105 research outputs found
Elasticity of highly cross-linked random networks
Starting from a microscopic model of randomly cross-linked particles with
quenched disorder, we calculate the Laudau-Wilson free energy S for arbitrary
cross-link densities. Considering pure shear deformations, S takes the form of
the elastic energy of an isotropic amorphous solid state, from which the shear
modulus can be identified. It is found to be an universal quantity, not
depending on any microscopic length-scales of the model.Comment: 6 pages, 5 figure
Glassy states and microphase separation in cross-linked homopolymer blends
The physical properties of blends of distinct homopolymers, cross-linked
beyond the gelation point, are addressed via a Landau approach involving a pair
of coupled order-parameter fields: one describing vulcanisation, the other
describing local phase separation. Thermal concentration fluctuations, present
at the time of cross-linking, are frozen in by cross-linking, and the structure
of the resulting glassy fluctuations is analysed at the Gaussian level in
various regimes, determined by the relative values of certain physical
length-scales. The enhancement, due to gelation, of the stability of the blend
with respect to demixing is also analysed. Beyond the corresponding stability
limit, gelation prevents complete demixing, replacing it by microphase
separation, which occurs up to a length-scale set by the rigidity of the
network, as a simple variational scheme reveals.Comment: 7 pages, 6 figure
Goldstone fluctuations in the amorphous solid state
Goldstone modes in the amorphous solid state, resulting from the spontaneous
breaking of translational symmetry due to random localisation of particles, are
discussed. Starting from a microscopic model with quenched disorder, the broken
symmetry is identified to be that of relative translations of the replicas.
Goldstone excitations, corresponding to pure shear deformations, are
constructed from long wavelength distortions of the order parameter. The
elastic free energy is computed, and it is shown that Goldstone fluctuations
destroy localisation in two spatial dimensions, yielding a two-dimensional
amorphous solid state characterised by power-law correlations.Comment: 7 pages, 2 figure
Statistical mechanics of permanent random atomic and molecular networks: Structure and heterogeneity of the amorphous solid state
Under sufficient permanent random covalent bonding, a fluid of atoms or small
molecules is transformed into an amorphous solid network. Being amorphous,
local structural properties in such networks vary across the sample. A natural
order parameter, resulting from a statistical-mechanical approach, captures
information concerning this heterogeneity via a certain joint probability
distribution. This joint probability distribution describes the variations in
the positional and orientational localization of the particles, reflecting the
random environments experienced by them, as well as further information
characterizing the thermal motion of particles. A complete solution, valid in
the vicinity of the amorphous solidification transition, is constructed
essentially analytically for the amorphous solid order parameter, in the
context of the random network model and approach introduced by Goldbart and
Zippelius [Europhys. Lett. 27, 599 (1994)]. Knowledge of this order parameter
allows us to draw certain conclusions about the stucture and heterogeneity of
randomly covalently bonded atomic or molecular network solids in the vicinity
of the amorphous solidification transition. Inter alia, the positional aspects
of particle localization are established to have precisely the structure
obtained perviously in the context of vulcanized media, and results are found
for the analogue of the spin glass order parameter describing the orientational
freezing of the bonds between particles.Comment: 31 pages, 5 figure
Solution of the local field equations for self-generated glasses
We present a self-consistent local approach to self generated glassiness
which is based on the concept of the dynamical mean field theory to many body
systems. Using a replica approach to self generated glassiness, we map the
problem onto an effective local problem which can be solved exactly. Applying
the approach to the Brazovskii-model, relevant to a large class of systems with
frustrated micro-phase separation, we are able to solve the self-consistent
local theory without using additional approximations. We demonstrate that a
glassy state found earlier in this model is generic and does not arise from the
use of perturbative approximations. In addition we demonstrate that the glassy
state depends strongly on the strength of the frustrated phase separation in
that model.Comment: 11 pages, 3 figure
‘‘Lozenge’’ contour plots in scattering from polymer networks
We present a consistent explanation for the appearance of “lozenge” shapes in contour plots of the two dimensional scattering intensity from stretched polymer networks. By explicitly averaging over quenched variables in a tube model, we show that lozenge patterns arise as a result of chain material that is not directly deformed by the stretch. We obtain excellent agreement with experimental data
