Nuclear magnetic resonance relaxation studies of polyacrylamide solution

 The cohesive interaction among polymer chains in a polyacrylamide (PAAm)–D₂O solution has been studied by NMR relaxation. The NMR relaxation times of PAAm in the good solvent D₂O were measured at different temperatures. The results show that the solution system has a high local viscosity and that its relaxation characteristic is soft-solid-like. The temperature dependence of the relaxation behavior of the solution is obviously different from that of ordinary polymer solutions. The difference lies in the relaxation behavior of the methylene protons in the main chain of PAAm, as shown by analyzing the relaxation process with single exponential and biexponential decays. As the temperature increases, the solvation is weakened, leading polymer chains to form curling coils, thus hindering the movement of the methylene protons among the main chains. It can be expected from the existence of 80% fast-relaxing protons that there are a zhigh number of entanglements among the polymer chains in PAAm solution. The information about entanglements among the polymer chains can be deduced from the biexponential dependence of the spin–spin relaxation on the concentration of the polymer solutions. Received: 14 April 1999/Accepted in revised form: 12 October 1999     

溶液中尼龙11的NMR弛豫研究

用 2DNMR(HMQC)技术归属了溶液中尼龙 11分子的主要1H和13 C NMR共振信号 ,并通过变温和变浓度 1H NMR弛豫时间的测定 ,得到了尼龙 11溶液中氢键结构变化的动力学信息 .结果表明 ,溶液中尼龙 11分子的弛豫行为与一般高聚物不同 ,随着温度升高 ,尼龙链间相互作用逐渐减弱 ,尼龙分子与溶剂小分子间相互作用逐渐增强 ,尼龙链间氢键逐渐离解 ,而离解出来的自由NH和CO基团又与溶剂小分子间生成氢键 .尼龙 11链卷曲堆积成无规线团状 ,一部分溶剂被包裹在内部并和α CO质子成为一个整体而一起运动 .变浓度实验弛豫过程呈现双指数特性 ,快弛豫部分随体系浓度增加而增多 ,表明聚合物溶液中凝聚缠结含量的增大 ,这种凝聚缠结是由溶液中氢键引起分子链物理交联成网而形成的 .随着浓度增加 ,溶液逐渐变成局部粘度较大的类似软固体     

The influence of shear rate, temperature and chain conformation on the critical concentration c

 When viscometry is used, a crossover phenomenon is observed separating the dilute solutions into extremely dilute solutions and dilute solutions. The critical concentration c ^**, determined from this crossover phenomenon, strongly depends on the shear rate in the solution. At very high values of shear rate the critical concentration c ^** becomes very low and depends only on the contour length of the elongated chains of different polymers. An increase of the temperature induces an increase of c ^** because the relaxation time of the chains decreases. If a polymer adopts a rodlike conformation (in a given solvent at a given temperature) the excluded volume of its chains increases and its critical concentration c ^** decreases. Received: 14 October 1996 Accepted: 3 March 1997     

Carboxylic acid functionalization of nylon 6 by radiation grafting and conversion to zinc salts: Effects on physical properties

 Functionalization of polymers by grafting monomeric species on to the backbone of molecular chains with the use of γ-radiation has been used extensively. In this work methacrylic acid was grafted onto a commercial grade of polycaproamide (Nylon 6) by preirradiating the polymer granules to 15 kGy at a rate of 1.0 kGy per hour and subsequently immersing these in a 10% aqueous solution of methacrylic acid in the presence of small quantities of FeSO₄ as homopolymerization inhibitor. The polymer was subsequently neutralized by mixing it with zinc acetylacetonate in a laboratory scale melt mixing device. The acid-grafting polymer modification resulted in an increase in glass transition temperature, while the addition of zinc acetylacetonate gave rise to two transitions: The lower transition corresponds to a miscible mixture of free polyamide and acid-grafted polymer, both plasticized with undecomposed zinc compound, while the upper transition corresponds to the zinc salt of the acid grafted polyamide. Through rheological measurements it was shown that both the acid-grafted polymer and the derived zinc salt have a branched structure, possibly containing also some crosslinked domains. Large improvements in solvent resistance were observed for both type of polymer modifications. Received: 13 December 1996 Accepted: 10 February 1997     

