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1.
Some new flexible and cross-linkable copolyimides containing rubbery unsaturated aliphatic chain moiety (CPLA) were prepared by low temperature polycondensation betweenm-phenylene diamine,bis- 3(4 carboxy phthalimido) benzene, and liquid, bis [2-(4 piperazinyl) ethyl aminocarbonyl] poly-(butadiene-co-acrylonitrile) (ATBN) in (DMAC) solution. The effect of rubbery aliphatic moiety in these copolyimides on the polymer properties has been reported. A comparative study on the properties of these copolyimides (CPLA) with the mixture of ATBN and a low molecular-weight cross-linkable copolyimide possessing the same molecular structure as the aromatic moiety of CPLA polymers has been made.  相似文献   

2.
The structure-property relationships derived here permit the prediction of both the zero-shear viscosity 0, as well as the shear rate dependent viscosity . Using this molecular modeling it is now possible to predict over the whole concentration range, independently of the molecular weight, polymer concentration and imposed shear rate. However, the widely accepted concept: dilute — concentrated, is insufficient. Moreover it is necessary to take five distinct states of solution into account if the viscous behavior of polymeric liquids is to be described satisfactorily. For non-homogeneous, semi-dilute (moderately concentrated) solutions the slope in the linear region of the flow curve (= must be standardized against the overlap parameterc · []. As with the 0-M-c-relationship, a-M -c- relationship can now be formulated for the complete range of concentration and molecular weight. Furthermore, it is possible to predict the onset of shear induced degradation of polymeric liquids subjected to a laminar velocity field on the basis of molecular modeling. These theoretically obtained results lead to the previously made ad hoc conclusion (Kulicke, Porter [32]) that, experimentally, it is not possible to detect the second Newtonian region.Roman and Italian symbols a exponent of the Mark-Houwink relationship - b exponent of the third term of the 0-M -c relationship - c concentration /g · cm–3 - E number of entanglements per molecule - F(r) connector tension - f function - G i A shear modulus; A indicates that it /Pa has been evaluated by a transient shear flow experiment; i is the shear rate to whichG A refers to - G storage modulus /Pa - G p plateau modulus /Pa - H() relaxation spectrum /Pa - h shift factor (0/r) - K H Huggins constant - K b third constant of the 0-M -c relationship - K constant of the Mark-Houwink relationship - M molecular weight /g · mol–1 - M e molecular weight between two /g · mol–1 entanglement couplings - N number of segments per molecule - n slope in the power-law region of the flow curve - p p-th mode of the relaxation time spectrum - R gas constant /8.314 J·K–1·mol–1 - r direction vector - T temperature /K Greek symbols ß reduced shear rate - shear rate /s–1 - shear viscosity /Pa·s - s solvent viscosity /Pa·s - sp specific viscosity - 0 zero-shear viscosity /Pa·s - apparent viscosity at shear rate - reduced viscosity - viscosity of polymeric liquid in /Pa·s the second Newtonian region - [] intrinsic viscosity/cm3·g–1 - screening length/m - /g·cm –3 density - relaxation time/s - 0 experimentally derived relaxation time/s - angular frequency of oscillation Indices conc concentrated - corr slope corrected - cr critical - deg degradation - e entanglement - exp experimental - mod moderately concentrated/semi-dilute - n number average - p polymer - R Rouse - rep reptation - s solvent - sp specific - theo theoretical - weight average - relaxation time - o experimental or steady state - * critical - ** transition moderately conc. — conc. - + transition dilute — moderately cone. Paper presented at the 2nd bilateral U.S.-West German Polymer Symposium, Yountville, the 7th–11th September 1987.  相似文献   

