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1.
C. Lorthioir P. Auroy B. Deloche Y. Gallot 《The European physical journal. E, Soft matter》2002,7(3):261-266
The chain segment dynamics in the bulk lamellar phase of polystyrene-polydimethylsiloxane (PS-PDMS) block copolymers has been
probed by NMR. The experiments were performed on a PS-PDMS diblock and on a PS-PDMS-PS triblock with twice the molecular weight.
In the diblock, at room temperature, the PDMS block segments undergo uniaxial reorientations around the normal to the lamellae.
In the triblock, the reorientational motions exhibit a lower degree of symmetry: deviations from a uniaxial dynamics are observed.
Such a behaviour originates in the anchorage of both PDMS chain ends into the PS glassy layers.
Received 27 September 2001 and Received in final form 18 January 2002 相似文献
2.
G. Strobl 《The European physical journal. E, Soft matter》2000,3(2):165-183
Based on broad and detailed evidence from a large variety of experiments on several polymer systems carried out by other authors
and ourselves, a novel concept for understanding the crystallization of polymers from the melt is developed. The experiments
generally indicate that the formation and growth of the lamellar crystallites is a multi-step process passing over intermediate
states. We suggest a specific route which is compatible with the observations. It is proposed that the initial step is always
the creation of a mesomorphic layer which spontaneously thickens, up to a critical value, where it solidifies through a cooperative
structural transition. The transition produces a granular crystalline layer, which transforms in the last step into homogeneous
lamellar crystallites. The model leads to predictions about the temperature dependencies of the crystal thickness and the
growth rate which are at variance with conventional views but in agreement with findings in recent experiments.
Received 17 February 2000 and Received in final form 30 March 2000 相似文献
3.
Ngai KL 《The European physical journal. E, Soft matter》2002,8(2):225-235
Large increases of mobility of local segmental relaxation observed in polymer films as the film thickness is decreased, as
evidenced by decreases of the glass temperature, are not found for relaxation mechanisms that have longer length scales including
the Rouse relaxation modes and the diffusion of entire polymer chains. We show that the coupling model predictions, when extended
to consider polymer thin films, are consistent with a large increase of the mobility of the local segmental motions and the
lack of such a change for the Rouse modes and the diffusion of entire polymer chains. There are two effects that can reduce
the coupling parameter of the local segmental relaxation in thin films. One is the chain orientation that is induced parallel
to the surface when the film thickness h becomes smaller than the end-to-end distance of the chains and the other is a finite-size effect when h is no longer large compared to the cooperative length scale. Extremely thin ( ≈ 1.5 nm) films obtained by intercalating a
polymer into layered silicates have thickness significantly less than the cooperative length scale near the bulk polymer glass
transition temperature. As a result, the coupling parameter of the local segmental relaxation in such thin films is reduced
almost to zero. With this plausible assumption, we show the coupling model can explain quantitatively the large decrease of
the local segmental relaxation time found experimentally.
Received 1 August 2001 and Received in final form 1 December 2001 相似文献
4.
Bernazzani P Simon SL Plazek DJ Ngai KL 《The European physical journal. E, Soft matter》2002,8(2):201-207
The process of spin-coating to fabricate thin polymer films with high molecular weight can produce samples with entanglement
concentrations that are far below the equilibrium value. It is not clear whether or not such low entanglement concentrations
are responsible for the depression of the glass temperature in thin polymer films. In this work, we measure the calorimetric
glass temperature and viscoelastic response of polystyrenes with molecular weights ranging from 3×103 to 43.7×106 g/mol, for both bulk material and for samples freeze-dried from dilute solution. We conclude that the reduction of the glass
temperature observed in thin polymer films cannot be due to the reduced entanglement concentration in the samples.
Received 15 August 2001 and Received in final form 2 March 2002 相似文献
5.
We present several ordering mechanisms in diblock copolymers. For temperatures above the order-disorder temperature and in the weak segregation regime, a linear response theory is presented which gives the polymer density in the vicinity of confining flat surfaces. The surfaces are chemically patterned where different regions attract different parts of the copolymer chain. The surface pattern or template is decomposed into its Fourier modes, and the decay of these modes is analyzed. The propagation of the surface pattern into the disordered bulk is given for several types of patterns (e.g. uniform and striped surface). It is further shown that complex morphology can be induced in a thin film even though the bulk is disordered. We next consider lamellar diblock copolymers (low temperature regime) in the presence of a striped surface. It is shown that lamellae acquire a tilt with respect to the surface, if the surface periodicity is larger than the bulk one. The lamellae close to the surface are strongly distorted from their perfect shape. When the surface and lamellar periodicities are equal, the lamellae are perpendicular to the surface. Lastly, the transition from parallel to perpendicular lamellae in a thin film is presented. The transition between the two states depends on the surface separation and strength of surface interactions. We further calculate the phase diagram in the presence of perpendicular electric field favoring perpendicular ordering. In the strong segregation limit we introduce a simple model to calculate the phase diagram of the fully parallel, fully perpendicular and mixed (parallel and perpendicular) states. 相似文献
6.
