Rheological Behavior for Polymer Melts and Concentrated Solutions——Part Ⅶ: A Quantitative Verification for the Molecular Theory of Non-linear Viscoelasticity with Entanglement Constraints in Polymer Melts

Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) over dot), psi (10)((gamma) over dot) and shear rate ((gamma) over dot), and topologically constrained dimension number n ' and a were derived. Linear viscoelastic parameters (eta (0) and G(N)(0)) and topologically constrained dimension number (n ' a and <(<upsilon>)over bar>) as a function of the primary molecular weight (M-n), molecular weight between entanglements (M-C) and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters (eta (0), psi (10), G(N)(0) and J(e)(0)), topologically constrained dimension number (n ', a and v) and molecular weight (M-n, M-c and M-e) from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.

Rheological Behaviour for Polymer Melts and Concentrated Solutions Part Ⅰ:A New Multiple Reptation Model to Predict the Nonlinear Visco-elasticity with Nagai Chain Constraints in Entangled Polymer Melts

An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model structure for a single polymer chain with n tail segments and N reversible entanglement sites on the test polymer chain is developed. Based on the above model structure and the mechanism of molecular flow by the dynamical reorganization of entanglement sites, the probability distribution function of the end-to-end vectr for a single polymer chain at entangled state and the viscoelastic free energy of deformation for polymer melts are calculated by using the method of the stochastically statistical mechanics. The four types of stress-strain relation and the memory function are derived from this thery. The above theoretical relations are verified by the experimentaf data for various polymer melts. These relations are found to be in good agreement with the experimental results

Electrostatic-Mediated Intramolecular Cross-Linking Polymers in Concentrated Solutions

Since Kuhn in 1956 first proposed intramolecular cross-linking of isolated single-polymer chains in dilute solutions,the method has been extensively employed to achieve single-chain colloids and tadpole colloids(Janus ones)from homopolymers and copolymers,respectively.

Probing the pH-dependent chain dynamics of poly(acrylate acid) in concentrated solution by using a cationic AIE fluorophore

We report a novel strategy to study the chain dynamics of poly(acrylic acid) (PAA) in a relative concentrated solution (1.0 g/L). The strategy is based on the fluorescent probe (DCTPE) with unique aggregation-induced emission (AIE) characteristics. Free DCTPE molecules are non-emissive in aqueous solution, but they become highly emissive when trapped in polymer coils. The fluorescence intensity is proportional to the efficiency of trapping DCTPE molecules in polymer coils. By correlation the change of fluorescence intensity with the variation of pH value (from 1.78 to 12.06), the PAA chain's dynamics in the relatively concentrated solution have been elucidated into three processes. In the pH range from 12.06 to 6.0, PAA chains take an extended and non-folding conformation. Changing pH from 6.0 to 3.86, PAA chains are partially protonated and loosely packed polymer coils are formed. Further lowering the pH value of the solution (from 3.86 to 1.78), protonated segments dominate the PAA chains, and at the same time, the intermolecular hydrogen bonding takes effect, thus the polymer chains posses in the conformation of more compact coils.

Molecular Dynamics Simulations of Displacement Cascade in Ni-Based Concentrated Solid Solution Alloys

Single-phase concentrated solid solution alloys(SP-CSAs),including high-entropy alloys,have received extensive attention due to their excellent irradiation resistance.In this work,displacement cascade simulations are conducted using the molecular dynamics method to study the evolution of defects in Ni-based SP-CSAs.Compared with pure Ni,the NiCr,NiCo,and NiCu alloys exhibit a larger number of Frankel pairs(FPs)in the thermal peak stage,but a smaller number of surviving FPs.However,the NiFe alloy displays the opposite phenomenon.To explain these different observations for NiFe and other alloys,the formation energy and migration energy of interstitials/vacancies are calculated.In the NiFe alloy,both the formation energy and migration energy barrier are higher.On the other hand,in NiCr and other alloys,the formation energy of interstitials/vacancies is lower,as is the migration energy barrier of interstitials.The energy analysis agrees well with previous observations.The present work provides new insights into the mechanism behind the irradiation resistance of binary Ni-based SP-CSAs.

