For a system of flexible polymer molecules, the concepts of two concentrations, namely the segmental and the molecular concentrations, have been proposed in this paper. The former is equivalent to the volume fraction. The latter can be defined as the number of the gravity centers of macromolecules in a unit volume. The two concentrations should be correlated with each other by the conformational function of the polymer chain and should be discussed in different thermodynamic equations. On the basis of these concepts it has been proved that the Flory-Huggins entropy of mixing should be the result of the mixing “ideal gases of the gravity centers of macromolecules“. The general correlation between the free energy of mixing and the scattering function (structural factor) of polymer blends has been studied based on the general fluctuation theory. When the Flory-Huggins free energy of mixing is adopted, the de Gennes scattering function of a polymer blend can be derived. 相似文献
Cellulose was dissolved rapidly in 9.5 wt.‐% NaOH/4.5 wt.‐% thiourea aqueous solution pre‐cooled to ?5 °C to prepare cellulose solution with different concentrations. The rheological properties of the cellulose solutions in wide concentration regimes from dilute (0.008 wt.‐%) to concentrated (4.0 wt.‐%) at 25 °C were investigated. On the basis of data from the steady‐shear flow test, the critical overlap (c*), the entanglement (ce) and the gel (cg) concentrations of the cellulose solution at 25 °C were determined, respectively, to be 0.10 wt.‐%, 0.53 wt.‐% and 2.50 wt.‐%, in accordance with the results of storage modulus (G′) versus c by dynamic test. Moreover, the Cox‐Merz deviation at relatively low concentrations was in good agreement with the micro‐gel particles in dilute regime. As the cellulose concentration increased, a homogeneous 3‐dimensional network formed in the cellulose solution in the concentrated regime, and further increasing of the concentration led to micro‐phase separation as determined by the time‐temperature superposition (tTS). So far, this complex cellulose solution has been successfully described by the concentration regime theory for the first time, and the relatively molecular morphologies in each regime have been determined, providing useful information for the applications of the cellulose solution systems.
Abstract A freeze concentration method was tested for its ability to concentrate uncharacterized organic carbon, measured by TOC analyzer, in tap water derived from a surface water reservoir in eastern Massachusetts. Freeze concentration was carried out in polypropylene bottles of 2 liter volume, stirred at either 140 rpm or 400 rpm, and placed in a freezer at either -15°C or -25°C. No effect of stirring speed or freezer temperature on the recovery efficiency was found except possibly at high (>10x) concentration factors. For theoretical concentration factors below approximately ten, measured TOC was reproducible but substantially less than the theoretical value (e.g., for a theoretical value of 10, the measured concentration factor was only 4.3. At higher concentration factors, the ratio of the actual to theoretical concentration decreased further and became variable from experiment to experiment. Lack of quantitative recovery of TOC indicates the likelihood that selective concentration of different components of this material occurred. 相似文献
The purpose of this work is to determine the values of critical premicelle concentration (CPMC), first critical micelle concentration (FCMC) and second critical micelle concentration (SCMC) of surfactants using a common spectrofluorophotometer by recording resonance Rayleigh scattering (RRS) signal without any probe. The plot of the RRS intensities at the maximum scattering wavelength (I(RRS)(max)) versus surfactant concentrations (c) was constructed to obtain the I(RRS)(max)-c curve. From the inflexions in I(RRS)(max)-c curve, the CPMC, FCMC and SCMC values of a surfactant can be obtained sensitively. The FCMC of some anionic, cationic and nonionic surfactants such as sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), cetyltrimethylammonium bromide (CTAB), cetylpyridinium chloride (CPC), Tween-20, and Tween-80 were determined by RRS method and the values are in good agreement with those obtained from conductivity and surface tension measurements and literature values. The CPMC and SCMC of SDS and CTAB were also determined by RRS method respectively and the values conform to literature values too. Furthermore, RRS method can also be used to determine the FCMC of an amphiphilic macromolecule-hemoglobin, whose structure resembles a surfactant. From the experimental results, it is concluded that RRS method can be applied to the simultaneous determination of the CPMC, FCMC and SCMC values in a sensitive, accurate and no probe way. 相似文献
