215 research outputs found
Harnessing entropy to enhance toughness in reversibly crosslinked polymer networks
Reversible crosslinking is a design paradigm for polymeric materials, wherein
they are microscopically reinforced with chemical species that form transient
crosslinks between the polymer chains. Besides the potential for self-healing,
recent experimental work suggests that freely diffusing reversible crosslinks
in polymer networks, such as gels, can enhance the toughness of the material
without substantial change in elasticity. This presents the opportunity for
making highly elastic materials that can be strained to a large extent before
rupturing. Here, we employ Gaussian chain theory, molecular simulation, and
polymer self-consistent field theory for networks to construct an equilibrium
picture for how reversible crosslinks can toughen a polymer network without
affecting its linear elasticity. Maximisation of polymer entropy drives the
reversible crosslinks to bind preferentially near the permanent crosslinks in
the network, leading to local molecular reinforcement without significant
alteration of the network topology. In equilibrium conditions, permanent
crosslinks share effectively the load with neighbouring reversible crosslinks,
forming multi-functional crosslink points. The network is thereby globally
toughened, while the linear elasticity is left largely unaltered. Practical
guidelines are proposed to optimise this design in experiment, along with a
discussion of key kinetic and timescale considerations
The Slowly Formed Guiselin Brush
We study polymer layers formed by irreversible adsorption from a polymer
melt. Our theory describes an experiment which is a ``slow'' version of that
proposed by Guiselin [Europhys. Lett., v. 17 (1992) p. 225] who considered
instantaneously irreversibly adsorbing chains and predicted a universal density
profile of the layer after swelling with solvent to produce the ``Guiselin
brush.'' Here we ask what happens when adsorption is not instantaneous. The
classic example is chemisorption. In this case the brush is formed slowly and
the final structure depends on the experiment's duration, . We find
the swollen layer consists of an inner region of thickness with approximately constant density and an outer region
extending up to height which has the same density decay as for the Guiselin case.Comment: 7 pages, submitted to Europhysics Letter
Equilibrium and transport properties of CO2+N2O and CO2+NO mixtures : a molecular simulation and equation of state modelling study.
International audienceIn the present study, the thermodynamic behaviour and transport properties of CO2+N2O and CO2+NO mixtures have been investigated using molecular simulation and equation of state modelling. Molecular simulations were based on Monte Carlo and Molecular Dynamics calculations using force fields calibrated from pure component properties and no adjustment of mixture properties was performed. Original force fields were proposed for N2O, NO and N2O2 molecules. Special attention must be paid when studying nitric oxide containing systems because this compound can exist as a mixture of monomers (NO) and dimers (N2O2) under certain pressure and temperature conditions. Liquid-vapour coexistence properties of the reacting NO-N2O2 system were thus first investigated using combined reaction ensemble and Gibbs ensemble Monte Carlo methods. Using the new force fields proposed, phase compositions, phase densities and phase viscosities were determined for CO2+NOx mixtures. Due to the strong similarities between carbon dioxide and nitrous oxide (Tc(CO2) = 304.21 K; Tc(N2O) = 309.57 K; Pc(CO2) = 7.38 MPa; Pc(N2O) = 7.24 MPa), the obtained thermodynamic and transport properties for a CO2+N2O mixture with 10 mol% of N2O are similar to pure CO2 properties in the whole range of studied temperatures (273 - 293 K), in agreement with available experimental data. Calculations of CO2+NO equilibrium and transport properties were also performed at three different temperatures in the range of 253 - 273 K. At these temperatures, only the monomer form of the nitric oxide (NO) has to be accounted for. The performed calculations are pure predictions since no experimental data are available in the open literature for this system. For a mixture containing 10 mol% of NO, the simulation results show a decrease of the liquid densities and viscosities of 9% and 24% with respect to corresponding pure CO2 values, respectively. The new pseudo-experimental data generated in this work were finally used to calibrate binary interaction parameters required in standard cubic equations of states. Both Peng-Robinson and Soave-Redlich-Kwong equations of state have been considered and after the regression, they display a decent match with experimental and pseudo-experimental data of the vapour-liquid equilibrium for the two studied mixtures
Molecular weight effects on chain pull-out fracture of reinforced polymeric interfaces
Using Brownian dynamics, we simulate the fracture of polymer interfaces
