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1.
Massa MV Dalnoki-Veress K Forrest JA 《The European physical journal. E, Soft matter》2003,11(2):191-198
We present a detailed study of the kinetics of
crystallization for thin films of poly(ethylene oxide) (PEO).
Measurements of the growth rate have been carried out using
optical-microscopy techniques on films of monodisperse PEO.
Films with thicknesses from 13 nm to ~2 m were crystallized
isothermally at temperatures ~20°C below the melting point. A
remarkable non-monotonic
slowing-down of the crystal growth is observed for films with
thickness less than ~400 nm. The changes in the growth rate from
bulk-like values is significant and corresponds to a factor of
40 decrease for the thinnest films studied. The morphologies of
isothermally crystallized samples are studied using atomic-force
microscopy. We find that a morphology, similar to
diffusion-controlled growth (dendritic growth and densely
branched growth), is observed for films with
h < 150 nm. In addition,
changes in the morphology occur for thicknesses consistent with
changes in the growth rate as a function of film thickness. 相似文献
2.
Jolanta Prywer 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,25(1):61-68
According to contemporary crystal growth theories, crystals are bound by low-index faces which are the most slowly growing.
However, high-index faces are observed in crystal habits more and more often. In this paper the growth of high-index faces
is analysed from a crystallographic perspective. It is shown that the crystallographic structure of a given crystal, expressed
by the trigonometric function of appropriate interfacial angles, influences to great degree the crystallisation process and
the morphology of crystals, in particular the behaviour of high-index faces. Additionally, it is concluded that at particular
crystallographic structure of a crystal, a given high-index face may exist in the habit and develop its size, although it
grows much faster than the neighbouring faces.
Received 31 July 2001 相似文献
3.
Ultra thin films of glassy polymers such as polystyrene (PS) can show a) anomalously large thickness changes, b) unexpected
dewetting properties, c) large shifts in the glass temperature Tg. The present discussion focusses mainly on point a). A certain cascade of metastable states is presented together with (tentative)
explanations.
Received 1 March 2001 and Received in final form 10 May 2001 相似文献
4.
G. Reiter G. Castelein P. Hoerner G. Riess J.-U. Sommer G. Floudas 《The European physical journal. E, Soft matter》2000,2(4):319-334
Spin-coated thin films of about 100nm of low-molecular-weight hydrogenated poly(butadiene-b- ethyleneoxide) (PBh-PEO) diblock copolymers have been crystallized at various constant temperatures. Crystallization has been observed in real
time by light microscopy. Detailed structural information was obtained by atomic force microscopy, mainly enabled by the large
viscoelastic contrast between amorphous and crystalline regions. The behavior in thin films is compared to the bulk properties
of the polymer. Crystallization started from an annealed microphase separated melt where optical microscopy indicated a lamellar
orientation parallel to the substrate. A small difference in the length of the crystallizable block produced significantly
different crystallization behavior, both in the bulk and in thin films. For thin films of the shortest diblock copolymer (45%
PEO content) and for an undercooling larger than about 10 degrees, crystallization created vertically oriented lamellae. These
vertical lamellae could be preferentially aligned over several micrometers when crystallization occurred close to a three-phase
contact line. Annealing at temperatures closer to the melting point or keeping the sample at room temperature for several
months allowed the formation of a lamellar structure parallel to the substrate. A tentative interpretation based on kinetically
caused chain folding and relaxation within the crystalline state, with implications on general aspects of polymer crystallization,
is presented.
Received 19 March 1999 and Received in final form 14 December 1999 相似文献
5.
B. Lotz 《The European physical journal. E, Soft matter》2000,3(2):185-194
Contrary to most or all other materials, crystallization of chiral but racemic polymers such as isotactic polypropylene is
accompanied by a conformational rearrangement which leads to helical geometries: the building units of the crystal are helical
stems, -20nm long, which can be either right-handed or left-handed. Helical hand cannot be reversed within the crystal structure: it is therefore a permanent marker and an indicator of molecular processes (in particular segregation/selection of helical hands) which take place during crystal
growth, and more precisely during the crucial step of “efficient” helical stem deposition. The issue of proper helical hand
selection during polymer crystal growth is mainly illustrated with isotactic polypropylene. Its various crystalline polymorphs
(, , and smectic) display virtually all possible combinations of helical hands, azimuthal settings and even non-parallel orientation
of helix axes in space. Furthermore, a specific homoepitaxy which generates a lamellar branching in the phase “quadrites” and composite structures makes it possible a) to determine the helical hand and associated azimuthal setting of every stem in
the crystalline entities and b) to determine the impact on the crystal structure and morphology of “mistakes” in helical hand
of the depositing stem. Analysis of these morphologies demonstrates that the crystallization of isotactic polypropylene (and
by implication of other achiral, helical polymers) is a highly sequential and “substrate-determined” process, i.e. that the depositing stem probes the topography of the growth face prior to attachment. These observations appear difficult to reconcile with crystallization schemes in which molecules (helical segments) are
prearranged in a kind of pseudo-crystalline bundle (and as such, are not subjected to the high constraints of crystal symmetry)
before deposition as a preassembled entity on the substrate.