Dynamic behavior of polymer surface and the time dependence of contact angle

The increased attention has been focused on the re-searches of soft materials proposed by Pierre-Gilles de Gennes, a Nobel Prize Laureate in Physics. A special issue of “Science” on soft surfaces was published in 2002 to review specific surface properti…     

Studies on the CMC and Thermodynamic Functions of a Cationic Surfactant in DMF/Long-Chain Alcohol Systems Using a Microcalorimetric Method

The power-time curves of the micelle formation process were determined at four temperatures for a cationic surfactant [cetyltrimethylammonium bromide (CTAB)] in a non-aqueous solvent [N,N-dimethylformamide (DMF)] by titration microcalorimetry. From the data of the minimum of the titration point and the area of the power-time curves, values of their CMC and ΔH _m ^θ were obtained. Values of ΔG _m ^θ and ΔS _m ^θ were also calculated according to standard thermodynamic relations. For the cationic surfactant CTAB, the relationships involving the carbon numbers of the alcohols, the alcohol’s concentration, and the temperature on the CMC, and also the thermodynamic functions for micellization are discussed. For systems containing an identical concentration of various alcohols, values of the CMC, ΔH _m ^θ and ΔS _m ^θ increased whereas those of ΔG _m ^θ decreased with increasing temperature. For systems containing identical alcohol concentrations at the same constant temperature, values of the CMC, ΔH _m ^θ ,ΔG _m ^θ and ΔS _m ^θ decreased with increasing carbon number of the alcohol. For systems containing the same alcohol at the same temperature, the CMC and ΔG _m ^θ values increased whereas ΔH _m ^θ and ΔS _m ^θ decreased with increasing alcohol concentration.     

Molecular Simulation to Explore the Dissolution Behavior of Sulfur in Carbon Disulfide

Soluble sulfur (S₈) and insoluble sulfur (IS) have different application fields, and molecular dynamics simulation can reveal their differences in solubility in solvents. It is found that in the simulated carbon disulfide (CS₂) solvent, soluble sulfur in the form of clusters mainly promotes the dissolution of clusters through van der Waals interaction between solvent molecules (CS₂) and S₈, and the solubility gradually increases with the increase in temperature. However, the strong interaction between polymer chains of insoluble sulfur in the form of polymer hinders the diffusion of IS into CS₂ solvent, which is not conducive to high-temperature dissolution. The simulated solubility parameter shows that the solubility parameter of soluble sulfur is closer to that of the solvent, which is consistent with the above explanation that soluble sulfur is easy to dissolve.     

A thermochemical study of the coordination reactions of La(III) with alanine and glycine

The solid-state coordination reactions of lanthanum chloride with alanine and glycine, and lanthanum nitrate with alanine have been studied by classical solution calorimetry. The molar dissolution enthalpies of the reactants and the products in 2 mol L^-1 HCl solvent of these three solid-solid coordination reactions have been measured using an isoperibol calorimeter. From the results and other auxiliary quantities, the standard molar formation enthalpies have been determined to be Δ_f H _m ^θ[La(Ala)₃Cl₃·3H₂O(s), 298.2 K]= -3716.3 kJ mol^-1, Δ_f H _m ^θ [La(Gly)₃Cl₃·5H₂O(s), 298.2 K]= -4223.0 kJ mol^-1 and Δ_f H _m ^θ [La(Ala)₄(NO₃)₃·H₂O(s), 298.2 K]= -3867.57 kJ mol^-1, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of solutions of amidomagnesium chlorides in poly(ethylene oxide) and their characterization by conductivity measurements

Polymer electrolyte systems were prepared for the first time by dissolution of amidomagnesium chlorides in poly(ethylene oxide), (PEO). For the preparation, solutions of (hexamethyldisilylamido)magnesium chloride, (dimethylpyrrolyl)magnesium chloride, (diisopropylamido)magnesium chloride, piperidinomagnesium chloride and morpholinomagnesium chloride were chosen. The composition of these polymer electrolyte systems corresponds to the general formula R₂NMgCl·P(EO)_n·THF. Most work has been done with the system (hexamethyldisilylamido)magnesium chloride in PEO, (Me₃Si)₂NMgCl·P(EO)_n·THF, with n= 3, 4, 5, or 7. The electrolytes have a soft rubber-like consistency. At 30 °C, electrical conductivities of 10⁻⁶–10⁻⁵ S/cm were found. The conductivities were measured in the temperature range 20–60 °C. Within this temperature range a linear dependence of the logarithms of the conductivity on the inverse temperature was found and activation energies for the conducting process of 30–60 kJ/mol were calculated. Using those polymer electrolytes with a high content of the amidomagnesium compound, a reversible magnesium deposition takes place by cathodic reduction at potentials below −1.9 V vs. a Ag/AgCl reference electrode. These polymer electrolytes were found to be stable against oxidation up to about −0.3 V vs. Ag/AgCl. Electronic Publication     

