高聚物细观损伤演化的研究进展

聚合物的银纹化损伤与断裂是一个复杂和重要的研究课题。简述了银纹引发的(热)力学条件和银纹成核的微观机理。结合最新的研究进展,对银纹向前扩展的弯月面不稳定机理、银纹增厚的蠕变机理和界面转入机理作了较详细的分析与综合。考虑银纹细观结构中横系的作用,对银纹结构模型、银纹微纤断裂判据、微纤断裂行为的分子量和缠结密度相关性以及银纹与裂纹相互作用等问题进行了较详细的综述。指出银纹生长和断裂的深入研究可望建立材料宏观断裂韧性和材料细观结构以及微观参数之间的关联,为进行材料韧性的微观设计提供一条可行的途径。并对今后这一领域的研究方向和重点进行了展望。      

Damage evolution and energy dissipation of polymers with crazes

Craze damage evolution and energy dissipation of amorphous polymers with crazes have been studied. A mathematical model of a single craze (SC) is proposed by adopting the fibril creep mechanism. The viscoelastic characteristics of craze fibrils are supposed to obey the Maxwell model and the craze fibrils are assumed to be compressible. The assumption of Kausch [H.H. Kausch, The role of network orientation and microstructure in fracture initiation, J. Polym. Sci. C 32 (1971) 1–44] is adopted to describe the rupture of stressed fibril bonds. The craze damage evolution and the energy dissipation equations of a SC are derived. The equations are solved numerically and the life of a SC is computed. In a significant range of far-field stress, the dissipated energy varies linearly with the stress. Using the proposed model, the uniaxial stress-strain relation of polymers with low-density craze arrays (PLDCA) is investigated. The damage evolution equation of PLDCA is derived, which shows the mathematical relation between the damage of a SC and that of PLDCA. Based on the computed results, the variation of life of PLDCA with respect to applied stress is determined. Discussions are then given to the results and some significant conclusions are drawn.     

Formulation of a damage internal state variable model for amorphous glassy polymers

The following article proposes a damage model that is implemented into a glassy, amorphous thermoplastic thermomechanical inelastic internal state variable framework. Internal state variable evolution equations are defined through thermodynamics, kinematics, and kinetics for isotropic damage arising from two different inclusion types: pores and particles. The damage arising from the particles and crazing is accounted for by three processes of damage: nucleation, growth, and coalescence. Nucleation is defined as the number density of voids/crazes with an associated internal state variable rate equation and is a function of stress state, molecular weight, fracture toughness, particle size, particle volume fraction, temperature, and strain rate. The damage growth is based upon a single void growing as an internal state variable rate equation that is a function of stress state, rate sensitivity, and strain rate. The coalescence internal state variable rate equation is an interactive term between voids and crazes and is a function of the nearest neighbor distance of voids/crazes and size of voids/crazes, temperature, and strain rate. The damage arising from the pre-existing voids employs the Cocks–Ashby void growth rule. The total damage progression is a summation of the damage volume fraction arising from particles and pores and subsequent crazing. The modeling results compare well to experimental findings garnered from the literature. Finally, this formulation can be readily implemented into a finite element analysis.     

Adiabatic decohesion in a thermoplastic craze thickening at constant or increasing rate

When a crack in a thermally non-diffusive material is impact loaded—or propagates at high speed—a cohesive process which resists slow crack extension may itself cause decohesion by adiabatic heating. By assuming that decohesion ultimately occurs by low-energy disentanglement within a melt layer of critical thickness, the fracture resistance of craze-forming crystalline polymers can be estimated quantitatively. Previous estimates used a simple, thermomechanically linear representation of craze fibril drawing. This paper presents a more physically realistic, numerical formulation, and demonstrates it for constant craze thickening rate (as imposed by an ideal full-notch tension test) and for linearly increasing thickening rate (as at the tip of an impact-loaded or rapidly propagating crack). For a linear material, the numerical formulation gives results which asymptotically approach those from analytical solutions, as craze density approaches zero. In more realistic model polymers, the enthalpy of fusion increasingly delays decohesion as impact speed increases, although the temperature distribution of an endotherm appears to have little effect. Increasing molecular weight, heuristically associated with decreasing craze density and increasing structural dimension, increases the predicted impact fracture resistance. In every case, fracture resistance passes through a minimum as impact speed increases. The conclusions encourage the use of impact fracture tests, and discourage the use of the full-notch tension test, to assess the dynamic fracture resistance of a craze-forming polymer.     

