that the cells based on in situ thermal polymeric gel electrolytes can overcome the drawbacks of the volatile liquid electrolyte. These results offer us a feasible method to explore new gel electrolytes for high‐performance Q‐DSSCs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42802.     

PFG‐NMR measurement of self‐diffusion coefficients of long‐chain α‐olefins and their mixtures in semi‐crystalline polyethylene

The self‐diffusion coefficients of C6–C16 long‐chain α‐olefins and their mixtures in semi‐crystalline polyethylene were measured through the pulsed field gradient nuclear magnetic resonance (PFG‐NMR). The effects of chain length, polyethylene (PE) type, and co‐monomer type in PE on the diffusion coefficients were investigated. Moreover, the influence of halohydrocarbon, cycloalkanes, and arene solvents on the diffusion coefficients of C12 α‐olefin in PE was characterized. The results have demonstrated that the diffusion coefficient of the single‐component α‐olefin in PE decreases exponentially with the increase of the carbon number of α‐olefin, and the crystallinity and crystal morphology of PE play a more important role than the co‐monomer type in determining the diffusion coefficients of α‐olefins. In addition, the apparent diffusion coefficients were used to represent the diffusion behaviors of the α‐olefin mixtures in PE. Owing to the presence of other hydrocarbon solvents, namely trichloromethane, cyclohexane, and benzene, the diffusion coefficients of C12 long‐chain α‐olefin in PE are significantly enhanced, and such promoting effect of the hydrocarbon solvents in polyolefin elastomer (POE) is much stronger than those in high‐density polyethylene (HDPE) and linear low‐density polyethylene (LLDPE). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44143.     

Coupled‐single‐particle and Monte Carlo model for propylene polymerization

A coupled‐single‐particle and Monte Carlo model was used to simulate propylene polymerization. To describe the effects of intraparticle transfer resistance on the polymerization kinetics, the polymeric multilayer model (PMLM) was applied. The reaction in each layer of the PMLM was described with the Monte Carlo method. The PMLM was solved together with the Monte Carlo model. Therefore, the model included the factors of the mass‐ and heat‐transfer resistance as well as the stochastic collision nature of the polymerization catalyzed with single‐site‐type/multiple‐site‐type catalysts. The model presented results such as the polymerization dynamics, the physical diffusion effect, and the polymer molecular weight and its distribution. The simulation data were compared with the experimental/actual data and the simulation results from the uniform Monte Carlo model. The results showed that the model was more accurate and offered deeper insight into propylene polymerization within such a microscopic reaction–diffusion system. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetic analysis of phenol adsorption from aqueous systems

The kinetic adsorption of mixtures of phenolic compounds onto a polymeric adsorbent from aqueous solutions was studied. Experimental data for single‐component solutions were obtained and fitted to a parallel diffusion model. Effective diffusion coefficients were related to liquid‐phase diffusion and surface diffusion. The effect of solute concentration and salinity on these parameters was also analysed. Van Laar's equation is proposed to evaluate the influence of concentration on diffusion. The adsorption kinetics for phenol and pcresol mixtures at different initial concentration ratios were determined and correctly adjusted to the mentioned kinetic model. Results confirm that adsorption from multicomponent aqueous solutions is a surface diffusion‐controlled process.     

Continuous production of polyester‐poly(ethylene terephthalate) resins in melt‐phase and solid‐state reactors