The segmental ordering within a lamellar polystyrene-polydimethylsiloxane diblock (PS-PDMS) was examined by NMR. A non-uniform
stretching of the PDMS chains was evidenced. Although chain segments displaying isotropic reorientational motions are present
along the chains, relaxation measurements on the free PDMS extremities demonstrate that these latter are oriented and submitted
to a non-zero constraint. This specific result allows to precise some features of the order distribution within the lamellae.
Received: 27 March 2003 / Accepted: 9 May 2003 / Published online: 4 June 2003
RID="a"
ID="a"e-mail: deloche@lps.u-psud.fr 相似文献
7.
Herminghaus S 《The European physical journal. E, Soft matter》2002,8(2):237-243
It is discussed how the proximity of a free surface or mobile interface may affect the strain relaxation behavior in a viscoelastic
material, such as a polymer melt. The eigenmodes of a viscoelastic film are thus derived, and applied in an attempt to explain
the experimentally observed substantial shift of the glass transition temperature of sufficiently thin polymer films with
respect to the bulk. Based on the idea that the polymer freezes due to memory effects in the material, and exploiting results
from mode-coupling theory, the experimental findings of several independent groups can be accounted for quantitatively, with
the elastic modulus at the glass transition temperature as the only fitting parameter. The model is finally applied discussing
the possibility of polymer surface melting. A surface molten layer is predicted to exist, with a thickness diverging as the
inverse of the reduced temperature. A simple model of thin polymer film freezing emerges which accounts for all features observed
experimentally so far.
Received 8 August 2001 相似文献
8.
The branched crystal morphology of linear polyethylene formed at various temperatures from thin films has been studied by
atomic-force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) pattern and polymer decoration
technique. Two types of branched patterns, i.e. dendrite and seaweed patterns, have been visualized. The fractal dimension d
f = 1.65 of both dendrite and some of seaweed patterns was obtained by using the box-counting method, although most of the
seaweed patterns are compact. Selected-area ED patterns indicate that the fold stems tilt about 34.5° around the b-axis and polymer decoration patterns show that the chain folding direction and regularity in two (200) regions are quite
different from each other. Because of chain tilting, branched crystals show three striking features: 1) the lamella-like branches
show two (200) regions with different thickness; 2) the crystals usually bend towards the thin region; 3) the thick region
grows faster by developing branches, thus branches usually occur outside the thick region. The branched patterns show a characteristic
width w, which gives a linear relationship with the crystallization temperature on a semilogarithmic plot.
Received 15 March 2002 and Received in final form 29 April 2002 相似文献
9.
D. Zanghi A. Traverse J.-P. Dallas E. Snoeck 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2000,12(1):171-179
Ni ions were implanted in bulk AlN with the goal to form embedded metallic clusters. Combining several characterisation techniques
such as X-ray absorption spectroscopy, X-ray diffraction and high resolution transmission electron microscopy, we determined
the lattice parameter of the Ni clusters that display a fcc crystalline structure. The average size increases when the ion
fluence is increased or after a thermal treatment. Thanks to moiré fringes observed by high resolution transmission electron
microscopy and to satellite peaks seen on the diffraction patterns, we concluded that the annealed Ni clusters orientate their
(002) planes on the (101) of AlN. Moreover, the satellite positions allowed us to calculate Ni cluster average diameters,
that are in agreement with average sizes deduced by X-ray absorption spectroscopy.
Received 25 August 1999 and Received in final form 8 February 2000 相似文献
10.
The substrate is shown to induce substantial ordering in diblock copolymer thin films above the bulk order-disorder transition
(ODT) where, thermodynamically, a phase mixed state is favored. Initially, uniform films reorganize to form a hierarchy of
transient surface patterns and stable film thicknesses that depend on the initial film thickness and on the substrate. Self-consistent
field calculations of the free energy of the system for different situations, depending on the relative tendency for the different
block components to be attracted to the substrate and/or free surface, provide an explanation of the formation of the stable
film thicknesses. A continuum picture proposed earlier by Brochard et al.rovides an explanation of the wetting characteristics of this system. In some cases the ordering destabilizes the film so
that dewetting occurs (wetting autophobicity), whereas in other cases the surface ordering results in a kinetic stabilization
of a film that would otherwise dewet.