伴随微孔洞生长的裂纹弹塑性定常扩展

裂纹在韧性材料中扩展时,将们随着微孔洞的萌生和生长,孔洞的萌生和深化将直接影响着材料的总体断裂韧性和强度,以往的研究主要集中在将裂纹的扩展刻划为微孔洞的萌生、生长和汇合这样一个过程。从传统的断裂过程区模型出发研究微孔洞的萌生和生长对材料总体断裂韧性的影响,通过采用Ｇｕｒｓｏｎ模型,建立塑性增量本构关系,然后针对定常扩展情况直接进行分析,孔洞对材料断裂韧性的影响由本构关系刻划,而在孔洞汇合模型中,上     

Über Spannungsrelaxation und zeitabhängige elastische Bruchvorgänge in orientierten Fasern

Zusammenfassung In der vorliegenden Arbeit wird der Zusammenhang zwischen der Spaltung von Molekülketten in belasteten Nylon-6-Fasern und dem makroskopischen, viskoelastischen Verhalten untersucht. Dazu wird die Morphologie orientierter Fasern diskutiert und auf die Spaltungswahrscheinlichkeit belasteter Einzelketten und Kettenbündel eingegangen. Aus experimentellen (ESR-)Ergebnissen wird hergeleitet, daß die Spaltung von Molekülen unter Last einen verschwindenden Einfluß auf die makroskopische Spannungsrelaxation, und einen beträchtlichen auf den Kriechvorgang hat. Die Bildungsrate freier Radikale (als Folge von Kettenspaltung) scheint unabhängig von der Spannungsrelaxation zu sein. Die zeitabhängige Bildung freier Radikale kann zutreffend durch eine aus den Modellvorstellungen gewonnene Funktion beschrieben werden. Dabei ergibt sich die Verteilung der relativen Längen derjenigen Kettensegmente, die bis zum makroskopischen Bruch der Probe gespalten werden.

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Summary The present paper deals with the correlation between chain scission in loaded Nylon 6 fibers and the macroscopic viscoelastic behavior. Therefore, the morphology of oriented fibers and the probability for scission of stressed single chains and bundles of chains are discussed. It is derived from experimental (ESR-) results that chain scission does hardly contribute to macroscopic stress relaxation, whereas creep is influenced significantly. The rate of formation of free radicals (as a consequence of chain scission) seems to be independent of the amount of stress relaxation. The time-dependent formation of free radicals may well be described by a function derived from the model representation. By optimal curve fitting the distribution of relative lengths of those chains is obtained which are broken until macroscopic failure occurs.

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Vorgetragen auf der Rheologentagung, Bad-Münster am Stein, 28.–30. Mai 1969.     

Fast flow behavior of highly entangled monodisperse polymers

A systematic experimental investigation is carried out to clarify the nature of a well-known capillary flow phenomenon in linear monodisperse polybutadienes (PBd). By varying the surface condition and the die diameter, it is alluded that a spurt-like stick-slip transition actually results from a breakdown of chain entanglement between adsorbed and next-layer unbound chains. In other words, the transition is not a manifestation of any constitutive properties, as previously asserted by Vinogradov and coworkers (1984). The melt viscosity dependence of the transition amplitude agrees with a Navier-de Gennes type analysis of wall slip. A comparison between the capillary flow and dynamic shear behavior of the same monodisperse PBd reveals that the interfacial stick-slip transition occurs at a stress level that is only a third of the plateau stress given by the elastic plateau modulus G _N ⁰=1.0 MPa at 40°C. The molecular weight independence of the critical stress for the transition provides a striking contrast with the transition characteristics observed in linear polyethylenes and suggests a different state of PBd chain adsorption on steel surfaces. Received: 2 April 1998 Accepted: 1 June 1998     

Dynamic void nucleation and growth in solids: A self-consistent statistical theory

We present a framework for a self-consistent theory of spall fracture in ductile materials, based on the dynamics of void nucleation and growth. The constitutive model for the material is divided into elastic and “plastic” parts, where the elastic part represents the volumetric response of a porous elastic material, and the “plastic” part is generated by a collection of representative volume elements (RVEs) of incompressible material. Each RVE is a thick-walled spherical shell, whose average porosity is the same as that of the surrounding porous continuum, thus simulating void interaction through the resulting lowered resistance to further void growth. All voids nucleate and grow according to the appropriate dynamics for a thick-walled sphere made of incompressible material. The macroscopic spherical stress in the material drives the response in all volume elements, which have a distribution of critical stresses for void nucleation, and the statistically weighted sum of the void volumes of all RVEs generates the global porosity. Thus, macroscopic pressure, porosity, and a distribution of growing microscopic voids are fully coupled dynamically. An example is given for a rate-independent, perfectly plastic material. The dynamics of void growth gives rise to a rate effect in the macroscopic material even though the parent material is rate independent.     