MULTIPLICITY AND CONCENTRATION BEHAVIOUR OF POSITIVE SOLUTIONS FOR SCHRDINGER-KIRCHHOFF TYPE EQUATIONS INVOLVING THE p-LAPLACIAN IN R^N

In this article, we study the multiplicity and concentration behavior of positive solutions for the p-Laplacian equation of SchrSdinger-Kirchhoff type -εpM（εp-N∫RN｜△u｜p）△pu＋v（x｜u｜p-2u=f（u）in RN, where △p is the p-Laplacian operator, 1 〈 p 〈 N, M ： R＋ → R＋ and V ： RN →R＋ are continuous functions, ε is a positive parameter, and f is a continuous function with subcritical growth. We assume that V satisfies the local condition introduced by M. del Pino and P. Felmer. By the variational methods, penalization techniques, and Lyusternik- Schnirelmann theory, we prove the existence, multiplicity, and concentration of solutions for the above equation.

Effects of precursor solution concentration on the properties and morphology of YBCO films deposited by TFA-MOD method

Epitaxial YBCO films were deposited on （100） LaAlO3 single-crystal substrates by metalorganic deposition of metal trifluoroacetate precursors with different concentrations. All the YBCO films have Tc around 91 K and Jc excess 2 MA/cm^2 at 77 K in zero field. XRD θ-2θscans show all the films have c-axis normal orientation. The FWHM （full width at half-maximum intensity） values of X-ray ω-scans of （005） reflection are 0.379°, 0.283°, and 0.543° for the YBCO thin films deposited with precursor solution concentrations of 1.52, 1.0, and 0.75 mol/L, respectively. With the concentration of the precursors decreasing, the thickness of the films decreases linearly. SEM micrographs show that porosities in the films become bigger with the precursor solution concentration decreasing. The big porosities in the film with the lowest concentration precursor deteriorate the superconducting property and make it have a wider superconducting transition and a lower Jc.

APPLICATION OF NONIONIC TEMPERATURE SENSITIVE HYDROGEL FOR CONCENTRATION OF PROTEIN AQUEOUS SOLUTION

Six different N-alkyl substituted acrylarnide nonionic hydrogels were prepared and their swelling characteristics were measured. Poly N-isopropyl acrylamide (PNIPA) and poly N-n-propyl-acrylamide (PNNPA) temperature sensitive hydrogels were chosen as the nonionic temperature sensitive hydrogels for concentration of very dilute aqueous protein solution. The separation properties of PNIPA and PNNPA hydr0gels with different network dimensions were studied and the modification of the hydrogels was surveyed in order to decrease their surface adsorption of protein molecules. The experimental results of the concentration of BSA (Bovin serum albumin) dilute aqueous solution by hydroxylpropyl methacrylate (HPMA) copolymerized PNIPA hydrogel were given. The value and the limitation of concentration of dilute aqueous protein solution by this method was evaluated.

AN EXPLICIT TENSOR EXPRESSION FOR THE FUNDAMENTAL SOLUTIONS OF A BIMATERIAL SPACE PROBLEM

In this paper, by using the method of tensor operation, the fundamental solutions, given in the references listed, for a concentrated force in a three-dimensional biphase-infinite solid were expressed in the tensor form, which enables them to be directly applied to the boundary integral equation and the boundary element method for solving elastic mechanics problems of the bimaterial space. The fundamental solutions for Mindlin's problem, Lorentz's problem and homogeneous space problem are involved in the present results.

Effects of precursor solution concentration on dielectric properties of (Pb,La)(Zr,Ti)O_3 antiferroelectric thick films by sol-gel processing

Pb0.97La0.02Zr0.95Ti0.05O3(PLZT)antiferroelectric thick films derived from different precursor solution concentrations are prepared on platinized silicon substrates by sol-gel processing.The films present polycrystalline perovskite structure with a(100)preferred orientation by X-ray diffraction(XRD)analysis.The antiferroelectricity of the films is confirmed by the double hysteresis behaviors of polarization and double-bufferfly response of dielectric constant under the applied electrical field.Antiferroelectric properties and dielectric constant are improved while the polarization characteristic values are reduced with the increase of precursor solution concentration.The films at higher precursor solution concentration exhibit excellent dielectric properties.