Received: 5 May 2000 相似文献
6.
Carvalho AJ Pereira-da-Silva MA Faria RM 《The European physical journal. E, Soft matter》2006,20(3):309-315
Self-organized block copolymer structures derived from dewetting of thin films are becoming important in nanotechnology because
of the various spontaneous and regular sub-micrometric surface patterns that may be obtained. Here, we report on the self-organization
of a poly(styrene)-b-poly(ethene-co-butene-1)-b-poly(styrene) triblock copolymer during drying of its solution over a mica
substrate. Regular submicrometric arrangements with long-range order were formed at critical polymer concentrations, consisting
of parallel ribbons and hexagonal arrays of dots (droplets). This variety of highly ordered structures is explained by the
interplay between forming mechanisms, mainly due to “fingering instabilities” at the three-phase line of the copolymer solution
during drying. The thickness of the structures was “quantized” due to the microphase separation of the block copolymer. The
formation of hexagonal patterns may be attributed to Marangoni instability at the liquid film surface prior to dewetting. 相似文献
7.
T. Albrecht S. Armbruster S. Keller G. Strobl 《The European physical journal. E, Soft matter》2001,6(3):237-243
Poly(ethylene oxide) (PEO) in the semi-crystalline state shows a reversible surface crystallization and melting; a temperature
decrease leads to a certain crystal thickening, a temperature increase reversely to an expansion of the amorphous intercrystallite
layers. Dynamic calorimetry provides a means to investigate the kinetics of the process. The structural rearrangement in the
region of the crystalline-amorphous interface can only be accomplished if the chains can slide through the crystallites. One
therefore expects the associated time to change with the crystallite thickness. Variations of the crystal thickness of PEO
can be achieved by choosing different crystallization temperatures. We studied the effect of the crystal thickness employing
temperature-modulated differential scanning calorimetry and heat wave spectroscopy, and by carrying out small-angle X-ray
scattering experiments for the structural characterization. The effect of the crystal thickness is clearly observed. Results
indicate that the sliding diffusion through the crystallites takes place by helical jumps of whole stems. Data yield the activation
energy per unit length of the stems.
Received 20 April 2001 and Received in final form 13 August 2001 相似文献
8.
Elastic rod model of a supercoiled DNA molecule 总被引:4,自引:0,他引:4
We study the elastic behaviour of a supercoiled DNA molecule. The simplest model is that of a rod-like chain, involving two
elastic constants, the bending and the twist rigidities. Writing this model in terms of Euler angles, we show that the corresponding
Hamiltonian is singular and needs a small distance cut-off, which is a natural length scale giving the limit of validity of
the model, of the order of the double-helix pitch. The rod-like chain in the presence of the cut-off is able to reproduce
quantitatively the experimentally observed effects of supercoiling on the elongation-force characteristics, in the small supercoiling
regime. An exact solution of the model, using both transfer matrix techniques and its mapping to a quantum mechanics problem,
allows to extract, from the experimental data, the value of the twist rigidity. We also analyse the variation of the torque
and the writhe-to-twist ratio versus supercoiling, showing analytically the existence of a rather sharp crossover regime which can be related to the excitation
of plectoneme-like structures. Finally we study the extension fluctuations of a stretched and supercoiled DNA molecule, both
at fixed torque and at fixed supercoiling angle, and we compare the theoretical predictions to some preliminary experimental
data.
Received 1 April 1999 and Received in final form 4 January 2000 相似文献
9.
The growth kinetics of self-assembled monolayers (SAMs) of thiophene compounds on Au(111) surfaces was revealed by Fourier-transform
infrared reflection absorption spectroscopy (FT-IR-RAS). Thiophene and terthiophene form well-ordered SAMs on Au(111) surfaces
by immersing gold substrates into their ethanol solutions for ca. 15 h. Gibbs free energies for the adsorption processes of thiophene and terthiophene were found to be identical. However,
the growth and molecular orientation of SAMs are different between two thiophene compounds. Terthiophene in SAMs orients parallel
to the surface. The SAM growth of terthiophene obeys a time-dependent Langmuir scheme. On the other hand, the thiophene SAM undergoes a two-step growth process with unique molecular orientations.
In the primary phase, thiophene assumes a parallel orientation on the Au(111) surface. In the second phase, thiophene is oriented
close to the normal of the surface. The different growth process between thiophene and terthiophene is attributable to the
topology of sulfur positions in the molecules.