Thermal de-cohesion model for time of craze failure in cohesive zone

The cohesive parameter corresponding to craze failure time is predicted for thermoplastics material. A craze failure separation criterion is proposed for a cohesive zone subjected to a melt layer formed and thickened by adiabatic deformation heat from a craze drawing. The numerical simulation of cohesive zone separation is based on non-linear thermal conduction and convection in the craze region and bulk region around the active layer, associated with a mechanical craze fibrils drawing in an uniaxial direction. The craze failure time is predicted with the assumption of the constant craze thickening rate and cohesive stress for a pipe-grade polyethylene. The numerically computed model reveals the inverse power law decay of the craze failure time, t_f, with increasing in craze thickening rate, v_c, (almost, t_f∝V_c⁻¹) for the thermoplastics. The full notch impact test experimental results are consistent with the analysis prediction. It is concluded that the craze failure time can be theoretically predicted using the numerical modeling.     

Size effects on stress concentration induced by a prolate ellipsoidal particle and void nucleation mechanism

There generally exist two void nucleation mechanisms in materials, i.e. the breakage of hard second-phase particle and the separation of particle–matrix interface. The role of particle shape in governing the void nucleation mechanism has already been investigated carefully in the literatures. In this study, the coupled effects of particle size and shape on the void nucleation mechanisms, which have not yet been carefully addressed, have been paid to special attention. To this end, a wide range of particle aspect ratios (but limited to the prolate spheroidal particle) is considered to reflect the shape effect; and the size effect is captured by the Fleck–Hutchinson phenomenological strain plasticity constitutive theory (Advance in Applied Mechanics, vol. 33, Academic Press, New York, 1997, p. 295). Detailed theoretical analyses and computations on an infinite block containing an isolated elastic prolate spheroidal particle are carried out to light the features of stress concentrations and their distributions at the matrix–particle interface and within the particle. Some results different from the scale-independent case are obtained as: (1) the maximum stress concentration factor (SCF) at the particle–matrix interface is dramatically increased by the size effect especially for the slender particle. This is likely to trigger the void nucleation at the matrix–particle interface by cleavage or atomic separation. (2) At a given overall effective strain, the particle size effect significantly elevates the stress level at the matrix–particle interface. This means that the size effect is likely to advance the interface separation at a smaller overall strain. (3) For scale-independent cases, the elongated particle fracture usually takes place before the interface debonding occurs. For scale-dependent cases, although the SCF within the particle is also accentuated by the particle size effect, the SCF at the interface rises at a much faster rate. It indicates that the probability of void nucleation by the interface separation would increase.     

Site of ductile fracture initiation in cold forging: A finite element model

Ductile fracture occurs due to micro-void nucleation, growth and finally coalescence into micro-crack. In this study a new ductile fracture condition that based on the microscopic phenomena of void nucleation, growth and coalescence was proposed. Using this condition and combining with finite element model to predict the fracture locations in bulk metal forming, the results show that it is in close accordance with observations of some experimental specimens. However, in order to obtaining the high trustiness many experiments have to be carried out.     

A physical model for nucleation and early growth of voids in ductile materials under dynamic loading

Spall fracture and other rapid tensile failures in ductile materials are often dominated by the rapid growth of voids. Recent research on the mechanics of void growth clearly shows that void nucleation may be represented as a bifurcation phenomenon, wherein a void forms spontaneously followed by highly localized plastic flow around the new void. Although thermal, viscoplastic, and work hardening effects all play an essential role in the earliest stages of nucleation and growth, the flow becomes dominated by spherical radial inertia, which soon causes all voids to grow asymptotically at the same rate, regardless of differences in initial conditions or constitutive details, provided only that there is the same density of matrix material and the same excess loading history beyond the cavitation stress.These two facts, initiation by bifurcation at a cavitation stress, at which a void first appears, and rapid domination by inertia, are used to postulate a simple, but physically realistic, model for nucleation and early growth of voids in a ductile material under rapid tensile loading. A reasonable statistical distribution for the cavitation stress at various nucleation sites and a simple similarity solution for inertially dominated void growth permit a simple calculation of the initiation and early growth of porosity in the material.Parametric analyses are presented to show the effect that loading rate, peak loading stress, density of nucleation sites, physical properties of the material, etc. have on the applied pressure and distribution of void sizes when a critical porosity is reached.     

