High performance polyester-based materials

Biaxially oriented films produced from semi-crystalline, semi-aromatic polyesters are utilised extensively as components within various applications, including the specialist packaging, flexible electronic and photovoltaic markets. However, the thermal performance of such polyesters, specifically poly(ethylene terephthalate) (PET) and poly(ethylene-2,6-naphthalate) (PEN), is inadequate for several applications that require greater dimensional stability at higher operating temperatures. The work described in this project is therefore primarily focussed upon the copolymerisation of rigid comonomers with PET and PEN, in order to produce novel polyester-based materials that exhibit superior thermomechanical performance, with retention of crystallinity, to achieve biaxial orientation. Rigid biphenyldiimide comonomers were readily incorporated into PEN and poly(butylene-2,6-naphthalate) (PBN) via a melt-polycondensation route. For each copoly(ester-imide) series, retention of semi-crystalline behaviour is observed throughout entire copolymer composition ratios. This phenomenon may be rationalised by cocrystallisation between isomorphic biphenyldiimide and naphthalenedicarboxylate residues, which enables statistically random copolymers to melt-crystallise despite high proportions of imide sub-units being present. In terms of thermal performance, the glass transition temperature, Tg, linearly increases with imide comonomer content for both series. This facilitated the production of several high performance PEN-based biaxially oriented films, which displayed analogous drawing, barrier and optical properties to PEN. Selected PBN copoly(ester-imide)s also possess the ability to either melt-crystallise, or form a mesophase from the isotropic state depending on the applied cooling rate. An equivalent synthetic approach based upon isomorphic comonomer crystallisation was subsequently applied to PET by copolymerisation with rigid diimide and Kevlar®-type amide comonomers, to afford several novel high performance PET-based copoly(ester-imide)s and copoly(ester-amide)s that all exhibited increased Tgs. Retention of crystallinity was achieved in these copolymers by either melt-crystallisation or thermal annealing. The initial production of a semi-crystalline, PET-based biaxially oriented film with a Tg in excess of 100 °C was successful, and this material has obvious scope for further industrial scale-up and process development.

On the existence of two-dimensional Euler flows satisfying energy-Casimir stability criteria

The energy-Casimir stability method, also known as the Arnold stability method, has been widely used in fluid dynamical applications to derive sufficient conditions for nonlinear stability. The most commonly studied system is two-dimensional Euler flow. It is shown that the set of two-dimensional Euler flows satisfying the energy-Casimir stability criteria is empty for two important cases: (i) domains having the topology of the sphere, and (ii) simply-connected bounded domains with zero net vorticity. The results apply to both the first and the second of Arnold’s stability theorems. In the spirit of Andrews’ theorem, this puts a further limitation on the applicability of the method. © 2000 American Institute of Physics.

Nonlinear stability of Euler flows in two-dimensional periodic domains

The non-quadratic conservation laws of the two-dimensional Euler equations are used to show that the gravest modes in a doubly-periodic domain with aspect ratio L = 1 are stable up to translations (or structurally stable) for finite-amplitude disturbances. This extends a previous result based on conservation of energy and enstrophy alone. When L 1, a saturation bound is established for the mode with wavenumber |k| = L −1 (the next-gravest mode), which is linearly unstable. The method is applied to prove nonlinear structural stability of planetary wave two on a rotating sphere.

On Arnol'd's second nonlinear stability theorem for two-dimensional quasi-geostrophic flow

Arnol'd's second hydrodynamical stability theorem, proven originally for the two-dimensional Euler equations, can establish nonlinear stability of steady flows that are maxima of a suitably chosen energy-Casimir invariant. The usual derivations of this theorem require an assumption of zero disturbance circulation. In the present work an analogue of Arnol'd's second theorem is developed in the more general case of two-dimensional quasi-geostrophic flow, with the important feature that the disturbances are allowed to have non-zero circulation. New nonlinear stability criteria are derived, and explicit bounds are obtained on both the disturbance energy and potential enstrophy which are expressed in terms of the initial disturbance fields. While Arnol'd's stability method relies on the second variation of the energy-Casimir invariant being sign-definite, the new criteria can be applied to cases where the second variation is sign-indefinite because of the disturbance circulations. A version of Andrews' theorem is also established for this problem.