A simple reaction model has applied net polycondensation rates to predict the steady‐state performance of three distinct continuous processes for manufacturing polyester‐PET resins. A net melt‐phase polycondensation rate was described by the simple second‐order kinetics. A net solid‐state polycondensation rate was assumed to follow the modified second‐order kinetics with respect to active end group concentration. A moving‐packed bed requires a longer residence time to deal with the diffusion‐limited SSP of standard pellets or challenging pastilles. The calculations and data showed low IV pastilles to have much slower diffusion‐controlled SSP rates than medium IV pellets. The tanks‐in‐series model demonstrated a narrow RTD in a gas fluidization bed with five mixing stages. Higher reaction temperatures may significantly increase the low diffusion resistance SSP rates of smaller beads or micro‐pellets in a gas‐fluidized reactor. The reaction‐controlled SSP of micro‐beads becomes apparent at 230°C. The high IV melt resins may challenge the slow reaction rates of Ti or Al‐catalyzed SSP resins. The efficacy of catalyst promoters on Ti activity enhancement may depend upon various ligands in Ti glycolate, Ti citrate, or titanic acid. The thermo‐oxidative stability of Ti or Al‐catalyzed resins may decrease at higher hot air drying temperatures (188°C or above). POLYM. ENG. SCI., 57:505–519, 2017. © 2016 Society of Plastics Engineers     

Stimuli‐sensitive behaviour of novel betaine‐type polyampholytes

Novel linear and crosslinked polyampholytes of betaine structure based on acrylic acid and ethyl 3‐aminocrotonate (ethyl ester of 3‐amino‐2‐butenoic acid) have been synthesized by Michael addition reaction followed by radical copolymerization. The mechanism of formation of monomer and polymer betaines is discussed. The linear polyampholyte has been characterized by potentiometric titration, IR, NMR and GPC. Crosslinked polymeric betaines were synthesized in the presence of N,N′‐methylenebisacrylamide. The stimuli‐sensitive properties of amphoteric gels have been studied as a function of pH, ionic strength, water–organic mixture composition, electric, and combined electric and magnetic fields. The isoelectric points of linear and crosslinked polymeric betaines correspond to pH 2.0–2.1. The effect of ionic strength on the solution and gel properties of polybetaine has been interpreted on the basis of destruction of inter‐chain, intra‐chain and intra‐group salt bonds. Water–acetone, water–ethanol or water–DMF mixtures cause the shrinking of amphoteric gel due to change of the dielectric constant of the medium and decrease of the osmotic pressure. Electrocollapse is observed under the action of DC electric field. Simultaneously cross action of electric and magnetic fields enhances the collapsing rate. Appearance of pH gradient within the volume of polyampholyte gel under the externally imposed DC electric field has been observed. Copyright © 2003 Society of Chemical Industry     

Preparation and morphology characterization of microcellular styrene‐co‐acrylonitrile (SAN) foam processed in supercritical CO2

Microcellular polymeric foam structures have been generated using a pressure‐induced phase separation in concentrated mixtures of supercritical CO₂ and styrene‐co‐acrylonitrile (SAN). The process typically generates a microcellular core structure encased by a non‐porous skin. Pore growth occurs through two mechanisms: diffusion of CO₂ from polymer‐rich regions into the pores and also through CO₂ gas expansion. The effects of saturation pressure, temperature and swelling time on the cell size, cell density and bulk density of the porous materials have been studied. Higher CO₂ pressures (hence, higher fluid density) provided more CO₂ molecules for foaming, generated lower interfacial tension and viscosity in the polymer matrix, and thus produced lower cell size but higher cell densities. This trend was similar to what was observed in swelling time series. While the average cell size increased with increasing temperature, the cell density decreased. The trend of bulk density was similar to that of cell size. © 2000 Society of Chemical Industry     

Microporous network‐assisted formation of copper‐in‐polymer gradient composite film

In this article, a copper‐in‐polymer‐gradient composite film (CPGCF) was synthesized by electrochemical strategy via reducing a solvent‐swollen cathode film (SCF). The latex nanoparticles of a ternary copolymer including styrene, butyl acrylate, and acrylic acid structural units play the key role to form well‐graded copper distribution in this ternary copolymer matrix through the porous morphological structure developed by latex nanoparticle semimelt joining. The morphological structure along cross‐section of CPGCF includes three layers: (1) a dense copper layer in ternary copolymer matrix whose most outside was originally attached to cathode in electrochemical reactor, (2) a shrublike layer that grew from dense copper layer, and (3) a clear layer in which there is no obvious reduced copper phase whose most outside was originally contacted with liquid electrolyte medium in electrochemical reactor. As experimental aspects, the influences of emulsion polymerization conditions of ternary copolymer, predrying time and temperature of SCF, dc voltage in electrochemical reduction on CPGCF structure were investigated. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Phase Equilibria for Ternary Liquid Systems of (Water + Carboxylic Acid + 1‐Heptanol) at 293.15 K: Modelling Considerations