Connecting the vulcanization transition to percolation
The vulcanization transition is addressed via a minimal
replica-field-theoretic model. The appropriate long-wave-length behavior of the
two- and three-point vertex functions is considered diagrammatically, to all
orders in perturbation theory, and identified with the corresponding quantities
in the Houghton-Reeve-Wallace field-theoretic approach to the percolation
critical phenomenon. Hence, it is shown that percolation theory correctly
captures the critical phenomenology of the vulcanization transition associated
with the liquid and critical states.Comment: 9 pages, 5 figure
Conformations of Randomly Linked Polymers
We consider polymers in which M randomly selected pairs of monomers are
restricted to be in contact. Analytical arguments and numerical simulations
show that an ideal (Gaussian) chain of N monomers remains expanded as long as
M<<N; its mean squared end to end distance growing as r^2 ~ M/N. A possible
collapse transition (to a region of order unity) is related to percolation in a
one dimensional model with long--ranged connections. A directed version of the
model is also solved exactly. Based on these results, we conjecture that the
typical size of a self-avoiding polymer is reduced by the links to R >
(N/M)^(nu). The number of links needed to collapse a polymer in three
dimensions thus scales as N^(phi), with (phi) > 0.43.Comment: 6 pages, 3 Postscript figures, LaTe
Random solids and random solidification: What can be learned by exploring systems obeying permanent random constraints?
In many interesting physical settings, such as the vulcanization of rubber,
the introduction of permanent random constraints between the constituents of a
homogeneous fluid can cause a phase transition to a random solid state. In this
random solid state, particles are permanently but randomly localized in space,
and a rigidity to shear deformations emerges. Owing to the permanence of the
random constraints, this phase transition is an equilibrium transition, which
confers on it a simplicity (at least relative to the conventional glass
transition) in the sense that it is amenable to established techniques of
equilibrium statistical mechanics. In this Paper I shall review recent
developments in the theory of random solidification for systems obeying
permanent random constraints, with the aim of bringing to the fore the
similarities and differences between such systems and those exhibiting the
conventional glass transition. I shall also report new results, obtained in
collaboration with Weiqun Peng, on equilibrium correlations and
susceptibilities that signal the approach of the random solidification
transition, discussing the physical interpretation and values of these
quantities both at the Gaussian level of approximation and, via a
renormalization-group approach, beyond.Comment: Paper presented at the "Unifying Concepts in Glass Physics" workshop,
International Centre for Theoretical Physics, Trieste, Italy (September
15-18, 1999
Universality and its Origins at the Amorphous Solidification Transition
Systems undergoing an equilibrium phase transition from a liquid state to an
amorphous solid state exhibit certain universal characteristics. Chief among
these are the fraction of particles that are randomly localized and the scaling
functions that describe the order parameter and (equivalently) the statistical
distribution of localization lengths for these localized particles. The purpose
of this Paper is to discuss the origins and consequences of this universality,
and in doing so, three themes are explored. First, a replica-Landau-type
approach is formulated for the universality class of systems that are composed
of extended objects connected by permanent random constraints and undergo
amorphous solidification at a critical density of constraints. This formulation
generalizes the cases of randomly cross-linked and end-linked macromolecular
systems, discussed previously. The universal replica free energy is
constructed, in terms of the replica order parameter appropriate to amorphous
solidification, the value of the order parameter is obtained in the liquid and
amorphous solid states, and the chief universal characteristics are determined.
Second, the theory is reformulated in terms of the distribution of local static
density fluctuations rather than the replica order parameter. It is shown that
a suitable free energy can be constructed, depending on the distribution of
static density fluctuations, and that this formulation yields precisely the
same conclusions as the replica approach. Third, the universal predictions of
the theory are compared with the results of extensive numerical simulations of
randomly cross-linked macromolecular systems, due to Barsky and Plischke, and
excellent agreement is found.Comment: 10 pages, including 3 figures (REVTEX
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