The stability of a two-dimensional vorticity filament under uniform strain

The quantitative effects of uniform strain and background rotation on the stability of a strip of constant vorticity (a simple shear layer) are examined. The thickness of the strip decreases in time under the strain, so it is necessary to formulate the linear stability analysis for a time-dependent basic flow. The results show that even a strain rate γ (scaled with the vorticity of the strip) as small as 0.25 suppresses the conventional Rayleigh shear instability mechanism, in the sense that the r.m.s. wave steepness cannot amplify by more than a certain factor, and must eventually decay. For γ < 0.25 the amplification factor increases as γ decreases; however, it is only 3 when γ e 0.065. Numerical simulations confirm the predictions of linear theory at small steepness and predict a threshold value necessary for the formation of coherent vortices. The results help to explain the impression from numerous simulations of two-dimensional turbulence reported in the literature that filaments of vorticity infrequently roll up into vortices. The stabilization effect may be expected to extend to two- and three-dimensional quasi-geostrophic flows.

Stability of stationary solutions of the forced Navier-Stokes equations on the two-torus

We study the linear and nonlinear stability of stationary solutions of the forced two-dimensional Navier-Stokes equations on the domain [0,2π]x[0,2π/α], where α ϵ(0,1], with doubly periodic boundary conditions. For the linear problem we employ the classical energy{enstrophy argument to derive some fundamental properties of unstable eigenmodes. From this it is shown that forces of pure χ2-modes having wavelengths greater than 2π do not give rise to linear instability of the corresponding primary stationary solutions. For the nonlinear problem, we prove the equivalence of nonlinear stability with respect to the energy and enstrophy norms. This equivalence is then applied to derive optimal conditions for nonlinear stability, including both the high-and low-Reynolds-number limits.

Nonlinear stability of multilayer quasi-geostrophic flow

New nonlinear stability theorems are derived for disturbances to steady basic flows in the context of the multilayer quasi-geostrophic equations. These theorems are analogues of Arnol’d's second stability theorem, the latter applying to the two-dimensional Euler equations. Explicit upper bounds are obtained on both the disturbance energy and disturbance potential enstrophy in terms of the initial disturbance fields. An important feature of the present analysis is that the disturbances are allowed to have non-zero circulation. While Arnol’d's stability method relies on the energy–Casimir invariant being sign-definite, the new criteria can be applied to cases where it is sign-indefinite because of the disturbance circulations. A version of Andrews’ theorem is established for this problem, and uniform potential vorticity flow is shown to be nonlinearly stable. The special case of two-layer flow is treated in detail, with particular attention paid to the Phillips model of baroclinic instability. It is found that the short-wave portion of the marginal stability curve found in linear theory is precisely captured by the new nonlinear stability criteria.

Non-ergodicity of inviscid two-dimensional flow on a beta-plane and on the surface of a rotating sphere

It is shown that, for a sufficiently large value of β, two-dimensional flow on a doubly-periodic beta-plane cannot be ergodic (phase-space filling) on the phase-space surface of constant energy and enstrophy. A corresponding result holds for flow on the surface of a rotating sphere, for a sufficiently rapid rotation rate Ω. This implies that the higher-order, non-quadratic invariants are exerting a significant influence on the statistical evolution of the flow. The proof relies on the existence of a finite-amplitude Liapunov stability theorem for zonally symmetric basic states with a non-vanishing absolute-vorticity gradient. When the domain size is much larger than the size of a typical eddy, then a sufficient condition for non-ergodicity is that the wave steepness ε < 1, where ε = 2[surd radical]2Z/βU in the planar case and $\epsilon = 2^{\frac{1}{4}} a^{\frac{5}{2}}Z^{\frac{7}{4}}/\Omega U^{\frac{5}{2}}$ in the spherical case, and where Z is the enstrophy, U the r.m.s. velocity, and a the radius of the sphere. This result may help to explain why numerical simulations of unforced beta-plane turbulence (in which ε decreases in time) seem to evolve into a non-ergodic regime at large scales.