Liquid‐liquid equilibrium data of the solubility curves and tie‐line end compositions are presented for mixtures of [water (1) + formic acid, or acetic acid, or propanoic acid (2) + 1‐heptanol (3)] at T = 293.15 K and P = (101.3 ± 0.7) kPa. The properties and liquid‐liquid equilibria (LLE) of associated ternary systems have been correlated using a solvatochromic approach SERLAS. The tie‐lines were also predicted using the UNIFAC‐original model. The proposed model appears to be an improvement in data fit for the ternary systems yielding a mean error of 3.8% for all the systems considered.     

Swelling kinetics of a hydrogel of poly(ethylene glycol) and poly(acrylamide‐co‐styrene)

A hydrogel incorporating the hydrophilic polymer poly(ethylene glycol) and a copolymer of acrylamide and styrene was synthesized, and the dynamics of the water‐sorption process were studied. The effects of the composition of the hydrogel and the temperature of the swelling medium were investigated with respect to the water‐sorption characteristics of the hydrogel, and the kinetic parameters, including the swelling exponent and diffusion constant, were evaluated. The hydrogel was also judged for the antithrombogenic property of its surface. The experimental findings were explained on the basis of the core–shell polymeric structure of the hydrogel. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1419–1428, 2002     

Synthesis of novel optically active pyrrolidine‐containing polyaniline: A new heterogeneous organo polymeric‐base catalyst for direct Aldol reaction

An optically active pyrrolidine containing polyaniline, poly‐(2‐anilinomethylpyrrolidine) (PANiMp) is synthesized for the first time. PANiMp material is synthesized by simple one‐pot synthetic route and is characterized by circular dichroism, NMR, FTIR, and electronic absoroption spectral techniques. This novel polyaniline base is evaluated as new heterogeneous organo polymeric‐base catalyst for direct Aldol reaction in water medium. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymorphism and Mixing Phase Behavior in Ternary Mixture Systems of SOS–SSO–OSO: Formation of Molecular Compound Crystals

This paper reports the phase behavior of ternary mixtures of saturated and cis‐monounsaturated mixed‐acid triacylglycerols (TAG) of SOS (1,3‐distearoyl‐2‐oleoyl‐glycerol), SSO (1,2‐distearoyl‐3‐oleoyl‐rac‐glycerol), and OSO (1,3‐dioleoyl‐2‐stearoyl‐glycerol) examined with X‐ray diffractometry and a differential scanning calorimeter. The ternary mixtures were crystallized by cooling from melt (60 °C) to 5 °C, and the crystals were then stabilized by storing the mixture samples at 28 °C for 10 days. The following results were obtained. (1) Molecular compound (MC) crystals of stable β polymorph having a double‐chain‐length structure (β‐2) were formed in mixtures of SOS/SSO/OSO in which the concentration of SOS was 50% with varying concentrations of SSO/OSO. This is in contrast to the fact that the stable polymorphic forms of the component TAG are β‐3 for SOS and OSO and β′‐3 for SSO. (2) When the concentration of SOS deviated from 50%, immiscible mixtures of β‐2 MC made of SOS/SSO/OSO and the component TAG (β‐3 of SOS and OSO and β′‐3 of SSO) were formed. Therefore, ternary mixtures of SOS/(SSO + OSO) = 50/50 with different concentrations of SSO and OSO are miscible mixtures of β‐2 of SOS/SSO and SOS/OSO.