Interfacial dilational properties of partly hydrolyzed polyacrylamide and gemini surfactant at the decane–water interface

The dilational viscoelastic properties of partly hydrolyzed polyacrylamide (HPAM) and surfactant (C₁₂COONa-p-C₉SO₃Na) in the absence or presence of electrolyte were investigated at the decane–water interface by means of longitudinal method and the interfacial tension relaxation method. The polymer plays different roles in influencing the structure of HPAM–surfactant mix-adsorbed layer at different surfactant concentration. At low surfactant concentration, the addition of polymer could sharply decrease the dilational elasticity mainly due to the weakening of the “entanglement” among long alkyl chains in surfactant molecules, while the addition of the polymer may enhance the dilational elasticity due to the slow diffusivity of the polymer chains at higher surfactant concentration. And the added electrolyte, which results in screening of electrostatic interactions between the ionized groups, generally decreases the interfacial dilational elasticity and increases the dilational viscosity. The data obtained on the relaxation processes via interfacial tension relaxation measurement can explain the results from dilational viscoelasticity measurements very well.     

Thermochemistry of some adducts of Indium(III) chloride with neutral donors

The [InCl₃(L) _n ] (where L is 2,2′-bipyridine (bipy), 2,2′-bipyridine N,N′-dioxide (bipyNO), N,N-dimethylacetamide (dma), urea (u), thiourea (tu) or 1,1,3,3-tetramethylthiourea (tmtu); n = 1.5, 3 or 4) were synthesized and characterized by melting points, elemental analysis, thermal analysis and IR spectroscopy. The enthalpies of dissolution of the adducts, Indium(III) chloride and ligands in 1.2 M aqueous HCl were measured and by using thermochemical cycles, the following thermochemical parameters for the adducts have been determined: the standard enthalpies for the Lewis acid/base reactions (Δ_r H ^θ), the standard enthalpies of formation (Δ_f H ^θ), the lattice standard enthalpies (Δ_M H ^θ), and the standard enthalpies of decomposition (Δ_D H ^θ).     

Investigation of thermally stimulated charge relaxation mechanism in SiO<Subscript>2</Subscript> filled polycarbonate nanocomposites

The thermally stimulated charge relaxation properties of polycarbonate (PC) filled with SiO₂ nanofiller were studied by means of thermally stimulated discharge current (TSDC). The nanocomposite samples were further characterized by UV–vis spectroscopy, scanning electron microscopy, energy dispersive X-ray spectra, and differential scanning calorimetry (DSC) techniques to investigate the dispersion of nanofillers in polymer matrix and glass transition temperature. All pristine and nanocomposites samples of thickness about 25 μm were prepared using solution mixing method. The suitable weight percentage of SiO₂ nanofillers has been chosen to prevent the nonuniform dispersion. TSDC measurement of PC (Pristine) and PC+ (7% SiO₂) shows the single peak, while TSDC characteristic of other nanocomposites are showing two peaks. The higher temperature TSDC peak of pristine and nanocomposites samples is originated due to the charge relaxation from shallower and deeper trapping sites, however, low temperature peak is caused by dipolar relaxation of charge carriers. Since the position of higher temperature TSDC peak is generally an analysis of glass transition temperature of polymer/polymer nanocomposites. The authors have observed that the temperature of this peak is almost same as the T _g measured by DSC with 0 to ±5% variation. This article presents the deeper understanding of charge relaxation mechanism caused by SiO₂ nanofillers in polycarbonate.     