Received 3 August 2001 and Received in final form 1 November 2001 相似文献
11.
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
12.
Hartmann L Gorbatschow W Hauwede J Kremer F 《The European physical journal. E, Soft matter》2002,8(2):145-154
The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights
embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz
to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the
dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions
of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a
shift of the glass transition temperature T
g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and
a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized
boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T
g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements
yield a gradual increase of T
g with decreasing film thickness. The findings concerning the different thickness dependences of T
g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T
g shifts incorporates recently developed models to describe the glass transition in thin polymer films.
Received 12 August 2001 and Received in final form 16 November 2001 相似文献
13.
P. Orgiani C. Aruta G. Balestrino S. Lavanga P.G. Medaglia A. Tebano 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,26(1):23-28
Transport properties of SrRuO3 thin films were studied as a function of the epitaxial strain. SrRuO3 films were grown on (100) SrTiO3 substrates by the Pulsed Laser Deposition technique equipped with Reflection High Energy Electrons Diffraction (RHEED). Samples
thickness has been varied from a few unit cells to above 1000 ? while monitoring RHEED intensity oscillations. In thicker
films epitaxial strain was found to be progressively relaxed. SrRuO3 relaxed films (thickness 1000 ?) show metallic behavior for the whole temperature range with a ferromagnetic ordering at about 150 K. For thinner
films, ferromagnetic ordering occurs at progressively lower temperatures, until in films thinner than 400 ? it disappears.
Films thinner than 80 ? show a semiconducting behavior at low temperatures. Our results provide direct evidence of the crucial
role of the strain effect for conducting and magnetic properties of SrRuO3.
Received 16 July 2001 and Received in final form 22 October 2001 相似文献
14.
Higgins AM Sferrazza M Jones RA Jukes PC Sharp JS Dryden LE Webster J 《The European physical journal. E, Soft matter》2002,8(2):137-143
We investigate the dynamics of spinodal dewetting in liquid-liquid polymer systems. Dewetting of poly(methyl-methacrylate)
(PMMA) thin films on polystyrene (PS) “substrates” is followed in situ using neutron reflectivity. By following the development of roughness at the PS/PMMA interface and the PMMA surface we extract
characteristic growth times for the dewetting process. These characteristic growth times are measured as a function of the
molecular weight of the two polymers. By also carrying out experiments in the regime where the dynamics are independent of
the PS molecular weight, we are able to use dewetting to probe the scaling of the PMMA thin film viscosity with temperature
and molecular weight. We find that this scaling reflects bulk behaviour. However, absolute values are low compared to bulk
viscosities, which we suggest may be due in part to slippage at the polymer/polymer interface.
Received 25 June 2001 and Received in final form 5 December 2001 相似文献
15.
The shear-induced ordering of lamellar and gyroid structures of a nonionic surfactant C16E7/D2O system in a Couette shear cell ( 0.001 < < 10 s-1, : shear rate) has been investigated by using a small angle neutron scattering technique. In the lamellar phase, the steady
shear flow having > 0.01 s-1 suppresses undulation fluctuations of lamellae (Maxwell effect). This suppression of fluctuations brings two effects; 1)
shear-induced lamellae ordering toward a parallel orientation and 2) obstruction of a lamellar↦gyroid transition. It is quite
interesting to note that there is a characteristic shear rate range ( 0.01 < < 0.3 s-1), where both effects take place. We have also investigated the shear effects on the gyroid phase. Below the characteristic
shear rate range, the gyroid structure keeps three-dimensional network lattice, while above the characteristic shear rate
range, the gyroid structure transforms to the parallel orientation lamellae (shear-induced gyroid-lamellar transition). Thus
the shear flow having the characteristic shear rate plays very important roles in shear ordering phenomena.
Received 26 June 2000 and Received in final form 12 January 2001 相似文献
16.
A. Brioude F. Lequevre J. Mugnier C. Bovier J. Dumas J.C. Plenet 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,26(1):115-119
Very thin ZrO
2
films (few nanometers) have been prepared by sol-gel process. These films were deposited onto a stack of a thin silver layer
evaporated on a glass substrate for Surface Plasmons Resonance (SPR) experiments. The first aim of this work is to study the
high densification of the sol-gel films followed by the refractive index and thickness accurate measurements at each step
of the annealing procedure, using an optical set-up based on SPR. Secondly, SPR excitation coupled with micro-Raman experiment
has also been performed to determine the thin films structure depending on layer thickness. Finally, Conventional Transmission
Electron Microscopy (CTEM) and High Resolution (HRTEM) studies have been conducted to check and complete Raman spectroscopy
results. A discussion compares the optical results and the Transmission Electron Microscopy observations and shows that ultra
thin layers structure is strongly depends on films thickness.
