The influences of both the volume of PS/toluene solution in the Ubbelohde viscometer and the precision of the time measuring on the viscosity behavior in dilute and extremely dilute concentration region are investigat...The influences of both the volume of PS/toluene solution in the Ubbelohde viscometer and the precision of the time measuring on the viscosity behavior in dilute and extremely dilute concentration region are investigated. It was found that the influence of the former can neglect, but that of the latter is so prominent that the data fluctuate bitterly and linearity of the curve of the reduced viscosity vs. concentration (hsp/c^c) becomes too bad to obey the Huggins equation down to the extremely dilute region, despite the error of the flow times Dt 0.2s, which is permitted by the conventional method of viscosity measurement. Through strict mathematical analyses, it was found that the error (E) of the reduced viscosity is in proportion and inverse proportion to Dt and concentration c, respectively. So the less the concentration, the more the error is. Consequently, a lowest concentration limit cL corresponding to given experimental error may exist and it will be meaningless for further operation below cL because of the great fluctuation of the data. Therefore, it needs to seriously reconsider the application of the conventional method of Ubbelohde viscosity measurement in the extremely dilute polymer solution under traditional conditions because of the great influence of the experimental error.展开更多
The calculations presented in this paper are based on the Sanchez-Lacombe（SL）lattice fluid theory.The interaction energy parameter,g12/k,required in this approach was obtained by fitting the cloud points of polystyr...The calculations presented in this paper are based on the Sanchez-Lacombe（SL）lattice fluid theory.The interaction energy parameter,g12/k,required in this approach was obtained by fitting the cloud points of polystyrene（PS）/methylcyclohexane（MCH）polymer solutions under pressure.The SL lattice fluid theory was used to calculate the spinodals,the binodals,and the Flory-Huggins（FH）interaction parameter of the solutions.The calculated results show that the SL lattice fluid theory can describe the dependences of thermodynamics of PS/MCH solutions on temperature and pressure very well.However,the calculated enthalpy and the excess volume changes indicate that the Clausius-Clapeyron equation cannot be suitable to describe pressure effect on PS/MCH solutions.Further analysis on the thermodynamics of this system under pressure shows that the role of entropy is more important than the excess volume in the present case.展开更多
文摘The influences of both the volume of PS/toluene solution in the Ubbelohde viscometer and the precision of the time measuring on the viscosity behavior in dilute and extremely dilute concentration region are investigated. It was found that the influence of the former can neglect, but that of the latter is so prominent that the data fluctuate bitterly and linearity of the curve of the reduced viscosity vs. concentration (hsp/c^c) becomes too bad to obey the Huggins equation down to the extremely dilute region, despite the error of the flow times Dt 0.2s, which is permitted by the conventional method of viscosity measurement. Through strict mathematical analyses, it was found that the error (E) of the reduced viscosity is in proportion and inverse proportion to Dt and concentration c, respectively. So the less the concentration, the more the error is. Consequently, a lowest concentration limit cL corresponding to given experimental error may exist and it will be meaningless for further operation below cL because of the great fluctuation of the data. Therefore, it needs to seriously reconsider the application of the conventional method of Ubbelohde viscosity measurement in the extremely dilute polymer solution under traditional conditions because of the great influence of the experimental error.
基金Supported by the National Natural Science Foundation of China(Nos.20574069,20490220,50303017,50373044and50340420392)Programs of the Chinese Academy of Sciences(No.KJCX2-SW-H07)the National Basic Research Program ofChina(No.2003CB615600).
文摘The calculations presented in this paper are based on the Sanchez-Lacombe（SL）lattice fluid theory.The interaction energy parameter,g12/k,required in this approach was obtained by fitting the cloud points of polystyrene（PS）/methylcyclohexane（MCH）polymer solutions under pressure.The SL lattice fluid theory was used to calculate the spinodals,the binodals,and the Flory-Huggins（FH）interaction parameter of the solutions.The calculated results show that the SL lattice fluid theory can describe the dependences of thermodynamics of PS/MCH solutions on temperature and pressure very well.However,the calculated enthalpy and the excess volume changes indicate that the Clausius-Clapeyron equation cannot be suitable to describe pressure effect on PS/MCH solutions.Further analysis on the thermodynamics of this system under pressure shows that the role of entropy is more important than the excess volume in the present case.
