Measuring surface and bulk relaxation in glassy polymers

We present a comprehensive study of gold nanoparticle embedding into polystyrene (PS) surfaces at temperatures ranging from T _g + 8 K to T _g − 83 K and times as long as 10⁵ minutes. This range in times and temperatures allows the first concurrent observation of and differentiation between surface and bulk behavior in the 20nm region nearest the free surface of the polymer film. Of particular importance is the temperature region near the bulk glass transition temperature where both surface and bulk processes can be measured. The results indicate that for the case of PS, enhanced surface mobility only exists at temperatures near or below the bulk T _g value. The surface relaxation times are only weakly temperature dependent and near T _g , the enhanced mobility extends less than 10nm into the bulk of the film. The results suggest that both the concept of a “surface glass transition” and the use of glass transition temperatures to measure local mobility near interfaces may not universally apply to all polymers. The results can also be used to make a quantitative connection to molecular dynamics simulations of polymer films and surfaces.     

Fatigue models for glassy polymers

Temperature effects on fatigue crack propagation in glassy polymers can be described by the Chudnovsky and Moet model, which is based on the propagation of microdefects near the crack tip. This was shown by fitting several models to fatigue data for polycarbonate and poly (methyl methacrylate). Statistical regression analysis and a global search method were used in the model fitting.     

Dynamic model of super-arrhenius relaxation rates in glassy materials

Super-Arrhenius relaxation rates in glassy materials can be associated with thermally activated rearrangements of increasing numbers of molecules at decreasing temperatures. We explore a model of such a mechanism in which stringlike fluctuations in the neighborhood of shear transformation zones provide routes along which rearrangements can propagate, and the entropy associated with critically long strings allows the rearrangement to be distributed stably in the surrounding material. We further postulate that, at low enough temperatures, these fluctuations are localized on the interfaces between frustration-limited domains, and in this way obtain a modified Vogel-Fulcher formula for the relaxation rate.     

Yielding behavior of glassy polymers. I. Free-volume model

Rigid, glassy polymers show a diversity of tensile behavior-ranging from apparently brittle to ductile. To delineate some of the factors that control the toughness or impact resistance of these polymers, the yielding behavior of poly (methyl methacrylate) (PMMA) was studied. Results of other workers have shown that the cold flow exhibited by many glassy polymers can be explained qualitatively by a free-volume model. The treatment assumes that molecular flow is permitted when the free volume increase, resulting from the dilatational component of the applied stress, is sufficient to bring the total free volume to that characteristic of the polymer liquid. The present study refines this approach by introducing an “effective temperature,” defined as that hypothetical temperature at which the glass would have an equilibrium free volume equal to the total free volume of the nonequilibrium glass at temperature T. Equations are derived which more satisfactorily describe the temperature and strain-rate dependences of the tensile yield strain of PMMA glass from -10° to 90°C at rates between 0.015 and 120%/sec.     

Segmental relaxation in semicrystalline polymers: A mean-field model for the distribution of relaxation times in confined regimes

The effect of confinement in the segmental relaxation of polymers is considered. On the basis of a thermodynamic model we discuss the emerging relevance of the fast degrees of freedom in stimulating the much slower segmental relaxation, as an effect of the constraints at the walls of the amorphous regions. In the case that confinement is due to the presence of crystalline domains, a quasi-Poissonian distribution of local constraining conditions is derived as a result of thermodynamic equilibrium. This implies that the average free-energy barrier F for conformational rearrangement is of the same order of the dispersion of the barrier heights, ( F) , around F . As an example, we apply the results to the analysis of the -relaxation as observed by dielectric broad-band spectroscopy in semicrystalline poly(ethylene terephthalate) cold-crystallized from either an isotropic or an oriented glass. It is found that in the latter case the regions of cooperative rearrangement are significantly larger than in the former.     

The fracture mechanics of glassy polymers

The application of fracture mechanics to glassy polymers, in particular crack growth in PMMA, is discussed. Particular attention is paid to two processes which modulate the energy supply to the crack tip: viscoelastic dissipation at slow crack speeds and specimen inertia at large crack speeds. The relation between fracture energy and crack speed is reviewed, and, where possible, fracture surface observations are correlated with dynamic behavior.     

Molecular conformation in molten and glassy polymers

As a consequence of enthalpy fluctuations in a small thermodynamic system, the conformation in molten and glassy polymers is predicted to be more nearly an irregularly folded molecule with 5 to 10 nearest neighbors than a random coil with 50 to 100 nearest neighbors.     

Distinction between two molecular mechanisms for deformation of glassy amorphous polymers

During deformation of glassy amorphous polymers the rotation of rigid chain segments around skeletal bonds is restricted simultaneously by configurational (intramolecular) and chain-chain (intermolecular) energy barriers. These barriers are modeled in a self-consistent manner for six polymers by use of an approximate analytical treatment. The comparative contribution of these barriers to the small-strain modulus of the bulk solid is used as a basis for distinguishing between two mechanisms of stiffening. With polycarbonate, polyphenylene oxide, and an aromatic polyimide, in which the rigid chain segment is relatively long, the modulus derives its value primarily from the resistance to displacements across chains due to intermolecular barriers. With vinyl polymers such as polystyrene, poly(vinyl chloride) and poly(methyl methacrylate), however, in which the rigid chain segment is short, resistance to displacements along the main chain due to intramolecular barriers contributes equally significantly to the modulus. Our calculations also show that the length of the rigid chain segment, acting as a mechanical moment arm, affects the resistance to intramolecular displacements much more than does the height of the rotational energy barrier.     

