The spreading of polymer nanodroplets upon a sudden change from partial to complete wetting on an ideally flat and structureless solid substrate has been studied by molecular dynamic simulations using a coarse‐grained bead‐spring model of flexible macromolecules. Tanner's law for the growth of the lateral droplet radius {R(t) ∝ t0.1} is found to hold as long as the droplet does not disintegrate into individually moving chains. The data for the contact angle θ following from Tanner's law correspond to a dependence on time {θ(t) ∝ t−0.3}. Our analysis of the mean square displacements of the polymer centers of mass reveals several dynamic regimes during the process of spreading. PACS numbers: 68.10.Gw, 05.70.Ln, 61.20.Ja, 8.45.Gd.
Molecular dynamics results for the average mean square displacement of all polymer chains plotted vs. time for a broad range of values for εwall. 相似文献
Chiral cyclic α,α‐disubstituted amino acids, (3S,4S)‐ and (3R,4R)‐1‐amino‐3,4‐(dialkoxy)cyclopentanecarboxylic acids ((S,S)‐ and (R,R)‐Ac5cdOR; R: methyl, methoxymethyl), were synthesized from dimethyl L ‐(+)‐ or D ‐(?)‐tartrate, and their homochiral homoligomers were prepared by solution‐phase methods. The preferred secondary structure of the (S,S)‐Ac5cdOMe hexapeptide was a left‐handed (M) 310 helix, whereas those of the (S,S)‐Ac5cdOMe octa‐ and decapeptides were left‐handed (M) α helices, both in solution and in the crystal state. The octa‐ and decapeptides can be well dissolved in pure water and are more α helical in water than in 2,2,2‐trifluoroethanol solution. The left‐handed (M) helices of the (S,S)‐Ac5cdOMe homochiral homopeptides were exclusively controlled by the side‐chain chiral centers, because the cyclic amino acid (S,S)‐Ac5cdOMe does not have an α‐carbon chiral center but has side‐chain γ‐carbon chiral centers. 相似文献
In this note microgels with and without excluded volume interactions are considered. Based on earlier exact computations on Gaussian mircogels, which are formed by self-crosslinking (with M crosslinks) of polymer chains with chainlength N, Flory type approximations are used to get first insight to their behavior in solution. It is shown that two different types of microgels exist: A special type of branched polymer whose size scales as R ∝ N2/5/M−1/5, instead of R ∝ N1/2. The second type are c*-microgels whose average mesh sizes r are swollen and form self avoiding walks with a scaling law of the form r = a(N/M)3/5. 相似文献
Graft copolymerization of styrene on rubber containing chlorine, e.g., chloroprene rubber (CR) and chlorosulfonated polyethylene (Hypalon), with chromous acetate (Cr2+) was carried out in DMF–THF mixed solvent at 50°C. From the kinetic study, the normal kinetic orders with respect to the concentration of initiator and monomer were obtained at low concentrations of CR, but the deviation from conventional first-order to second-order kinetics with respect to the monomer concentration was observed at high CR concentrations: Rp ∝ [CR]1/2 [Cr2+]1/2[styrene]1 (at low CR concentration); Rp ∝ [CR]1/2 [Cr2+]1/2[styrene]1 (at high CR concentration). This result was explained in terms of the high viscosity of the reaction medium due to the rubber contained in solution. An initiation site along the polymer chain was assumed from the graft copolymerization with three kinds of CR having different microstructures. The results of fractionation of obtained polymer showed that the graft efficiency was high but a large amount of gel was formed. 相似文献
We have analyzed chain conformations and the existence — or otherwise — of chain overlaps and entanglements in dilute polymer solutions (at concentrations c < C*, c* = critical concentration). The fundamental problem of existence of chain overlaps in dilute solutions is also related to the drag reduction phenomenon (DR). Some experimental results pertinent to DR are explained in terms of entanglements even for solutions at concentrations defined in ppm. We report results of Brownian dynamics simulations of polymer solutions in which the equations of motion of the chains are solved by using the Langevin equation. Chains move according to actions of a systematic frictional force and a randomly fluctuating force w(t), where t is time. In addition, a shear flow field can be introduced into the model. To evaluate the structure of polymer chains in solution we have devised a measure of interchain contacts and two different measures of entanglements. The results for c = 0.3 c* demonstrate that both chain entanglements and overlaps take place even in dilute solution. They also confirm predictions from an earlier combinatorial model. 相似文献
The internal dynamics of semiflexible fibrin gels has been investigated by means of dynamic light scattering (DLS). Fibrin gels, grown at room temperature from fibrinogen solutions at different NaCl concentrations, exhibit rather different structural features. High salt concentrations produce “fine” gels characterized by thin fibers and small mesh sizes, while low salt concentrations give rise to “coarse” gels with thick fibers and much larger mesh sizes. The observed dynamics of these two kinds of gels are quite different as well. “Fine” gels behave as typical semiflexible polymer gels, in which the dynamic structure factor f(q,t) shows an initial monoexponential decay followed by a stretched exponential decay, f(q,t) ∼ exp ‐(Γqt)β. Conversely, “coarse” gels exhibit a highly arrested dynamics, in which the dynamic structure factor does not relax to zero, but decays to a plateau whose value depends on the scattering wavevector q. Moreover, only the stretched exponential decay is observed at the fastest decay times, with the exponent β = 0.63±0.07 being independently of q. This behaviour can be interpreted as given by the contributions of the internal elastic modes of many different length scales. 相似文献
The radiation-induced heterogeneous polymerization of ethylene in ethyl alcohol was carried out in a reactor with a capacity of 100 ml under the following reaction conditions: temperature, 24 ± 3°C; pressure, 200–400 kg/cm2; amount of ethyl alcohol, 30–70 ml; dose rate, 3.7 × 104?1.05 × 105 rad hr. The effects of amount of ethyl alcohol, pressure, and dose rate on the rate of polymerization at the steady state, the amount of polymerized monomer, the molecular weight of polymer, and the number of polymer chains were studied compared with the results obtained in the polymerization in tert-butyl alcohol. It was found that there is an acceleration period in the early stage of reaction followed by a steady state. The rate of polymerization was maximum when about 50 ml of ethyl alcohol was used. The molecular weight of polymer increased with a decrease in the amount of ethyl alcohol. The dependences of pressure (p) and dose rate (I) on the rate of polymerization at steady state (Rs) and the molecular weight of polymer (M?n) were expressed as follows; Rs ∝ p0.74, M?n ∝ p0.3?0.4, Rs ∝ I0.9 and M?n ∝ I?0.1 ?0.0. The results were analyzed by a kinetic treatment based on a reaction mechanism containing both first-and second-order terminations. The rate constant of first-order termination by radical occlusion was considerably larger than that in the polymerization in tert-butyl alcohol, because the affinity of ethyl alcohol for polyethylene is smaller than that of tert-butyl alcohol. It was found that chain transfer to ethyl alcohol takes place easily and the G value of ethyl alcohol for initiation is larger than 1.5. 相似文献