3.
The electrostatic interaction pressure of charged surface layers is considered qualitatively and quantitatively. In the case of mutual penetration of the surface layers in addition to Maxwell stress and osmotic resp. hydrostatic pressure an isotropic stress on the fixed charges carrying molecules of the surface layers has to be taken into account. The derivation of the pressure-distance equations is given starting from both thermodynamic/electrostatic and hydrostatic/electrostatic principles. A possible biological significance of the additional stress is discussed emphasizing its role in modifying the structure of surface layer molecules.List of symbols e 0 elementary charge - k Boltzmann constant - n i concentration of theith ionic species in the bulk solution - P hydrostatic pressure - P hydrostatic pressure in the bulk volume (× ) - P h integration constant, independent on ×:P h =P(h) - T absolute temperature - Z i electrovalence of theith ionic species - thickness of the surface layer - , 0 relative and absolute permittivities - II(×) osmotic pressure at position × - II osmotic pressure in the bulk solution (× ) - osmotic pressure in the symmetry plane of interacting identical surface layers (electric field strength equals zero) - integration constant, independent on ×: - e h electrostatic component of the disjoining pressure e h = e (h) - (×) mobile charge density profile (cations and anions of the electrolyte) - (×) fixed charge density profile - t(x) total charge density profile ( t = +) - 1(x) fixed charge density profile of one of the two surface layers ( 1(×) 0 for 0×) - (×) electric potential profile  相似文献   

4.
Monte Carlo studies of symmetrical polymer mixturesAB, modelled by selfavoiding walks withN A =N B =N steps on a simple cubic lattice, are presented for arbitrary concentrations of vacancies v in the range from v =0.2 to v =0.8 and chain lengthsN64. We obtained the phase diagrams and the equation of state for three choices of the ratio / AB ( being the energy between monomers of the same kind, AB being the energy between different monomers). Flory-Huggins theory provides only a qualitative understanding of these results. If the equation of state is fitted with an effective Flory-Huggins parameter eff , the latter turns out to be strongly dependent on both concentration and temperature.Contributed paper delivered at the Tagung der Deutschen Physikalischen Gesellschaft, Fachausschuß Polymerphysik, Berlin, March 30–April 3, 1987.  相似文献   

5.
The permeability of styrene-butadiene block copolymer foils with different composition prepared by casting and pressing has been investigated for the gases Ar, CO2, and CH4 at pressure difference of 400 mbar and at the temperature range 298 T [K] 333.The permeation process can be described by the solution diffusion mechanism. The diffusion coefficients decrease in the sequence of the gases Ar, CO2, and CH4 and the solubility coefficients increase in the sequence Ar, CH4, CO2.The dependence of the permeability on the composition of the block copolymer can be interpreted by the help of percolation theory and the effective medium theory. It follows the critical volume fraction of the percolation of the transport phase PB c (= 0,23) and the coordination numberz (= 4) giving an information concerning the multiphase structure of the block copolymer.Presented in part at the 33rd Annual Meeting of the Colloid-Gesellschaft, Graz, Austria, September 14–16, 1987.  相似文献   

6.
The dielectric behavior (, ) of three well-cleaned monodisperse polystyrene latexes having the same particle size and the same number of chemically-bound surface groups has been studied at a fixed microwave frequency (9.4 GHz), as a function of temperature and surface group (SO 4 , COO, OH).A large dielectric relaxation was observed in the sulfate-stabilized latex, which has the most polar surface end-group. The anomalous behavior in the thermal dependence of the hydroxyl and carboxyl-stabilized latexes (the OH latex being more pronounced than the COO latex) may originate from differences in the experimental conditions used for the preparation of such polymer colloids, or due to the presence of ionic species.On the basis of various dielectric models, the apparent volume fractions of the latexes were calculated. The amount of bound water around the latex particle was quantitatively correlated to the polarity of surface end-group (SO 4 > COO > OH). The differences between the calculated and actual values were not only a reflection of the thickness of vicinal water, but could also be indicative of the presence of oligomeric species in the suspension's medium (serum) of the latex. The permittivities of hydrated particle and of bound water were obtained with a non-linear iterative procedure.  相似文献   