Received 23 May 2001 and Received in final form 11 February 2002 相似文献
10.
11.
L.-H. Tang P. Smilauer D.D. Vvedensky 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,2(3):409-412
Two types of mechanisms are proposed for mound coarsening during unstable epitaxial growth: stochastic, due to deposition
noise, and deterministic, due to mass currents driven by surface energy differences. Both yield the relation H=(RWL)2 between the typical mound height W, mound size L, and the film thickness H. An analysis of simulations and experimental data shows that the parameter R saturates to a value which discriminates sharply between stochastic () and deterministic () coarsening. We derive a scaling relation between the coarsening exponent 1/z and the mound-height exponent which, for a saturated mound slope, yields .
Received: 11 November 1997 / Revised in final form: 28 November 1997 /
Accepted: 28 November 1997 相似文献
12.
S. Schinzer S. Köhler G. Reents 《The European Physical Journal B - Condensed Matter and Complex Systems》2000,15(1):161-168
We examine the step dynamics in a 1+1-dimensional model of epitaxial growth based on the BCF-theory. The model takes analytically
into account the diffusion of adatoms, an incorporation mechanism and an Ehrlich-Schwoebel barrier at step edges. We find
that the formation of mounds with a stable slope is closely related to the presence of an incorporation mechanism. We confirm
this finding using a solid-on-solid model in 2+1 dimensions. In the case of an infinite step edge barrier we are able to calculate
the saturation profile analytically. Without incorporation but with inclusion of desorption and detachment we find a critical
flux for instable growth but no slope selection. In particular, we show that the temperature dependence of the selected slope
is solely determined by the Ehrlich-Schwoebel barrier which opens a new possibility in order to measure this fundamental barrier
in experiments.
Received 11 May 1999 and Received in final form 6 November 1999 相似文献
13.
Shiqi Zhou 《The European physical journal. E, Soft matter》2000,3(4):343-353
A density functional theory is proposed for nonuniform freely jointed tangential hard sphere polymer melts in which the bonding
interaction is treated on the basis of the properties of the Dirac δ-function, thus avoiding the use of the single chain simulation
in the theory. The excess free energy is treated by making use of the universality of the free energy density functional and
the Verlet-modified (VM) bridge function. To proceed numerically, one of the input parameters, the second-order direct correlation
function of a uniform polymer melt is obtained by solving numerically the Polymer-RISM integral equation with the Percus-Yevick
(PY) closure. The predictions of the present theory for the site density distribution, the partition coefficient and the adsorption
isotherm, near a hard wall or between two hard walls are compared with computer simulation results and with those of previous
theories. Comparison indicates that the present approach is more accurate than the previous integral equation theory and the
most accurate Monte Carlo density functional theories. The predicted oscillations of the medium-induced force between two
hard walls immersed in polymer melts are consistent with the experimental results available in the literature.
Received 18 April 2000 相似文献
14.
M. Deserno C. Holm J. Blaul M. Ballauff M. Rehahn 《The European physical journal. E, Soft matter》2001,5(1):97-103
The osmotic coefficient of solutions of rod-like polyelectrolytes is considered by comparing current theoretical treatments
and simulations to recent experimental data. The discussion is restricted to the case of monovalent counterions and dilute,
salt-free solutions. The classical Poisson-Boltzmann solution of the cell model correctly predicts a strong decrease in the
osmotic coefficient, but upon closer look systematically overestimates its value. The contribution of ion-ion-correlations
are quantitatively studied by MD simulations and the recently proposed DHHC theory. However, our comparison with experimental
data obtained on synthetic, stiff-chain polyelectrolytes shows that correlation effects can only partly explain the discrepancy.
A quantitative understanding thus requires theoretical efforts beyond the restricted primitive model of electrolytes.
Received 25 July 2000 and Received in final form 4 December 2000 相似文献
15.
H.J. Angerman G. ten Brinke J.J.M. Slot 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,12(3):397-404
In this paper we investigate in a systematic way the influence of polydispersity in the block lengths on the phase behavior
of AB-multiblock copolymer melts. As model system we take a polydisperse multiblock copolymer for which both the A-blocks and the B-blocks satisfy a Schultz-Zimm distribution. In the limit of low polydispersity the expressions for the vertex functions are
clarified by using simple physical arguments. For various values of the polydispersity the phase diagram is presented, which
shows that the region of stability of the bcc phase increases considerably with increasing polydispersity. The strong dependence
of the periodicity of the microstructure on the polydispersity and on the interaction strength is presented.
Received 2 July 1998 相似文献
16.