An exact local conservation theorem for finite-amplitude disturbances to non-parallel shear flows, with remarks on Hamiltonian structure and on Arnol'd's stability theorems

Disturbances of arbitrary amplitude are superposed on a basic flow which is assumed to be steady and either (a) two-dimensional, homogeneous, and incompressible (rotating or non-rotating) or (b) stably stratified and quasi-geostrophic. Flow over shallow topography is allowed in either case. The basic flow, as well as the disturbance, is assumed to be subject neither to external forcing nor to dissipative processes like viscosity. An exact, local ‘wave-activity conservation theorem’ is derived in which the density A and flux F are second-order ‘wave properties’ or ‘disturbance properties’, meaning that they are O(a2) in magnitude as disturbance amplitude a [rightward arrow] 0, and that they are evaluable correct to O(a2) from linear theory, to O(a3) from second-order theory, and so on to higher orders in a. For a disturbance in the form of a single, slowly varying, non-stationary Rossby wavetrain, $\overline{F}/\overline{A}$ reduces approximately to the Rossby-wave group velocity, where (${}^{-}$) is an appropriate averaging operator. F and A have the formal appearance of Eulerian quantities, but generally involve a multivalued function the correct branch of which requires a certain amount of Lagrangian information for its determination. It is shown that, in a certain sense, the construction of conservable, quasi-Eulerian wave properties like A is unique and that the multivaluedness is inescapable in general. The connection with the concepts of pseudoenergy (quasi-energy), pseudomomentum (quasi-momentum), and ‘Eliassen-Palm wave activity’ is noted. The relationship of this and similar conservation theorems to dynamical fundamentals and to Arnol'd's nonlinear stability theorems is discussed in the light of recent advances in Hamiltonian dynamics. These show where such conservation theorems come from and how to construct them in other cases. An elementary proof of the Hamiltonian structure of two-dimensional Eulerian vortex dynamics is put on record, with explicit attention to the boundary conditions. The connection between Arnol'd's second stability theorem and the suppression of shear and self-tuning resonant instabilities by boundary constraints is discussed, and a finite-amplitude counterpart to Rayleigh's inflection-point theorem noted

Stability of an ice sheet on an elastic bed

The stability of stationary flow of a two-dimensional ice sheet is studied when the ice obeys a power flow law (Glen's flow law). The mass accumulation rate at the top is assumed to depend on elevation and span and the bed supporting the ice sheet consists of an elastic layer lying on a rigid surface. The normal perturbation of the free surface of the ice sheet is a singular eigenvalue problem. The singularity of the perturbation at the front of the ice sheet is considered using matched asymptotic expansions, and the eigenvalue problem is seen to reduce to that with fixed ice front. Numerical solution of the perturbation eigenvalue problem shows that the dependence of accumulation rate on elevation permits the existence of unstable solutions when the equilibrium line is higher than the bed at the ice divide. Alternatively, when the equilibrium line is lower than the bed, there are only stable solutions. Softening of the bed, expressed through a decrease of its elastic modulus, has a stabilising effect on the ice sheet.

In silico identification and three-dimensional modelling of the missense mutation in ADAMTS2 in a sheep flock with dermatosparaxis

Background Dermatosparaxis (Ehlers–Danlos syndrome in humans) is characterized by extreme fragility of the skin. It is due to the lack of mature collagen caused by a failure in the enzymatic processing of procollagen I. We investigated the condition in a commercial sheep flock. Hypothesis/Objectives Mutations in the ADAM metallopeptidase with thrombospondin type 1 motif, 2 (ADAMTS2) locus, are involved in the development of dermatosparaxis in humans, cattle and the dorper sheep breed; consequently, this locus was investigated in the flock. Animals A single affected lamb, its dam, the dam of a second affected lamb and the rams in the flock were studied. Methods DNA was purified from blood, PCR primers were used to detect parts of the ADAMS2 gene and nucleotide sequencing was performed using Sanger's procedure. Skin samples were examined using standard histology procedures. Results A missense mutation was identified in the catalytic domain of ADAMTS2. The mutation is predicted to cause the substitution in the mature ADAMTS2 of a valine molecule by a methionine molecule (V15M) affecting the catalytic domain of the enzyme. Both the ‘sorting intolerant from tolerant’ (SIFT) and the PolyPhen-2 methodologies predicted a damaging effect for the mutation. Three-dimensional modelling suggested that this mutation may alter the stability of the protein folding or distort the structure, causing the protein to malfunction. Conclusions and clinical importance Detection of the mutation responsible for the pathology allowed us to remove the heterozygote ram, thus preventing additional cases in the flock.