Cohesional Entanglement of Amorphous Polymer in Glass State as Probed by Equilibrium Swelling in a "Non-Solvent

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Aggregation effects on evaporation and the air/water interface of dodecyltrimethylammonium hydroxide solutions

 The system dodecyltrimethylammonium hydroxide (DTAOH)–water was studied by surface tension, ion-selective electrodes and evaporation in an electrobalance. Results confirmed earlier conclusions about a stepwise aggregation mechanism in DTAOH solutions. The aggregation process started at a total concentration C _T=(2.51±0.10)×10^-4 mol dm^-3) which probably corresponds to the formation of dimers. At C _T= (1.300±0.041)×10^-3 mol dm^-3 there was a change in the surface and evaporation behavior, corresponding to the formation of small, fully ionized aggregates which grew with increasing concentration. At C _T= (1.108±0.010)×10^-2 mol dm^-3 the formation of true micelles with hydroxide counterions in the Stern layer did not change significantly the evaporation and adsorption behavior. This means that between this concentration and C _T=(3.02±0.28)× M28.8n10^-2 mol dm^-3, the changes in structure were gradual. At the latter concentration there was a sudden change in the monolayer state at the air/water interface, with a strong surfactant desorption, and a major change in evaporation behavior. The changes are compatible with the formation of few, large aggregates reducing the total concentration of kinetically independent solute units, which in turn increased the activity of the solvent. This phenomenon is in agreement with literature information. The reduction in the evaporation rate of water was mainly due to the reduction of the water activity, caused by colligative effects. The reduction of the effective area available for evaporation had only a slight effect in water evaporation. Received: 9 January 1997 Accepted: 19 October 1997     

Wettability of biodegradable surfaces

The study of the interfacial characteristics of biodegradable polymers/copolymers is of importance from the point of view of both surface science and pharmaceutical/cosmetic applications. Films formed from biodegradable polymers allow systematic wettability studies on surfaces with a wide range of copolymer (chemical) compositions. The possibility of interchanging these drug carrier polymers, if their wetting characteristics are similar, could be beneficial to diverse applications. Low-rate dynamic contact angles on films (solvent cast on polar substrates, i.e. on silicon wafer) of poly(lactic acid), and its copolymers with poly(glycolic acid), (with four different copolymer ratios of 85/15, 75/25, 65/35 and 50/50) were measured by axisymmetric drop shape analysis-profile (ADSA-P) with four liquids: water, formamide, 2,2′-thiodiethanol and 3-pyridylcarbinol. The solid surface tensions, γ_sv, were calculated from the advancing contact angles, θ_A. The surface topography of the polymer films was investigated by atomic force microscopy (AFM). The surface composition of the polymer layers was analyzed by X-ray photoelectron spectroscopy (XPS). The advancing contact angles were found to be independent of the composition of the copolymers, while the receding angles, θ_R, did decrease with increasing ratio of the polar component [poly(glycolic acid)] in the copolymers. The solid surface tensions calculated from the advancing contact angles of the liquids for all homo- and copolymers were the same within the error limit; the mean value being γ_sv=35.6 ± 0.2 mJ/m². The surface roughness, which was obtained from AFM images, increased with increasing poly(glycolic acid) ratio, without affecting the advancing contact angles. The constancy of γ_sv is attributed to the effect of the surface activity of the nonpolar segments of the polymer chains, which oriented to form the outermost layer of the film. This was confirmed by XPS analysis. Received: 06 November 2000 Accepted: 09 May 2001     

Preparation of a novel polymer gel electrolyte based on N-methyl-quinoline iodide and its application in quasi-solid-state dye-sensitized solar cell

Using poly(acrylonitrile-co-styrene) as polymer host, 1,2-propanediol carbonate, dimethyl carbonate and ethylene carbonate as mixture solvent, N-methyl-quinoline iodide and iodine as the source of I⁻/I₃ ⁻, a novel polymer gel electrolyte with ionic conductivity of 5.12 × 10⁻³ S· cm⁻¹ at 25°C was prepared by sol-gel and hydrothermal methods. Based on the polymer gel electrolyte, a quasi-solid-state dye-sensitized solar cell was fabricated. The solar cell possess better long-term stability and light-to-electrical energy conversion efficiency of 4.04% under irradiation of 100 mW· cm⁻². The influences of polymer host, solvent, N-methyl-quinoline iodide and temperature on ionic conductivity of the polymer gel electrolyte and the performance of the dye-sensitized solar cell was discussed.     