Towards a rheological classification of flow induced crystallization experiments of polymer melts

Departing from molecular based rheology and rubber theory, four different flow regimes are identified associated to (1) the equilibrium configuration of the chains, (2) orientation of the contour path, (3) stretching of the contour path, and (4) rotational isomerization and a deviation from the Gaussian configuration of the polymer chain under strong stretching conditions. The influence of the ordering of the polymer chains on the enhanced point nucleation, from which spherulites grow, and on fibrous nucleation, from which the shish-kebab structure develops, is discussed in terms of kinetic and thermodynamic processes. The transitions between the different flow regimes, and the associated physical processes governing the flow induced crystallization process, are defined by Deborah numbers based on the reptation and stretching time of the chain, respectively, as well as a critical chain stretch. An evaluation of flow induced crystallization experiments reported in the literature performed in shear, uniaxial and planar elongational flows quantitatively illustrates that the transition from an enhanced nucleation rate of spherulites towards the development of the shish-kebab structure correlates with the transition from the orientation of the chain segments to the rotational isomerization of the high molecular weight chains in the melt. For one particular case this correlation is quantified by coupling the wide angle X-ray diffraction and birefringence measurements of the crystallization process to numerical simulations of the chain stretch of the high molecular weight chains using the extended Pom-Pom model in a cross-slot flow.     

半晶态聚合物拉伸变形的微观机理

应用大规模分子动力学方法,采用粗粒化聚乙烯醇模型,模拟了晶区与非晶区随机交杂的半晶态聚合物模型系统,研究了半晶态聚合物在单轴拉伸变形过程中的应力-应变行为和微观结构演变.应力-应变曲线表现出4个典型变形阶段:弹性变形、屈服、应变软化和应变强化.在拉伸变形过程中,主要存在晶区折叠链之间的滑移、晶区破坏、非晶区的解缠结,以及分子链沿拉伸方向重新取向等4种主要的微结构演变形式.在屈服点附近,晶区分子链之间排列紧密程度减小而发生滑移,之后晶区变化需要的应力变小,从而形成应变软化现象.随着应变的增大,经各分子链段协同作用使非晶区分子链的解缠结和重新取向行为扩展到相对宏观尺度,导致拉伸应力增大而形成应变强化现象.      

Two mechanisms of ductile fracture: void by void growth versus multiple void interaction

Two distinct mechanisms of crack initiation and advance by void growth have been identified in the literature on the mechanics of ductile fracture. One is the interaction a single void with the crack tip characterizing initiation and the subsequent void by void advance of the tip. This mechanism is represented by the early model of Rice and Johnson and the subsequent more detailed numerical computations of McMeeking and coworkers on a single void interacting with a crack tip. The second mechanism involves the simultaneous interaction of multiple voids on the plane ahead of the crack tip both during initiation and in subsequent crack growth. This mechanism is revealed by models with an embedded fracture process zone, such as those developed by Tvergaard and Hutchinson. While both mechanisms are based on void nucleation, growth and coalescence, the inferences from them with regard to crack growth initiation and growth are quantitatively different. The present paper provides a formulation and numerical analysis of a two-dimensional plane strain model with multiple discrete voids located ahead of a pre-existing crack tip. At initial void volume fractions that are sufficiently low, initiation and growth is approximately represented by the void by void mechanism. At somewhat higher initial void volume fractions, a transition in behavior occurs whereby many voids ahead of the tip grow at comparable rates and their interaction determines initiation toughness and crack growth resistance. The study demonstrates that improvements to be expected in fracture toughness by reducing the population of second phase particles responsible for nucleating voids cannot be understood in terms of trends of one mechanism alone. The transition from one mechanism to the other must be taken into account.     

A void–crack nucleation model for ductile metals

A phenomenological void–crack nucleation model for ductile metals with secondphases is described which is motivated from fracture mechanics and microscale physicalobservations. The void–crack nucleation model is a function of the fracture toughness of theaggregate material, length scale parameter (taken to be the average size of the second phaseparticles in the examples shown in this writing) , the volume fraction of the second phase, strainlevel, and stress state. These parameters are varied to explore their effects upon the nucleationand damage rates. Examples of correlating the void–crack nucleation model to tension data in theliterature illustrate the utility of the model for several ductile metals. Furthermore, compression,tension, and torsion experiments on a cast Al–Si–Mg alloy were conducted to determinevoid–crack nucleation rates under different loading conditions. The nucleation model was thencorrelated to the cast Al–Si–Mg data as well.     

