Rheological Behaviour for Polymer Melts and Concentrated SolutionsPart Ⅱ: Material Function with Nagai Chain Constraints and Determination of Their Parameters from Flow Curves

An integral constitutive equation and a set of material functions for describing the strain history of polymer melts were formulated in terms of the Cauchy-Green and Finger tensors. A simple memory function and the dependence of ηo and τt on M3.4 were derived from the theory of non-linear viscoelasticity with constraints of entanglements for polymer melts and substituted into the Oldroye-Walters-Fredickson constitutive equation. An integral constitutive equation for polymer melts was consequently obtained. Some material functions of the constitutive equation related to certain 'test flow' are examined as follows : (1) simple steady shear flow; (2) steady elongation flow; (3) small-amplitude oscillatory shear flow; (4) stress growth upon the inception of steady shear elongation flow; (5) stress relaxation (modulus and compllance). These theoretical relations for simple steady shear flow were compared with experimental data from our laboratory and references for various polymer melts and concentrated solutions. A good agreement between the theory and experiment was achieved.

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

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 th

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

RHEOLOGICAL BEHAVIOURS OF CAST STEEL DURING SOLIDIFICATION

The stress-strain relation for cast low alloy carbon steel at solidification temperature has been examined by the authors' own desingned apparatus for rheological properties measurement.The rheology model,the stress-strain constitutive equation and the rheological parameters therefrom of the cast steel were proposed.Thus the theoretical basis and calcula- ting data for computerized s#nulation on the stress-strain relation and thermal cracking of the cast steel were suggested.

Rheological and physicochemical characteristics of asphalt mastics incorporating lime kiln dust and dolomite powder as sustainable fillers

The filler-bitumen interaction mechanism is one of the most essential phases for comprehending the asphalt mixture's performance.However,despite numerous studies,in-depth knowledge of filler-bitumen reciprocity at a microscale level is yet to be ascertained.The goal of this research is to gain a better understanding of the fillerbitumen microscale interaction in terms of the synergy and coaction between the physicochemical and rheological performance of mastics due to filler inclusions.The rheological properties of two sustainable mastics,dolomite powder(DP)and lime kiln dust(LKD),together with a neat PEN 60/70 binder,were analysed based on a temperature sweep at elevated temperature conditions.Meanwhile,frequency sweep and multiple stress creep recovery(MSCR)tests were also conducted at pavement serviceability temperature using the dynamic shear rheometer(DSR).Physicochemical tests using a scanning electron microscope(SEM)and energy dispersive X-rays(EDX)were conducted to analyse the impact of parameters such as particle shape,grain size,texture,and chemical compositions.The DSR test results showcased how the incorporation of fillers in asphalt binder considerably improved the performance of the binder in terms of rutting and fatigue.Likewise,its strain and nonrecoverable compliance parameters were substantially reduced at higher filler and binder concentrations.Physical filler attributes of low rigden voids(R.V),high fineness modulus(FM),and high specific surface area(SSA)led to greater interfacial stiffness and elasticity in LKD mastics compared to DP mastics at different loading frequencies and temperature levels.The SEM/EDX results also indicated that the elemental calcium and carbon composition of each filler component,together with its grain morphology,strongly influenced its rheological performance.

Preparation and Characterization of Biobased Dehydroabietyl Polyethylene Glycol Glycidyl Ether-Grafted Hydroxyethyl Cellulose with High Emulsifying Property