7.
The enumeration theory is extended in this work into a more general theory, taking back-reactions into consideration. The solutions may faithfully reproduce real processes from arbitrary starting points to a steady-state. Therefore, the presented theory includes the equilibrium theory by Jacobson-Stockmayer, the numerical solution by Gordon-Temple, and the irreversible theory by the present authors. The solutions are described first in general forms of transition probabilities {P}, and then explicitly with the aid of rate equations; simple proofs are given. The presented theory was applied to an experimental data: the distribution of cyclic species in poly(ethylene terephthalate). We shall show that agreement between theory and experiment is nearly perfect.AB model N 0 Total number of units - V System volume - C 0=N 0/N A ·V Initial concentration (N A : Avogadro's number) - L x AB type chain x-mer; (AB)x - N x Number of AB type x-mers - R x Ring x-mer - N Rx Number of ring x-mers - E Small molecule eliminated by bond-formation - N E Number of small molecules eliminated by bond-formation - h k Number of reacted functional units (f.u.) in statek - k Number of reacted functional units (f.u.) in chains in statek - k Total number of units in chains in statek - D=h k /N 0 Extent of reaction in statek - D *= k / k Extent of reaction in chains in statek - k L Chain-propagation rate constant - k Rx Cyclization rate constant of chain x-mers - k B Bond breakage rate constant of chains - k B,Rx Bond breakage rate constant of cyclic x-mers - <k Rx > k Mean cyclization rate constant in statek - g(x)=k B,Rx /k B Ring-opening factor of cyclic x-mers - P Lx,k Probability that a chain x-mer will be formed in statek - {P} Set of transition probabilities per single jump in forward direction or reverse direction (see the text on individual transition probabilities) AB model M A Total AA monomer unit number - M B Total BB monomer unit number - M 0=M A +M B Total particle number - A,i =2M A h i Unreacted A functional unit (f.u.) number in statei - B,i =2M B h i Unreacted B f.u. number in statei - Ax Unreacted A f.u. number on x-mers - h i Number of reacted A (or B) f.u. in statei - i Number of reacted A (or B) f.u. in chains in statei - A,i =2M A h i + i A f.u. number in chains in statei - B,i =2M B h i + i B f.u. number in chains in statei - i =2(M 0h i + i ) Total f.u. number in chains in statei - D=h i /M 0 Extent of reaction in statei - D A * = i / A,i Extent of reaction of A f.u. in chains in statei - D B * = i / B,i Extent of reaction of B f.u. in chains in statei - D *=2 i / i Extent of reaction in chains in statei - L x (AA-BB)x-1-AA type chain x-mer;x=1,2,3,... - L x BB-(AA-BB)x type chain x-mer;x=0,1,2,... - L x (AA-BB)x type chain x-mer;x=1,2,3,... - N x Number of type x-mers - N x Number of type x-mers - N x Number of type x-mers  相似文献   

8.
Three series of segmented polyurethanes based on MDI, variable chain extender, and polypropylene oxide of MW=1000, 2000, and 3000 were synthesized and their dielectric behavior examined.Dielectric relaxations in the segmented polyurethanes were investigated between –150°C and +150°C in the 100 Hz to 10 kHz range. In general, three transitions, designated as, , and were observed, and ascribed in accordance with calorimetric relaxations to glass transitions of the hard and soft segments, and Shatzki-type motions, respectively. The effect of structure variables such as soft segment size, type of chain extender (ethylene glycol, butane diol, and hexane diol) and soft segment concentration, as well as the effect of interaction of the phases on dielectric properties was discussed. It was found that a certain degree of phase mixing exists in all series, detected by the variation of theT g of the soft segment with soft segment concentration, contrary to DSC results, which was ascribed to thermal treatment prior to the dielectric measurements. It appears that interfacial polarization becomes important only above the transition temperature.  相似文献   