A constitutive model for elastoplastic solids containing primary and secondary voids

In many ductile metallic alloys, the damage process controlled by the growth and coalescence of primary voids nucleated on particles with a size varying typically between 1 and 100 μm, is affected by the growth of much smaller secondary voids nucleated on inclusions with a size varying typically between 0.1 and 3 μm. The goal of this work is first to quantify the potential effect of the growth of these secondary voids on the coalescence of primary voids using finite element (FE) unit cell calculations and second to formulate a new constitutive model incorporating this effect. The nucleation and growth of secondary voids do essentially not affect the growth of the primary voids but mainly accelerate the void coalescence process. The drop of the ductility caused by the presence of secondary voids increases if the nucleation strain decreases and/or if their volume fraction increases and/or if the primary voids are flat. A strong coupling is indeed observed between the shape of the primary voids and the growth of the second population enhancing the anisotropy of the ductility induced by void shape effects. The new micromechanics-based coalescence condition for internal necking introduces the softening induced by secondary voids growing in the ligament between two primary voids. The FE cell calculations were used to guide and assess the development of this model. The use of the coalescence condition relies on a closed-form model for estimating the evolution of the secondary voids in the vicinity of a primary cavity. This coalescence criterion is connected to an extended Gurson model for the first population including the effect of the void aspect ratio. With respect to classical models for single void population, this new constitutive model improves the predictive potential of damage constitutive models devoted to ductile metal while requiring only two new parameters, i.e. the initial porosity of second population and a void nucleation stress, without any additional adjustment.     

Rupture in rapid uniaxial extension of linear entangled melts

We have carried out uniaxial extension experiments on a monodisperse entangled melt to illustrate the origin of failure in the glass-like zone defined by Malkin and Petrie (J Rheol 41:1–25, 1997). The entangled melt was found to undergo a yield-to-rupture transition beyond a critical rate. We show that the onset of the “glass-like” zone defined by Malkin and Petrie is actually in the middle of the rubbery plateau where the mechanical response of entangled melts is not dictated by glassy chain dynamics. The rupture occurs plausibly through chain scission in the limit of finite chain extensibility.     

Damage of ductile materials deforming under multiple plastic or viscoplastic mechanisms

This work presents a model to represent ductile failure (i.e. failure controlled by nucleation, growth and coalescence) of materials whose irreversible deformation is controlled by several plastic or viscoplastic deformation mechanisms. In addition work hardening may result from both isotropic and kinematic hardening. Damage is represented by a single variable representing void volume fraction. The model uses an additive decomposition of the plastic strain rate tensor. The model is developed based on the definition of damage dependant effective scalar stresses. The model is first developed within the generalized standard material framework and expressions for Helmholtz free energy, yield potential and dissipation potential are proposed. In absence of void nucleation, the evolution of the void volume fraction is governed by mass conservation and damage does not need to be represented by state variables. The model is extended to account for void nucleation. It is implemented in a finite element software to perform structural computations. The model is applied to three case studies: (i) failure by void growth and coalescence by internal necking (pipeline steel) where plastic flow is either governed by the Gurson–Tvergaard–Needleman model or the Thomason model, (ii) creep failure (Grade 91 creep resistant steel) where viscoplastic flow is controlled by dislocation creep or diffusional creep and (iii) ductile rupture after pre-compression (aluminum alloy) where kinematic hardening plays an important role.     

Entangled polymer orientation and stretch under large step shear deformations in primitive chain network simulations

Orientation and stretch of entangled polymers under large step shear deformations were investigated through primitive chain network simulations. In the simulations, entangled polymer dynamics is described by 3D motion of entanglements, 1D sliding of monomers along the chain, and creation/destruction of entanglements described by hooking/unhooking with surrounding chains at chain ends. In addition to the conventionally proposed relaxation mechanisms that are reptation, contour length fluctuations, and constraint release (both thermal and convective), the simulations also account for force balance among entanglement strands converging to an entanglement node, and nodes also fluctuate in space. Nonlinear step strain data for monodisperse polystyrene melts (Ferri and Greco, Macromolecules, 37:5931, 2006) were quantitatively reproduced by using the same two molecular-weight-independent parameters already adopted by Masubuchi et al. (J Non-Newt Fluid Mech, 149:87, 2008) to fit linear viscoelastic data of several monodisperse polystyrene melts. Analysis of the orientation tensor and of the chain stretch ratio indicates that the segment orientation and stretch realized in the simulation are quantitatively described by a simple three-chain model (Marrucci et al., Macromol Symp, 158:57, 2000a).