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 and shear rat...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 and shear rate (), and topologically constrained dimension number and a were derived. Linear viscoelastic parameters and and topologically constrained dimension number and as a function of the primary molecular weight, molecular weight between entanglements and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters G and topologically constrained dimension number a and and molecular weight and 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.展开更多
A double-network model is established, which consists of the segments, E and A-constituent chains, the polymeric chains entangled with other ones by multi-entanglement and polymeric chains connected to a great number ...A double-network model is established, which consists of the segments, E and A-constituent chains, the polymeric chains entangled with other ones by multi-entanglement and polymeric chains connected to a great number of destructible particles by multi-adsorption, based on which the E and A-constituent chains can be recreated and released dynamically. The distribution function of the end-to-end vector, the statistical distribution function of conformation for two kinds of chains in the multi-entanglement and multi-adsorption states and their number of polymeric chains are calculated by the combination of statistical mechanics and kinetics. Then the viscoelastic free energies of deformation for two kinds of the networks and suspensions are calculated by Boltzmann’s statistical theory. Also. elastic modulus and memory function for two kinds of the network and suspensions are derived. Consequently, a new molecular theory of the non-linear viscoelasticity for polymeric suspensions is proposed, and the constitutive equation and material function with yielding and thinning for the polymeric suspensions in different flow fields are derived from this theory.展开更多
Matric suction is an important state variable required for the assessment of unsaturated soil properties.Tensiometers are commonly used for direct matric suction measurement but have a limited measuring range up to 90...Matric suction is an important state variable required for the assessment of unsaturated soil properties.Tensiometers are commonly used for direct matric suction measurement but have a limited measuring range up to 90 kPa due to the cavitation problem.Osmotic tensiometer(OT)can improve the measuring range of tensiometers by increasing the osmotic pressure of water to avoid the cavitation.However,the long-term water pressure decay that appeared in OTs caused a gradual decrease in their measuring range.In this study,crosslinked poly(acrylamide-co-acrylic acid)potassium salt(PAM-co-PAAK)was used for the preparation of OTs(five in total)to explore the mechanism of water pressure decay of OTs.The maximum water pressure in the OT versus the volume fraction of polymer filled in the OT was described based on the Flory-Huggins polymer theories and validated using WP4C dewpoint hygrometer.The long-term pressure decay of OT-1,OT-2,and OT-3 was observed for 130 d and constant pressures were found for OT-1 and OT-2,indicating that the pressure decay of OT was mainly caused by the stress relaxation of the polymer hydrogels,and standard linear solid(SLS)rheological model was appropriate to fit the decay data.For OT-1,OT-2 and OT-3,the theoretical osmotic pressure that was calculated based on the mass of retrieved polymer from OTs after 130-d pressure observation was higher than the actual osmotic pressure as observed,indicating that polymer leakage cannot explain the pressure decay of the OT.The ultravioletevisible(UVevisible)spectrophotometry examined the change in polymer concentrations in the water containers of OT-4 and OT-5 and demonstrated that there was no increase in polymer leakage during the period of pressure decay of OT-4 and OT-5.As a result,the pressure decay of OT was not caused by polymer leakage.The results of this research suggested that the viscoelastic properties of polymers should be taken into consideration in further OT development.展开更多
基金The authors gratefully a.cknowledge financial supportfrom th6 Natiol-al Natural Science Foundatiol- of CI-h-a. The number of
文摘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 and shear rate (), and topologically constrained dimension number and a were derived. Linear viscoelastic parameters and and topologically constrained dimension number and as a function of the primary molecular weight, molecular weight between entanglements and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters G and topologically constrained dimension number a and and molecular weight and 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.
文摘A double-network model is established, which consists of the segments, E and A-constituent chains, the polymeric chains entangled with other ones by multi-entanglement and polymeric chains connected to a great number of destructible particles by multi-adsorption, based on which the E and A-constituent chains can be recreated and released dynamically. The distribution function of the end-to-end vector, the statistical distribution function of conformation for two kinds of chains in the multi-entanglement and multi-adsorption states and their number of polymeric chains are calculated by the combination of statistical mechanics and kinetics. Then the viscoelastic free energies of deformation for two kinds of the networks and suspensions are calculated by Boltzmann’s statistical theory. Also. elastic modulus and memory function for two kinds of the network and suspensions are derived. Consequently, a new molecular theory of the non-linear viscoelasticity for polymeric suspensions is proposed, and the constitutive equation and material function with yielding and thinning for the polymeric suspensions in different flow fields are derived from this theory.
文摘Matric suction is an important state variable required for the assessment of unsaturated soil properties.Tensiometers are commonly used for direct matric suction measurement but have a limited measuring range up to 90 kPa due to the cavitation problem.Osmotic tensiometer(OT)can improve the measuring range of tensiometers by increasing the osmotic pressure of water to avoid the cavitation.However,the long-term water pressure decay that appeared in OTs caused a gradual decrease in their measuring range.In this study,crosslinked poly(acrylamide-co-acrylic acid)potassium salt(PAM-co-PAAK)was used for the preparation of OTs(five in total)to explore the mechanism of water pressure decay of OTs.The maximum water pressure in the OT versus the volume fraction of polymer filled in the OT was described based on the Flory-Huggins polymer theories and validated using WP4C dewpoint hygrometer.The long-term pressure decay of OT-1,OT-2,and OT-3 was observed for 130 d and constant pressures were found for OT-1 and OT-2,indicating that the pressure decay of OT was mainly caused by the stress relaxation of the polymer hydrogels,and standard linear solid(SLS)rheological model was appropriate to fit the decay data.For OT-1,OT-2 and OT-3,the theoretical osmotic pressure that was calculated based on the mass of retrieved polymer from OTs after 130-d pressure observation was higher than the actual osmotic pressure as observed,indicating that polymer leakage cannot explain the pressure decay of the OT.The ultravioletevisible(UVevisible)spectrophotometry examined the change in polymer concentrations in the water containers of OT-4 and OT-5 and demonstrated that there was no increase in polymer leakage during the period of pressure decay of OT-4 and OT-5.As a result,the pressure decay of OT was not caused by polymer leakage.The results of this research suggested that the viscoelastic properties of polymers should be taken into consideration in further OT development.