9.
Torsional potentialV() for the single bond transformation in an extended hexadecane, subjected to elongation, has been determined by molecular mechanics calculations. The stored elastic energy significantly modifies the potentialV(), the conformational energies and the barriers of transition. Apart from the soft torsional coordinate, elastic energy is also dissipated considerably by bond stretching and angle bending. Maximal variations of the valence coordinates occur in the vicinity of the torsional defect and dampen along the chain. At higher elongation, the gauche minimum on the potentialV() disappears and the calculations predict the abrupt gauche to trans transition. The energetics of torsion of a deformed chain are compared with the experimental data on the hydrodynamic extension of polymers in dilute solution by elongational flow. The calculations also provide details of a single bond transformation mechanism at conformational interconversions in a long chain, proposed by Helfand.  相似文献   

10.
The special nature of the outer-most water-rich region of theL 2-phase in the ternary system sodium octanoate-octanoic acid-water is evidenced by its somewhat turbid appearance and by the character of its equilibria with adjacent phases. The phase contains aggregated acid sodium octanoate which is dispersed in a very dilute aqueous solution of sodium octanoate. The acid octanoate has the composition 1 NaC82 HC8x H2O and is composed of closely packed amphiphilic units, all with the polar groups in the same direction. This acid soap obviously forms double-layered aggregates with the lipophilic hydrocarbon chains pointing inwards and the polar groups pointing outwards towards the surrounding bulk-water. The phase is formed when octanoic acid is added to theL 1-phase of the system just above the l.a.c.; in this aqueous solution, the acid reacts with dissolved acid octanoate 1 NaC81 HC8x H2O and that results in the formation of the slightly soluble acid soap 1 NaC8 2 HC8x H2O that separates as a new phase, the turbidL 2 phase. On further addition of octanoic acid, the content of the mentioned acid soap increases until the solution phase is transformed into a liquid crystalline lamellarD-phase with the same acid soap composition. This formation of acid soap 1 NaA2 HA on addition of fatty acid to the dilute soap solution just above the l.a.c., has been known for a long time to occur in various systems containing a long-chain sodium soap. However, at suitably low temperatures, the reaction in these systems does not result in separation of the acid soap in the liquid crystalline, but in the solid crystalline state.  相似文献   

11.
The diffusion of six azo and five anthraquinone derivatives through nylon 6, poly(ethylene terephthalate) and secondary cellulose acetate films were studied under high hydrostatic pressures of up to 3000 bar and at temperatures 80–130 °C, by analyzing the diffusion profiles yielded in a stacked multiple film, placed in the solution of the diffusant. It was found that the diffusion coefficient,D, of the diffusant decreased with increasing pressure, giving a linear relationship between InD and the pressure, the slope of which gave the activation volume for the diffusion,V . It was revealedV increased linearly with increasing intrinsic molecular volume of the diffusant,V w , the slopes being different between the azo and the anthraquinone derivatives. The ratio ofV toV w (V /V w ) ranged from 0.13 to 0.93, depending in a sensitive manner on the degree of swelling of the polymer matrix which in turn was varied by the solvent. The overall results could be explained in accordance with the formulation,V f, local +V =V w , whereV f, local represents the free volume contribution. It was proposed thatV w is increased by solvation when the solvent is good for the diffusant.  相似文献   

12.
Molecular motions in poly(diethyl siloxane) were studied by solid-state29Si-NMR in the temperature range 180–350 K. In this temperature range two solid phases 1 and 2, a mesophase m, and an amorphous isotropic phase exist. The nature of the chain mobility in the different phases was deduced from the resulting changes in the NMR line-shape governed by anisotropic chemical shift. In the intermediate solid phase 2 its anisotropy is reduced by 25% compared with the low temperature phase 1 due to the onset of oscillations around the chain axis and conformational transitions. In the mesophase m the polymer chain rotates about its long axis yielding an axially symmetric chemical shift tensor opposite in sign to that in the 1, 2 phases. The broad transition of the mesophase into the isotropic phase is accompanied by an increase in a narrow Lorentzian line arising from the amorphous phase. The results are compared with previous1H NMR, Raman-spectroscopy and x-ray measurements.After completion of this work we learnt that PDES has recently also been studied through13C-MAS and29Si-NMR by Möller et al. [13].  相似文献   

