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71.
D. C. Venerus J. D. Schieber H. Iddir J. D. Guzman A. W. Broerman 《Journal of Polymer Science.Polymer Physics》1999,37(11):1069-1078
Thermal diffusivity measurements on three polymer melts were made using the Forced Rayleigh Light Scattering technique. The polymers, which were tested at room temperature where they are in the molten state, included a polydimethylsiloxane and two polyisobutylenes. The optical setup and procedures developed in this study to conduct thermal Forced Rayleigh Light Scattering experiments are shown to be capable of producing thermal diffusivity data with a high degree of accuracy and precision. From measurements on a reference fluid (ethanol), experimental error was estimated to be no greater than 2%, and could be reduced to less than 1% by appropriate design of a series of experiments. Discrepancies of 4 and 14% in thermal diffusivity data on the polymer samples between measured values and those found in the literature were observed. It is suggested that these deviations are attributable to either sample variations or to errors in the techniques used in previous investigations. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1069–1078, 1999 相似文献
72.
Yong-kuk Yun Jung-Il Jin Myungsoo Lee 《Journal of polymer science. Part A, Polymer chemistry》1997,35(13):2777-2786
Two series of new aromatic copolyesters have been synthesized and their properties including liquid crystallinity have been studied. The first series was synthesized by polymerizing mixtures of diacetates of 2-(α-phenylisopropyl)hydroquinone and 1,1′-biphenyl-4,4′-diol with terephthalic acid, and the second by polymerizing mixtures of diacetates of 2-(α-phenylisopropyl)hydroquinone and 2,6-dihydroxynaphthalene with terephthalic acid. These polyesters were characterized by differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffractomerty, and optical microscopy. The glass transition temperatures of the first series decrease from 167 to 138°C as one increases the content of the 1,1′-biphenyl-4,4′-diol unit to 50 mol %. The Tg values of the second series are slightly higher than those of the first series, and appear to be less dependent on their composition. The degree of crystallinity of the first series decreases rapidly by copolymerization, much faster than that of the second series. The melting points of the first series copolymers are significantly lower than those of the second series. All of the copolyesters reported in this investigation form nematic melts. The initial decomposition temperatures of the copolymers were higher than 450°C. It was confirmed that thermal stability of the homopolyester, PIBPL-1.00, containing the isopropylidene units is significantly improved when compared with that carrying benzylic hydrogens. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2777–2786, 1997 相似文献
73.
E.P.K. Currie G.J. Fleer M.A. Cohen Stuart O.V. Borisov 《The European physical journal. E, Soft matter》2000,1(1):27-40
We present an analytical self-consistent-field (SCF) theory for a neutral polymer brush (a layer of long polymer chains end-grafted
to a surface) with annealed excluded volume interactions between the monomer units. This model mimics the reversible adsorption
of solute molecules or aggregates, such as small globular proteins or surfactant micelles, on the grafted chains. The equilibrium
structural properties of the brush (the brush thickness, the monomer density profile, the distribution of the end segments
of the grafted chains) as well as the overall adsorbed amount and the adsorbate density profile are analyzed as a function
of the grafting density, the excluded volume parameters and the chemical potential (the concentration) of the adsorbate in
the solution. We demonstrate that, when the grafting density is varied, the overall adsorbed amount always exhibits a maximum,
whereas the root-mean-square brush thickness either increases monotonically or passes through a (local) minimum. At high grafting
densities the chains are loaded by adsorbed aggregates preferentially in the distal region of the brush, whereas in the region
proximal to the grafting surface depletion of aggregates occurs and the polymer brush retains an unperturbed structure. Depending
on the relative strength of the excluded volume interactions between unloaded and loaded monomers both the degree of loading
of the chains and the polymer density profile are either continuous or they exhibit a discontinuity as a function of the distance
from the grafting surface. In the latter case intrinsic phase separation occurs in the brush: the dense phase consists of
unloaded and weakly extended chains and occupies the region proximal to the surface, whereas a more dilute phase consisting
of highly loaded and strongly extended chains forms the periphery of the brush.
Received 26 November 1998 and Received in final form 2 April 1999 相似文献
74.
Electric field light scattering results on aqueous solutions of linear, flexible NaPSS at minimal ionic strength are reported.
Samples of molecular weights between 356 kg/mol and 2870 kg/mol were investigated. With increasing field strength the intensity
as a function of wavenumber develops a pronounced oscillating behaviour. Besides the well-known first peak a second maximum
is observed at the position at which a weak maximum for some samples already occurs at zero field. The overall intensity strongly
depends on the frequency of the electric field. The electro-optical effect shows a maximum at 300 kHz. Increasing the particle
concentration gives a large increase of the peak maximum, normalized to concentration. If plotted versus scattering angle the relative intensity increase is maximum for samples of medium molecular weight. The results strongly
indicate a stretching and alignment of the chains, thus leading to or enlarging the short range order of the chains.
Received 9 April 1999 and Received in final form 18 August 1999 相似文献
75.