reinforced by diblock connector chains. We find that for short chains the
interface fracture toughness depends linearly on the degree of polymerization
of the connector chains, while for longer chains the dependence becomes
. Based on the geometry of initial chain configuration, we propose a
scaling argument that accounts for both short and long chain limits and
crossover between them.Comment: 5 pages, 3 figure
Continuous EB welding of the reinforcement of the CMS conductor
The Compact Muon Solenoid (CMS) is one of the general-purpose detectors to be provided for the LHC project at CERN. The design field of the CMS superconducting magnet is 4 T, the magnetic length is 12.5 m and the free bore is 6 m. In order to withstand the electro-mechanical forces during the operation of the CMS magnet, the superconducting cable embedded in a 99.998% pure aluminum matrix is reinforced with two sections of aluminum alloy EN AW-6082 assembled by continuous Electron Beam Welding (EBW). A dedicated production line has been designed by Techmeta, a leading company in the field of EBW. The production line has a total length of 70 m. Non-stop welding of each of the 20 lengths of 2.5 km, required to build the coil, will last 22 hours. EBW is the most critical process involved in the production line. The main advantage of the EBW process is to minimize the Heat Affected Zone; this is particularly important for avoiding damage to the superconducting cable located only 4.7 mm from the welded joints. Two welding guns of 20 kW each operate in parallel in a vacuum chamber fitted with dynamic airlocks. After welding, the conductor is continuously machined on the four faces and on each corner to obtain the required dimensions and surface finish. Special emphasis has been put on quality monitoring. All significant production parameters are recorded during operation and relevant samples are taken from each produced length for destructive testing purposes. In addition, a continuous phased array ultrasonic checking device is located immediately after the welding unit for the continuous welding quality control, along with a dimension laser measurement unit following the machining. (8 refs)
On the nature of surface roughness with application to contact mechanics, sealing, rubber friction and adhesion
Surface roughness has a huge impact on many important phenomena. The most
important property of rough surfaces is the surface roughness power spectrum
C(q). We present surface roughness power spectra of many surfaces of practical
importance, obtained from the surface height profile measured using optical
methods and the Atomic Force Microscope. We show how the power spectrum
determines the contact area between two solids. We also present applications to
sealing, rubber friction and adhesion for rough surfaces, where the power
spectrum enters as an important input.Comment: Topical review; 82 pages, 61 figures; Format: Latex (iopart). Some
figures are in Postscript Level
Irreversible Adsorption from Dilute Polymer Solutions
We study irreversible polymer adsorption from dilute solutions theoretically.
Universal features of the resultant non-equilibrium layers are predicted. Two
cases are considered, distinguished by the value of the local monomer-surface
sticking rate Q: chemisorption (very small Q) and physisorption (large Q).
Early stages of layer formation entail single chain adsorption. While single
chain physisorption times tau_ads are typically microsecs, for chemisorbing
chains of N units we find experimentally accessible times tau_ads = Q^{-1}
N^{3/5}, ranging from secs to hrs. We establish 3 chemisorption universality
classes, determined by a critical contact exponent: zipping, accelerated
zipping and homogeneous collapse. For dilute solutions, the mechanism is
accelerated zipping: zipping propagates outwards from the first attachment,
accelerated by occasional formation of large loops which nucleate further
zipping. This leads to a transient distribution omega(s) \sim s^{-7/5} of loop
lengths s up to a size s_max \approx (Q t)^{5/3} after time t. By tau_ads the
entire chain is adsorbed. The outcome of the single chain adsorption episode is
a monolayer of fully collapsed chains. Having only a few vacant sites to adsorb
onto, late arriving chains form a diffuse outer layer. In a simple picture we
find for both chemisorption and physisorption a final loop distribution
Omega(s) \sim s^{-11/5} and density profile c(z) \sim z^{-4/3} whose forms are
the same as for equilibrium layers. In contrast to equilibrium layers, however,
the statistical properties of a given chain depend on its adsorption time; the
outer layer contains many classes of chain, each characterized by different
fraction of adsorbed monomers f. Consistent with strong physisorption
experiments, we find the f values follow a distribution P(f) \sim f^{-4/5}.Comment: 18 pages, submitted to Eur. Phys. J. E, expanded discussion sectio
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