13.
The viscosity B coefficients of polyethylene glycols (M=62–1000) are determined at 25 °C. The B coefficient increases non-linearly with the number of ethyleneoxide (EO) units. The increase of the B coefficient per EO(0.111 dm3/mole) is less than the B value for two methylene groups (0.160 dm3/mole). This is discussed in terms of changes in the configurations of polyethylene glycols with long EO chains.Molecular size is the major factor that contributes to B at shorter chains, but solvation (hydration) becomes dominant as the number of ethyleneoxide groups increases. The hydration parameter,(gH2O/g ethyleneglycol), shows a linear dependence on B at low mass followed by a non-linear increase at high molecular mass and the viscosity C coefficient accounts for the solute-solute interactions.Symbols absolute viscosity - d absolute viscosity of dispersion medium - r relative viscosity - sp specific viscosity - ¦ o ¦ intrinsic viscosity at infinite dilution - ¦ c ¦ intrinsic viscosity as a function of solute concentration - partial specific volume - volume fraction - hydration (weight of H2O hydrating 1 g of polyethylene glycol) - c hydration as a function of solute concentration - K shape function - K c shape function as a function of solute concentration  相似文献   

14.
The technique of small angle neutron scattering (SANS) has been used to study the conformation of polystyrene chains in dilute solution under a constant shear gradient. The experiments reveal a distinct anisotropy of the molecular dimensions with regard to the directions parallel and perpendicular to the flow direction on the 2D-multidetector. The deformation ratio of the single polymer chain (R 2/R iso 2 )–1 as a function of the reduced shear gradient=([] · · M w G)/RT shows a transition from the ideal 2-behaviour for dynamic infinitely flexible coils found at small gradients, to a behaviour with smaller increase at larger. These results are qualitatively consistent with the theory of Cerf for a polymer with finite internal viscosity in a shear gradient. At low(<1), a better agreement with the model of a free-draining coil (Rouse behaviour) than with the Zimm model is observed.  相似文献   

15.
The results of X-ray diffraction patterns of homologous thallium soaps TlC n (n-8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 20 and 22) in dependence on the temperature showed that the structures of the phases below the temperature range of the liquid-crystalline neat phase (so called phase C1, phase C2, phase I, phase II) are crystalline-like, not liquid-crystalline.As function of the chain length of the fatty acid group, we found the following phase sequences to be a function of temperature: TlC8: phase Ineat phase: TlC9–Tl14: phase C2phase IIphase Ineat phase; TlC15, TlC16: phase C1phase IIphase Ineat phase; TlC17–TlC22: phase C1phase IIneat phase.From the X-ray patterns of the thallium soaps were calculated the lattice parameters and the unit cells of these homologues at various temperatures. The comparison between the lattice parameters of the homologues showed, surprisingly, that these parameters were independent of chain length and temperature. This X-ray data are the basis for the following development of structure models of the phase C1, phase C2, phase I, and phase II, including the neat phase (see Part 2).  相似文献   

16.
Anomalous polymer microspheres having uneven surfaces were produced by stepwise heterocoagulation technique of small polymer particles (SPs) onto large polymer particles (LPs).SPs andLPs have surface charges opposite to each other in the emulsion states.SPs were produced by emulsion copolymerization of styrene and methacryloyloxyethyltrimethylammonium chloride, andLPs by emulsion terpolymerization of styrene, butyl acrylate and methacrylic acid, with nonionic emulsifier being used in both cases. Maximum covering ofLP bySPs was obtained under the conditions that both emulsions were blended without the coagulation at pH 3 at room temperature and then left stand to coagulate with each other at 70 °C for 4 h at pH 9.Part CXI of the series Studies on Suspension and Emulsion.  相似文献   