Men YF Rieger J Enderle HF Lilge D 《The European physical journal. E, Soft matter》2004,15(4):421-425
Polyethylene (PE) pipes generally exhibit a limited lifetime, which is considerably shorter than their chemical degradation period. Slow crack growth failure occurs when pipes are used in long-distance water or gas distribution though being exposed to a pressure lower than the corresponding yield stress. This slow crack growth failure is characterized by localized craze growth and craze fibril rupture. In the literature, the lifetime of PE pipes is often considered as being determined by the density of tie chains connecting adjacent crystalline lamellae. But this consideration cannot explain the excellent durability of the recent bimodal grade PE for pipe application. We show in this paper the importance of the craze fibril length as the determining factor for the pipe lifetime. The conclusions are drawn from stress analysis. It is found that longer craze fibrils sustain lower stress and are deformed to a lesser degree. The mobility of the amorphous phase is found to control the amount of material that can be sucked in by the craze fibrils and thus the length of the craze fibrils. The mobility of the amorphous phase can be monitored by dynamic mechanical analysis measurements. Excellent agreement between the mobility thus derived and lifetimes of PE materials as derived from FNCT (full notch creep test) is given, thus providing an effective means to estimate the lifetime of PE pipes by considering well-defined physical properties. 相似文献
17.
It has been shown over the last few years that the dynamics close to the glass transition is strongly heterogeneous, both
by measuring the diffusion coefficient of tagged particles or by NMR studies. Recent experiments have also demonstrated that
the glass transition temperature of thin polymer films can be shifted as compared to the same polymer in the bulk. We propose
here first a thermodynamical model for van der Waals liquids, which accounts for experimental results regarding the bulk modulus
of polymer melts and the evolution of the density with temperature. This model allows us to describe the density fluctuations
in such van der Waals liquids. Then, by considering the thermally induced density fluctuations in the bulk, we propose that
the 3D glass transition is controlled by the percolation of small domains of slow dynamics, which allows to explain the heterogeneous
dynamics close to T
g. We show then that these domains percolate at a lower temperature in the quasi-2D case of thin suspended polymer films and
we calculate the corresponding glass transition temperature reduction, in quantitative agreement with experimental results
of Jones and co-workers. In the case of strongly adsorbed films, we show that the strong adsorption amounts to enhance the
slow domains percolation. This effect leads to 1) a broadening of the glass transition and 2) an increase of T
g in quantitative agreement with experimental results. For both strongly and weakly adsorbed films, the shift in T
g is given by a power law, the exponent being the inverse of that of the correlation length of 3D percolation.
Received 21 March 2000 and Received in final form 4 December 2000 相似文献
18.
J. van Mourik 《The European physical journal. E, Soft matter》2000,2(1):75-89
We introduce -dimensional lattice gas versions of three common models of random hetero-polymers, in which both the polymer density and
the density of the polymer-solvent mixture are finite. These solvable models give valuable insight into the problems related
to the (quenched) average over the randomness in statistical mechanical models of proteins, without having to deal with the
hard geometrical constraints occurring in finite-dimensional models. Our exact solution, which is specific to the -dimensional case, is compared to the results obtained by a saddle-point analysis and by the grand ensemble approach, both
of which can also be applied to models of finite dimension. We find, somewhat surprisingly, that the saddle-point analysis
can lead to qualitatively incorrect results.
Received 15 June 1999 and Received in final form 14 October 1999 相似文献
19.
Recent experiments have demonstrated that the dynamics in liquids close to the glass transition temperature is strongly heterogeneous.
The characteristic size of these heterogeneities has been measured to be a few nanometers at T
g. We extend here a recent model for describing the heterogeneous nature of the dynamics which allows both to derive this length
scale and the right orders of magnitude of the heterogeneities of the dynamics close to the glass transition. Our model allows
then to interpret quantitatively small probes diffusion experiments.
Received 29 March 2002 and Received in final form 11 November 2002
RID="a"
ID="a"e-mail: long@lps.u-psud.fr 相似文献
20.
P.I.C. Teixeira 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,9(3):471-477
A model is proposed for the reorientation dynamics of a confined nematic liquid crystal elastomer, where the effect of crosslinks
is to couple the director to deformations of the elastic matrix. The model combines the (equilibrium) `neo-classical' theory
of liquid crystal rubber elasticity with the simplest time evolution equations for a system described by two coupled, non-conserved
order parameters. Relaxation from an orientation imposed by an electric field is studied as a function of elastic softness,
starting angle, surface pretilt, and the relative mobilities of director and strain. Most importantly, the absence of a `semi-soft'
elastic threshold changes the long-time behaviour of the effective refractive index of the medium from exponential to inverse
power law decay. Predictions are compatible with recent experimental results by Chang, Chien and Meyer [Phys. Rev. E 56, 595 (1997)].
Received 22 June 1998 相似文献