Micromechanical model of deformation-induced surface roughening in polycrystalline materials

A micromechanical model has been developed to describe deformation-induced surface roughening in polycrystalline materials. The three-dimensional polycrystalline structure is taken into account in an explicit form with regard to the crystallographic orientation of grains to simulate the micro- and mesoscale deformation processes. Constitutive relations for describing the grain response are derived on the basis of crystal plasticity theory that accounts for the anisotropy of elastic-plastic properties governed by the crystal lattice structure. The micromechanical model is used to numerically study surface roughening in microvolumes of polycrystalline aluminum and titanium under uniaxial tensile deformation. Two characteristic roughness scales are distinguished in the both cases. At the microscale, normal displacements relative to the free surface are caused by the formation of dislocation steps in grains emerging on the surface and by the displacement of neighboring grains relative to each other. Microscale roughness is more pronounced in titanium, which is due to the high level of elastic-plastic anisotropy typical of hcp crystals. The mesoscale roughness includes undulations and cluster structures formed with the involvement of groups of grains. The roughness is quantitatively evaluated using a dimensionless parameter, called the degree of roughness, which reflects the degree of surface shape deviation from a plane. An exponential dependence of the roughness degree on the strain degree is obtained.     

Hypersonic relaxation in amorphous polymers

In order to more fully understand the viscoelastic properties of amorphous polymers, it is desireable to have dynamic mechanical data over as wide a range in frequency as possible. One useful technique for studying the high-frequency behavior of polymers is to measure the velocity and attenuation of sound waves in the polymer fluid. When the frequency exceeds 109Hz. the sound waves are called hypersonic acoustic phonons. The present review examines the dynamic data obtained in the GHz frequency range for amorphous polymers.     

Periodic surface photoreliefs in glassy and hyperelastic polymers

The formation and degradation of periodic photoreliefs on the surface of polymer layers having significantly different glass-transition temperatures are investigated for various process activation temperatures. It is established that the main factor limiting the resolution of periodic relaxation photoreliefs at the surface of glassy polymer layers containing dimerizing anthracene derivatives is the presence of shear stresses. Their action is suppressed by the thermal decomposition of dimers, a process which gives rise to inverted reliefs of higher spatial frequencies. It is shown that the resolution can be enhanced by more than an order of magnitude by using a polymer matrix in the hyperelastic state. Zh. Tekh. Fiz. 69, 79–83 (August 1999)     

The relaxation dynamics of a confined glassy simple liquid

We use molecular-dynamics computer simulations to study the relaxation dynamics of a confined simple liquid. Two types of confining walls are considered: A rough wall and a smooth wall. The simulation is set up in such a way that the static properties of the confined system are identical to the ones of the bulk. Nevertheless, we find that upon cooling the relaxation dynamics of the confined systems differ strongly from the one of the bulk. In particular, we find that close to the rough/smooth wall this dynamics is slowed down/accelerated by orders of magnitude. Using these results we are able to extract a dynamical length scale of the system and we show that this length shows an Arrhenius dependence.Received: 1 January 2003, Published online: 14 October 2003PACS: 64.70.Pf Glass transitions - 68.15. + e Liquid thin films - 02.70.Ns Molecular dynamics and particle methods     

Simple model for spin-crisis

Starting from the additive quarkSU(6) model and taking into account the pion and kaon (η) emission during the initial stage of evolution (fromq ²～m _quark ² toq ²～1 GeV²) we convert the main fraction of the proton spin into the orbital momentum of the pseudoscalar mesons. The results are in a good agreement with the experimental data. We get ∫g ₁(x)dx=0.152 for proton and +0.007 for the Λ hyperon (i.e. the quarks carry out only about 39% of the Λ spin). In the same model we explain the violation of the Gottfried sum rule ?∫(F ₂ ^p(x)?F ₂ ⁿ(x))dx=0.23 due to the charged meson exchanges at the beginning of the evolution. The Gribov-Lipatov relation between the polarized structure functions in DIS ande ⁺ e ^?-annihilation is discussed. It gives the possibility to study the spin structure of Λ hyperon produced through the decay of the jet originated by a polarized quark ine ⁺ e ^?-annihilation or in DIS.     

Yielding of glassy polymers in the second quadrant of principal stress space

Second quadrant crazing and shear yielding studies were performed on glassy poly(methyl methacrylate) by means of combined torsion-tension loading. The results are in quantitative agreement with the shear and normal stress yielding criteria proposed by Sternstein and Ongchin. It is shown that four distinct regions of material response exist in the second quadrant and, depending on the stress state, 1) no crazing and no shear yielding, 2) crazing alone, 3) shear yielding alone, or 4) crazing and shear yielding can occur. An analysis of stress field induced brittle-ductile transitions is presented which is in agreement with other studies of high-pressure yielding.     

聚合物介电弛豫的温度特性

运用极限的概率模型和Ngai的耦合概念,导出了聚合物介电弛豫的KohlrauschWilliamsWatts(KWW)方程(t)=exp[-(tτ)β],证明了弛豫的能量势垒为Ngai的活化能量E.由β的温度关系推出了适用于聚合物的WilliamsLandelFerry方程和过冷液体的VogelTammannFulcher方程,特别是提出了由聚合物的β(T)可导出弛豫时间的温度函数.认为KWW行为由单个衰减单元产生,幂律行为由局部区域内多个衰减单元的协同衰减造成.将活化能量E引入热刺激电流公式,得到了可通过改变升温速率测量β(T)的公式. 关键词： 介电弛豫 聚合物 极限概率模型 KWW方程