Dehydroabietyl polyethylene glycol glycidyl ether-grafted hydroxyethyl cellulose(HEC)polymer surfactant(DA(EO)5GE-g-HEC)was prepared using ring-opening polymerization with biobased rosin and hydroxyethyl cellulose as feedstocks.Dehydroabietyl polyethylene glycol glycidyl ether(DA(EO)5GE)was formed by condensation of dehydroabietyl alcohol polyoxyethylene ether(Rosin derivative:DA(EO)5H)and epichlorohydrin.The grafting degree of DA(EO)5GE-g-HEC was manipulated by adjusting the mass ratio of HEC and DA(EO)5GE and confirmed by EA.According to the formula,when m(HEC)/m(DA(EO)2GE)was 1:1~1:5,the grafting rate of DA(EO)5GE in DA(EO)5GE-g-HEC varied from 34.43%to 38.33%.The surface activity and foam properties of DA(EO)5GE-g-HEC aqueous solution were studied.The results showed that with the increase in grafting rate,the critical micellar concentration(CMC)in aqueous solution changed from 1.28 to 0.96 g/L.The results of the thermogravimetric analysis showed that the temperature range of the main stage of mass loss of DA(EO)5GE-g-HEC was 310°C~410°C,and the thermal decomposition processes of the samples with five mass ratios were similar.An oil in water emulsion was prepared by choosing cyclohexane as the oil phase and DA(EO)5GE-g-HEC as the emulsifier.The effect of DA(EO)5GE-g-HEC mass fraction on emulsion particle size and stability was analyzed.The results suggested that when the oil-water ratio was 8:2 with 0.4%emulsifier,the emulsion droplets were the smallest in terms of particle size and were the most stable.The rheological test results showed that the apparent viscosity decreased with the increase in shear rate and showed a typical elastic gel phenomenon.

Rheology of Steel Fibre Containing Alumina-Magnesia-Extruded Graphite Pellets Self-Flowing Castables

The influences of adding steel fibres of different lengths up to 3 volume percentages, on the rheological behaviour of an alumina-magnesia-extruded graphite pellet containing castables have been studied using a rheometer. Free-flow measurements have shown that the flow is severely affected by increasing the length of steel fibres. The calculated values of rheological constants indicate that 19 mm and 25 mm fibre up to 2 volume percentage is permitted while one volume percentage of 50 mm fibres severely degrades the rheology of the castable.

Numerical Simulation and Experimental Characterization of Clay Paste under Loads for Energy Saving in Clay Materials Processing

Requirements for the respect of the environment encourage to reduce the impact of human activity on the nature. Civil engineering answers these requirements by the development of ecological construction materials. This paper deals with the transformation of clay raw materials which enable the processing of environmentally friendly construction materials: in addition to their biodegradability, the alveolar fired clay materials allow energy saving in home heating thanks to their thermal isolation properties. But their manufacturing is a high energy consumption process, in particular during compaction, drying and firing which contribute to the emission of greenhouse gases. The goal of this paper is to study the rheology of clay pastes in order to develop low energy in manufacturing processes. For this purpose, theoretical and experimental approaches were carried out on six clay varieties. In the theoretical approach, a finite element (FE) simulation model has been developed for pressing a non-rigid material predicting deformations and stresses occurring within the clay structure. Experiments have then been carried out to validate the finite element modelling. In this experimental approach, the clay pastes were transformed with water content respecting the Atterberg limits which determine the plasticity of clays. The samples compaction has been carried out under variable loadings in order to determine the suitable low energy consumption loading.

Synthesis and performances of poly(butylene-succinate) with enhanced viscosity and crystallization rate via introducing a small amount of diacetylene groups

A cross-linkable comonomer containing a diacetylene group,named dimethyl 4,4＇-（buta-l,3-diyne-l,4-diyl）dibenzoate（DA） was synthesized and copolymerized with dimethyl succinate and 1,4-butanediol to prepare a series of slightly cross-linked PBS copolyesters（PBDASx）.The chemical structure,crystallization and Theological behaviours of PBDASx were well investigated.Compared to neat PBS,PBDASx showed the greatly increased crystallization rate because of the promoting nucleation of the cross-linking domains,and the XRD results indicated that it had no influence on crystallization structure of PBS.The rheological behaviours indicate that PBDASx possessed higher viscosity than neat PBS even at high shear rate and temperature.PBDAS0.3 exhibited better comprehensive properties than neat PBS,which will widen applications of PBS.

DISPERSION PRODUCTION BY SEMI-CONTINUOUS RADICAL VINYL ACETATE EMULSION POLYMERIZATION WITH SILANE CO-MONOMER AND CHARACTERIZATION OF FINAL PRODUCTS

Vinyl acetate radical emulsion polymerization in water with GF51 silane co-monomer was performed by semi continuous way. The GF51 impacts on dispersion rheology as well on films and bonding strength properties were determined. It should be stated that even low quantities of GF51 （up to 6% from VAc） determined high viscosity of dispersions. The GF51 modified films have low water absorption and high affinity to glass. Molecular mass and thermal properties of GF51 modified polymers were determined accordingly.