Studies performed on strong polyelectrolytes and on a weak polyelectrolyte, sodium poly(acrylate), show that their stability
in presence of multivalent cations depends on the chemical nature of the charged side groups of the polymer. For sulfonate
groups (SO3
-) or sulfate groups (OSO3
-) phase separation generally occurs in presence of inorganic cations of valency 3 (as La3+) or larger and a resolubilization takes place at high salt concentration. The interactions of the polyelectrolyte with multivalent
cations are of electrostatic origin and the phase diagrams are weakly dependent on the chemical nature of the polymer backbone
and on the specificity of the counterions. For acrylate groups, (COO-), the phase separation was observed with inorganic cations of valency 2 (as Ca2+) or larger without resolubilization at high salt concentration. The phase separation is due to a chemical association between
cations and acrylate groups of two neighboring monomers of the same chain. This chemical association creates a hydrophobic
complex by dehydrating both monomer and cation. With organic trivalent cation, as spermidine +H3N(CH2)4NH2
+(CH2)3NH3
+, where no chemical association occurs with the charged side groups COO- or SO3
- of the polyelectrolyte, similar phase diagrams were observed whatever was the polyelectrolyte with a resolubilization at
high trivalent cation concentration.
Received 3 March 1999 and Received in final form 2 September 1999 相似文献
76.
Manfred H. Wagner Heike Bastian Peter Hachmann Joachim Meissner Stefan Kurzbeck H. Münstedt F. Langouche 《Rheologica Acta》2000,39(2):97-109
By generalizing the Doi-Edwards model to the Molecular Stress Function theory of Wagner and Schaeffer, the extensional viscosities
of polyolefin melts in uniaxial, equibiaxial and planar constant strain-rate experiments starting from the isotropic state
can be described quantitatively. While the strain hardening of four linear polymer melts (two high-density polyethylenes,
a polystyrene and a polypropylene) can be accounted for by a tube diameter that decreases affinely with the average stretch,
the two long-chain-branched polymer melts considered (a low-density polyethylene and a long-chain branched polypropylene)
show enhanced strain hardening in extensional flows due to the presence of long-chain branches. This can be quantified by
a molecular stress function, the square of which is quadratic in the average stretch and which follows from the junction fluctuation
theory of Flory. The ultimate magnitude of the strain-hardening effect is governed by a maximum value of the molecular stress,
which is specific to the polymer melt considered and which is the only free non-linear parameter of the theory.
Received: 1 June 1999/Accepted: 24 November 1999 相似文献
77.
A time-stepping finite element method is used to predict the viscoelastic stresses that arise in a tube-tooling wire-coating problem. The polymer melt HDPE is modelled by a multi-mode Phan-Thien/Tanner constitutive equation. Different flow geometries are considered to address optimisation of the process with respect to minimising the stress induced within the coating produced. The influence of the die itself and the various modes are considered. Relaxation times range for a three-mode model from 10−2 to 102 s and for a seven-mode model from 10−3 to 103 s. Typical Weissenberg numbers may range up to 104. Three modes are sufficient to adequately describe the flow, and shorter/narrower draw-down regions are identified as being preferable. Once an adequate land length has been gathered, that has relaxed the flow stresses prior to draw-down, the actual details of die design are found to be inconsequential to the induced stresses in the delivered coatings. 相似文献
78.
S.T. Hyde C. Oguey 《The European Physical Journal B - Condensed Matter and Complex Systems》2000,16(4):613-630
A method is developed to construct and analyse a wide class of graphs embedded in Euclidean 3D space, including multiply-connected
and entangled examples. The graphs are derived via embeddings of infinite families of trees (forests) in the hyperbolic plane, and subsequent folding into triply periodic minimal
surfaces, including the P, D, gyroid and H surfaces. Some of these graphs are natural generalisations of bicontinuous topologies to bi-, tri-, quadra- and octa-continuous
forms. Interwoven layer graphs and periodic sets of finite clusters also emerge from the algorithm. Many of the graphs are
chiral. The generated graphs are compared with some organo-metallic molecular crystals with multiple frameworks and molecular
mesophases found in copolymer melts.
Received 10 December 1999 相似文献
79.
G. Bouglet C. Ligoure 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,9(1):137-147
Small angle X-ray and neutron scattering data on an effective three-component lamellar phase composed of water, a non adsorbing
water-soluble polymer (polyvynilpyrolidone), fluid membranes, made from a mixture of a cationic surfactant (cetylpiridiumchloride)
and a cosurfactant (hexanol), are presented for various membrane as well as polymer concentrations. The data are fitted with
a recently proposed model which takes into account the geometry and the fluctuations of these periodic structures. This allows
a quantitative study of the polymer contribution to the smectic compression modulus of the lamellar phase. Four different regimes of polymer confinement are expected. The associated variations in are compared to a recent theoretical model, which predicts the polymer-mediated contribution to the smectic compression modulus.
Received 20 January 1998 相似文献
80.
O.V. Borisov A. Halperin 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,9(2):251-259
A theoretical model of the extension and confinement of globular polysoaps predicts novel force laws. Polysoaps are polymers
comprising of a flexible hydrophilic backbone incorporating, at intervals, amphiphilic monomers. The equilibrium configuration
of long polysoaps, that form numerous spherical intrachain micelles, is a spherical globule of close packed micelles. The
coupling of the deformation to the hierarchical self organization of the chain gives rise to a distinctive force law involving,
for extension, two plateau regimes. When the chain is stretched by extensional flow the two regimes merge and the polysoap
exhibits a single globule-stretch transition.
Received 16 June 1998 and Received in final form 19 November 1998 相似文献