Synthesize of ZnO Nanorods on Quartz Substrates with Seed Layer via Hydrothermal Method: Influence of Solution Concentration

Vertically oriented ZnO nanorods have been synthesized by hydrothermal method on quartz substrates with a seed layer. The influence of solution concentration on the morphology, structural and optical properties was analyzed. Results indicated that with the increase of solution concentration, the diameter and uniformity of ZnO nanorods increased. And the preferred orientation is obviously which shows better crystal quality. Typically, when the solution concentration is 0.03 mol/L, the nanorods exhibit a stronger UV emission peak located around 380 nm. In the visible region, all synthesized samples demonstrate more than 80% of optical transparency.

The Influence of Ce(NO_3)_3·6H_2O on the Inhibitive Effect of Ca(NO_2)_2 in Simulated Concrete Pore Solution

The effects of cerium nitrite on corrosion behaviors of carbon steel in simulated concrete pore solutions were studied with the methods of linear polarization, electrochemical impedance spectroscopy and surface analysis. In pore solutions in the presence of Ce（NO3）3？6H2O, the corrosion potential, polarization resistance and impedance of carbon steel obviously increased in contrast to the situation in the absence of cerium salts. The pore solution with [NO2-] / [Cl-] = 0.3 and 0.1% Ce（NO3）3？6H2O, carbon steel shows better corrosion resistance than that in the pore solution with [NO2-] / [Cl-] = 0.6, which indicates that a small amount of Ce（NO3）3？6H2O in pore solutions can effectively promote passivation of the steel and reduce the threshold [NO2-] / [Cl-] ratio for corrosion control. The surface layer formed in cerium salt containing pore solutions is more compact and smooth and 1.36%Ce is examined on the sample surface. The addition of 0.1% Ce（NO3）3？6H2O in pore solutions can decrease the corrosion rate of steel in pore solutions and has little influence on pH change of the solutions. However, more cerium nitrate addition above 0.1% may result in pH decrease of the solution.

Temperature Compensated Solution Concentration Measurement Based on a Cascaded SMS/LPFG Fiber Structure

In this paper, a hybrid optical fiber structure for solution concentration measurement with the temperature compensation is proposed. The structure consists of long period fiber grating (LPFG) and single mode-multimode-single mode (SMS) fiber structures. The sensing mechanism of the device is studied and verified by experiments. LPFG is sensitive to solution concentration and is affected by temperature crosstalk. SMS structure is not affected by solution concentration, but sensitive to ambient temperature. It can be used as a temperature compensation system. The sensitivity coefficients of LPFG and SMS on temperature and concentration were measured experimentally, and a dual-wavelength matrix was established to realize simultaneous measurement of solution temperature and concentration.

Grain-boundary segregation and grain growth in nanocrystalline substitutional solid solution alloys

A model for describing solute segregation at grain boundaries has been developed for substitutional solid solution alloys,which integrates multiple factors from atomic to microstructural scales.A concept of mo-lar Gibbs free energy of segregation was introduced to evaluate the segregating capability of the solute elements in a closed system,through which the influences of grain boundary structure,grain size,ma-terial composition,and external conditions were described.Based on the evaluation of various energy forms related to solute segregation and grain growth processes,the nature of the thermal stabilization of nanograin structures by solute segregation was disclosed.A criterion for the destabilization of nanostruc-tures,which is determined by the competition of the change rates between the molar Gibbs free energy of segregation and the total energy of grain boundaries with grain size,has been proposed.This study provided guideline to achieve high-temperature stability of nanograin structures of solid solution alloys even for the weakly segregating nanocrystalline systems.

Separation of macro amounts of tungsten and molybdenum by ion exchange with D309 resin

Based on the difference in tendency to polymerize between tungsten and molybdenum, a new method using D309 resin was propounded. The batch tests indicate that the optimum pH value and contact time for the separation are 7.0 and 4 h respectively, the maxium separation factor of W and Mo is 9.29. And the experimental resules show that isothermal absorbing tungsten and molybdenum belongs to Langmuir model and Freundlich model respectively, and the absorbing kinetics for tungsten is controlled by intra-particle diffusion. With a solution containing 70 g/L WO3 and 28.97 g/L Mo, the effluent with a mass ratio of Mo to WO3 of 76 and the eluate with a mass ratio of WO3 to Mo of 53.33 are obtained after column test.