Received 14 May 2001 and Received in final form 2 January 2002 相似文献
17.
Molecular-Dynamics computer simulations were used to study 2 nm wide polystyrene films confined in slit pores, defined by
inorganic crystalline surfaces. The simulated systems mimic experimentally studied hybrid materials, where polystyrene is
intercalated between mica-type, atomically smooth, crystalline layers. A comparison between the experimental findings and
the simulation results aims at revealing the molecular origins of the macroscopically observed behavior, and thus provide
insight about polymers in severe/nanoscopic confinements, as well as polymers in the immediate vicinity of solid surfaces.
Pronounced dynamic inhomogeneities are found across the 2 nm thin film, with fast relaxing moieties located in low local density
regions throughout the film. The origins of this behavior are traced to the confinement-induced density inhomogeneities, which
are stabilized over extended time scales by the solid surfaces.
Received 9 August 2001 and Received in final form 7 January 2002 相似文献
18.
J. Rysz H. Ermer A. Budkowski A. Bernasik J. Lekki G. Juengst R. Brenn K. Kowalski J. Camra M. Lekka J. Jedliński 《The European physical journal. E, Soft matter》2001,5(2):207-219
We have studied surface-directed phase separation in thin films of deuterated polystyrene and poly(bromostyrene) (with 22.7%
of monomers brominated) using 3He nuclear reaction analysis, dynamic secondary ion mass spectroscopy and atomic force microscopy combined with preferential
dissolution. The crossover from competing to neutral surfaces of the critical blend film (cast onto Au) was commenced: polyisoprene-polystyrene
diblock copolymers were added and segregated to both surfaces reducing in a tuneable manner the effective interactions. Two
main stages of phase evolution are characterised by i) the growth of two surface layers and by ii) the transition from the
four-layer to the final bilayer morphology. For increasing copolymer content the kinetics of the first stage is hardly affected
but the amplitude of composition oscillations is reduced indicating more fragmented inner layers. As a result, a faster mass
flow to the surfaces and an earlier completion of the second stage were observed. The hydrodynamic flow mechanism, driving
both stages, is evidenced by nearly linear growth of the surface layer and by mass flow channels extending from the surface
layer into the bulk. The final bilayer structure, formed even for the surfaces covered by strongly overlapped copolymers,
is indicative of long-range (antisymmetric) surface forces.
Received 15 March 2000 and Received in final form 9 February 2001 相似文献
19.
The T
g of organic liquids confined to nanoporous matrices and that of thin polymer films can decrease dramatically from the bulk
value. One possible explanation for this phenomenon is the development of hydrostatic tension during vitrification under confinement
that results in a concomitant increase in the free volume. Here we present experimental evidence and modeling results for
ortho-terphenyl (o-TP) confined in pores as small as 11.6 nm that indicate that, although there is an important hydrostatic
tension in the liquid in the pores, it does not develop until near the reduced T
g of the constrained material --well below the bulk T
g. Enthalpy recovery for the o-TP in the nanopores exhibits accelerated physical aging relative to the bulk, as well as a leveling
off of the fictive temperature at equilibrium values greater than the aging temperature. An adaptation of the structural recovery
model that incorporates vitrification under isochoric conditions is able to provide a quantitative explanation for the apparently
anomalous aging observed in nanopore confined liquids and in thin polymeric films. The results strongly support the existence
of an intrinsic size effect as the cause of the reduced T
g.
Received 3 September 2001 相似文献
20.
Grohens Y Hamon L Reiter G Soldera A Holl Y 《The European physical journal. E, Soft matter》2002,8(2):217-224
We have measured, the thickness dependence of the glass transition temperature T(g)( h), using ellipsometry at variable temperature, for poly(methyl-methacrylate) (PMMA) of various tacticity in confined geometry. We report that several factors significantly affect T(g)( h): i) polymer microstructure (stereoregularity of PMMA) related to local dynamics; ii) interfacial interactions; iii) conformation of the polymer chains. These results raise many fundamental questions on the origin of the thickness-dependent glass transition. Why and how do the interactions with the substrate significantly affect T(g)( h)? Does T(g)( h) depend on the modifications of conformational parameters of the chains (their entropy)? What is the correlation between local dynamics and T(g)( h) in thin films? The aim of this paper is to summarise these open questions, which should stimulate further investigations in the thin polymer film scientific community. 相似文献