17.
Adsorption of acetone on active carbon and active carbon supported metals (Ni, Cu, Zn and Cd) have been studied as a function of temperature. Thermodynamic parameters such as G 0, H 0, and S 0 are calculated from virial and Langmuir isotherm expressions. It is observed that active carbon supported metals have more adsorption affinity for acetone as compared to active carbon. Results show that the increase in adsorption affinity for active carbon supported metals is not due to configurational factors affecting the entropy of adsorption, but because of enhanced enthalpy of adsorption. XRD spectra show that active carbon supported metals adsorbents are amorphous and metal residues are present on the surface of active carbon in its reduced form. From adsorption data, isosteric heats and molar entropies of adsorption were calculated as a function of coverages and temperature. The values of isosteric heats of adsorption were found to be higher for active carbon supported metals, which may be due to the chemisorption of adsorbate molecules with metal sites present on the surface of active carbon. The extent of coordination of adsorbate molecules with metal sites is discussed on the basis of the acidic character of metal.  相似文献   

18.
Two ternary phase diagrams of the cationic perfluorosurfactant diethanolheptadecafluoro-2-undecanolmethylammonium chloride (DEFUMAC) with an anionic perfluorosurfactant lithium perfluorooctanesulfonate (LiFOS) and an anionic hydrocarbon surfactant lithium dodecyl sulfate (LiDS) have been established at 25°C. The total surfactant concentration was less than 20wt%. In a wide mixing region of the LiFOS/DEFUMAC system, a lamellar-type phase,P , was identified by its texture under a polarization microscope and by its x-ray diffraction pattern. Dispersed fragments ofP -phase are present in the dilute solutions in which one surfactant was in excess. The anisotropy of electrical conductivity, flow birefringence, dynamic light scattering, and electric briefringence demonstrate that theP fragments are disk-like with a radius of 0.7 m. The disk-likeP particles are transformed by shear into a spherical aggregate ofL above a critical shear gradient. LiDS/DEFUMAC mixed solution forms dispersed and precipitatedL in the dominant region. Radius and micropolarity of the dispersedL aggregates are decreased as the ratio of LiDS:DEFUMAC approaches 1:1. On the basis of x-ray diffraction measurement the structure of precipitatedL -phase seems to consist of monolayers.  相似文献   

19.
The capacitance and the dielectric loss tangents of CaCO3 filled polyethylene composites were studied. Composite samples, prepared by polymerizing ethylene on the surfaces of fillers, pre-treated by polymerization catalysts, were compared to normal mechanical mixtures. Dielectric dispersion,, and loss, , proved to be sensitive to heating or vacuum treatment. Investigation of samples under conditions of different relative humidities showed that the dielectric dispersion is due to adsorbed water. Both and increased with decreasing frequency and the ratio of loss and dispersion was nearly constant. Dielectric data measured at different relative humidities could be represented by a single Cole-Cole plot. Samples soaked in water for different periods yielded qualitatively similar but quantitatively different Cole-Cole plots. Composite samples showed higher losses at similar humidities.Possible interpretations in terms of a molecular relaxation model, an interfacial relaxation model, including a charged double layer mechanism, percolation theory and the universal response theory were examined, but none was able to fully explain the observed phenomena.  相似文献   

20.
Viscosity measurements were made in the temperature range of 10 °–40 °C. The equation= o exp(B/(T-T o )) was used with the parameterT 0 as structure indicator, which is called the limiting temperature. For instance, hydrocarbons, as liquids with quasifree molecules, haveT 0=O; water as a highly structured liquid hasT 0= 140–150 K.The polymer investigated was ovalbumin in aqueous solution in a concentration comparable to that of blood. Acetylsalicylic acid produces a protein conformation which breaks the water structure in solution at a pH of within the in vivo region.The question of whether only the acidity determines the water structure breaking properties of the protein is investigated by acidifying albumin-water solutions with hydrochloric acid, lysine chloride and ascorbic acid. All these acids exhibit similar effects. A stronger influence is observed for ammonium chloride. Its interaction with ovalbumin produces a strong structure-breaking effect. The most powerful water structure breaker in albumin-water solutions is dextrane. In a concentration of 10 % it changes the polymer conformation so that the water structure is broken to such an extent that the solution behaves as an almost quasifree liquid withT 0=O.  相似文献   

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