Hierarchical intercalation of tetrafluoroborate anion into graphite electrode from sulfolane

The anion storage behavior of graphite positive electrode in a dual-ion battery is closely related to the solvation of anion in the corresponding electrolyte solution.The classical electrolyte solutions of Li BF_(4)^(-)sulfolane(SL)have long been recognized in the community of lithium batteries and still appear promising in dual-ion batteries.Nevertheless,the solvation of BF_(4)^(-)by SL has seldom been addressed before.In this study,the solvation states of SL-BF_(4)^(-)are adjusted by varying LiBF_(4)concentration or introducing auxiliary salts of LiPF_6or SBPBF_(4)(SBP:spiro-(1,1')-bipyrrolidinium)in the electrolyte solutions of Li/graphite dualion cells.The electrochemical storage processes of SL-BF_(4)^(-)anions in graphite electrodes are investigated through in situ X-ray diffraction measurements.Two kinds of graphite intercalation compounds(GICs)with contrastive intercalation gallery heights(IGHs)have been discovered,which are ascribed to the storage of different kinds of SL-BF_(4)^(-)anions in graphite electrode.The interactions between ions and SL in the electrolyte solutions are characterized by Fourier transform infrared spectroscopy and then correlated with the performance of Li/graphite cells.

The Transference Number

The performance of rechargeable batteries and other electrochemical systems depends on the rate at which the working ion(often a cation)is transported from one electrode to the other.The cation transference number is an important transport parameter that affects this rate.The purpose of this perspective is to distinguish between approximate and rigorous methods used in the literature to measure the transference number.We emphasize the fact that this parameter is dependent on the reference frame used in the analysis;care must be taken when comparing values obtained from different sources to account for differences in reference frames.We present data obtained from a well-characterized electrolyte.We compare rigorously determined transference numbers in two reference frames with values obtained by an approximate method.We conclude with a qualitative discussion of the relationship between the transference number and salt concentration gradients that are obtained when current is drawn through a battery。

Rheological Behaviour for Polymer Melts and Concentrated Solutions Part Ⅲ: A New Multiple Entanglement Model to Predict the Dependence of Linear Viscoelastic Function (η_0, Ψ_(10)~0,η_(ext)~0) on the Ranges of Primary Molecular Weights and the Species of Polymers

It is shown theoretically that the viscoelasticity of polymer melts is determined by three combining factorst they are the primary molecular weight and its distribution, the number of entanglement sites on polymer chain and the sequence distribution of constituent chains in entanglement spacings. A unified quantity for the three combing factors is the average constrained dimensional number of constituent chains in the long entanglement spacings (v). A new relation of v to the primary molecular weight and the number of testing polymers were derived from the multiple entanglement and reptation model, and a new method for determining v was proposed. The dependences of linear viscoelastic functions on the primary molecular weight and its distribution were derived by the statistical method. When Mn=6Me to 18 Me, the values of (v) can range from 3.33 to 3.70. Their values are in a good agreement with the experiment data, and it can slightjy vary with the different species of polymers and the different ranges of molecular weight of polymers

Quantitative characterization of lamellarαprecipitation behavior of IMI834 Ti-alloy in isothermal and non-isothermal heat treatments

To reveal the affecting mechanism of cooling rate on lamellarαprecipitation,the precipitation behaviors of lamellarαphase in IMI834 titanium alloy during isothermal and non-isothermal heat treatments were quantitatively characterized using experimental analysis.Critical precipitation temperatures at various cooling rates were obtained using thermal dilatation testing.Using metallographic microscopy,electron microprobe analysis,and data fitting methods,the quantitative evolution models of average width,volume fraction,and solute concentration in theαandβphases were built for different temperatures or cooling rates.A comparison between the two precipitation behaviors showed that the average width and volume fraction of lamellarαphase under non-isothermal conditions were smaller than those under isothermal conditions.With increasing cooling rate,the average width and volume fraction were decreased significantly,and the critical precipitation temperatures were reduced.This phenomenon is mainly attributed to the decreased diffusion velocity of solutes Al,Mo,and Nb with increasing cooling rate.