Anchoring of hydrophobically modified poly(sodium acrylate)s into DDP vesicle bilayers: hydrophobic match and mismatch

 Differential scanning microcalorimetric thermograms have been recorded for aqueous solutions containing vesicles formed by sodium di-n-dodecyl phosphate, in the presence of different concentrations of poly(sodium acrylate-co-n-alkyl methacrylate), where n-alkyl= C₉H₁₉, C₁₂H₂₅, C₁₈H₃₇. The mole fraction of hydrophobic moieties in the copolymer is 0.04. The main phase transition temperature (T _m) is hardly affected by the presence of poly(sodium acrylate)s bearing n-dodecyl chains, whereas the anchoring of polymers bearing n-nonyl or n-octadecyl groups reduces the main phase transition temperature significantly from ca. 34 °C to ca. 32 °C. In parallel, the enthalpy of transition per mole of DDP monomer (Δ_m H _int) is lowered upon adding polymer. Again, the polymer containing n-dodecyl moieties hardly affects Δ_m H _int. These patterns are explained by the notion that the extent of the disruptive effect of alkyl chains incorporated into the bilayer depends on the extent of the mismatch between the chain lengths of the intruding alkyl chains and the hydrophobic moieties composing the vesicle bilayer. Added hydrophobically modified polymers increase the cooperativity of the melting process, as shown by the increase of n _DDP. We suggest that the anchoring poly(sodium acrylate-co-n-alkyl methacrylate) relieves the strain in the curved outer monolayer of a pure DDP bilayer by allowing the presence of larger “patches” characterized by low curvature. Received: 12 May 1997 Accepted: 20 October 1997     

Transition of polymers from rubbery elastic state to fluid state

On increasing the temperature of a polymer, the transition of the polymer from a rubbery elastic state to a fluid state could occur. The transition temperature is termed the fluid temperature of the polymer, T _f, which has a direct relationship with the polymer molecular weight. As one of polymer parameters, T _f is as important as the glass transition temperature of a polymer, T _g. Moreover, special attention to T _f should be paid for polymer processing. In research on the transition of a polymer from a rubbery elastic state to a fluid state, the concept of T _f would be more reasonable and more effective than the concept of T _l,l because it is neglected in the concept of T _l,l in that the molecular weight of a polymer may affect the transition of the polymer. In this paper the discussion on the fluid temperature involves the characters of polymers, such as the deformation—temperature curve, the temperature range of the rubbery state and the shear viscosity of polymer melt. From the viewpoint of the cohesional state of polymers, the transition of a polymer from a rubbery elastic state to a fluid state responds to destruction and construction of the cohesional entanglement network in the polymer. The relaxing network of polymer melt would be worthy to be considered as an object of study. __________ Translated from Huaxue Tongbao (Chemistry), 2008,71(3) (in Chinese)     

Ultrasonic studies of polysaccharide (pectin) in aqueous media at 298.15 K

The ultrasonic velocity, density and viscosity of pectin in aqueous medium were measured at 298.15 K. The acoustical parameters such as adiabatic compressibility (β), free length (L _f), free volume (V _f), internal pressure (π_i), acoustical impedance (Z), and relative association (R _A), Rao’s constant (R) and Wada’s constant (W) are calculated. The results are interpreted in terms of molecular interaction between the components of the mixtures. Further, some more acoustical parameters such as relaxation time (τ), absorption coefficient (α/f ²) and relaxation strength (r) are calculated with various percentage of pectin has been studied which reveals interaction between the solvent and the polymer (pectin) at various concentration of the polymer. The observed values suggested the solute-solvent interaction is favored.     

Low-rate dynamic contact angles on poly(n-butyl methacrylate) and the determination of solid surface tensions

 Low-rate dynamic contact angles of 22 liquids on a poly(n-butyl methacrylate) (PnBMA) polymer are measured by an automated axisymmetric drop shape analysis-profile (ADSA-P). It is found that 16 liquids yielded non-constant contact angles, and/or dissolved the polymer on contact. From the experimental contact angles of the remaining 6 liquids, it is found that the liquid–vapor surface tension times cosine of the contact angle changes smoothly with the liquid–vapor surface tension, i.e. γ_lv cos θ depends only on γ_lv for a given solid surface (or solid surface tension). This contact angle pattern is in harmony with those from other inert and non-inert (polar and non-polar) surfaces [34–37, 45–47]. The solid–vapor surface tension calculated from the equation-of-state approach for solid-liquid interfacial tensions [14] is found to be 28.8 mJ/m², with a 95% confidence limit of ±0.5 mJ/m², from the experimental contact angles of the 6 liquids. Received: 12 September 1997 Accepted: 22 January 1998