Jumplike deformation of polymer materials on the micrometer and submicrometer structural levels

Jumplike creep is considered as a reflection of the structural heterogeneity of amorphous polymers on the mesoscopic and nanoscopic levels. The D-450 epoxy resin, poly(vinyl chloride), poly(vinyl butyral), and a composite consisting of the D-450 epoxy resin and diabase microparticles are studied at a temperature of 290 K. The creep rate of the specimens under compression is measured with a laser interferometer in submicrometer-scale deformation increments. Periodic variations of the creep rate with time or under deformation correspond to a jumplike (stepwise) behavior of the creep. It is shown that diabase particles (5–10 μm in size) are responsible for the appearance of micrometer-scale jumps in the creep of the composite and that the deformation jumps on the nanometer level are comparable to the sizes of the globules. The role of the resolution of the method employed in the evaluation of the scale of deformation jumps and structural units is considered.     

Inhomogeneity of the strain rate of polymer materials with different supramolecular structures

The characteristics of rate oscillations in submicron deformation increments in the course of creep under compression of polymer materials of different classes, namely, amorphous poly(vinyl butyral), amorphous-crystalline poly(tetrafluoroethylene), and a composite consisting of polyimide with graphite particles, have been investigated. The strain rate has been measured using an interferometer on a deformation base of 300 nm. The periods of rate oscillations have been used to determine the deformation jumps, and the amplitude of rate oscillations has been used to determine the jump sharpness. It has been demonstrated that the radical differences in the structure of materials manifest themselves in the parameters of deformation jumps at different stages of creep. The type of jumps makes it possible to reveal the type of molecular packing in the starting polymer or the packing formed during deformation.     

Jumplike microdeformation of nanostructured metals

The parameters of microdeformation jumps for copper, aluminum, titanium, and Armco iron with the initial (annealed) structure and after equal-channel angular pressing are investigated in a creep mode under low compressive stresses. The strain rate is measured with a laser interferometer in 0.15-μm linear displacements. It is demonstrated that the values of the microstrain rate and the mean sizes of jumps for the annealed metals are larger than those for the metals subjected to severe deformation. It is revealed that there is a correlation between the jumps of microplastic deformation and the size of nanometal grains. The inference is made that, for nanostructured metals, as for other materials, the structural heterogeneity is one of the factors responsible for the jumplike deformation.     

Effect of the magnetic field on nanometer-scale deformation jumps in polymers

The effect of a constant magnetic field on the rate of jumplike creep under compression is investigated for vitreous polymers with a globular structure. The interferometric method used for recording the creep makes it possible to measure deformation jumps from 300 nm and larger. It is demonstrated that the sizes of deformation jumps in polyester and epoxy resins decrease in the magnetic field (B = 0.2 T). Taking into account that the deformation jump size corresponds to the size of structural inhomogeneities, it is assumed that macroglobules under the action of a constant magnetic field are separated into smaller structural units on the nanometer level.     

Discontinuous deformation and morphology of polymers

The morphological nature of discontinuous (jumplike) deformation is studied. Recording creep behavior of materials using a laser interferometer permits one to determine the parameters of deformation jumps on a micron scale. The objects of investigation were poly(dimethylsiloxane) (PDMS) and a composite material consisting of PDMS and quartz (SiO₂). It is shown that the height and sharpness of jumps depend on the composition of the material and the stage of deformation. An analysis of differential scanning calorimetry (DSC) curves of the materials in the deformed and initial states suggests that deformation results in ordered domains in rubberlike polymers. This confirms the assumption that deformation jumps reflect the presence and the evolution of structural inhomogeneities in amorphous polymers.     

Inhomogeneity of deformation of solids at the nanometer level

A new method for processing interferometrically recorded deformation data has been implemented for studying an inhomogeneity in the rate and parameters of deformation jumps at the nanostructure level, which provides detection of deformation jumps of less than 300 nm. It is shown that the lower limit for deformation jumps lies in the range 10–30 nm for aluminum and is 130 nm for amorphous polymer (poly(methyl methacrylate)). It is assumed that the sizes of jumps correspond to scales of ordered structures, as was previously established for higher level structures. The results obtained make it possible to investigate more thoroughly the multilevel character of deformation and to evaluate the sizes of the nanostructural units, their evolution during deformation and under the effect of external fields, as well as their relation to the microscopic and macroscopic inhomogeneities of deformation.     

Nanoscale deformation irregularities of γ-irradiated poly(methyl methacrylate)

Development of deformation jumps in the creep of poly(methyl methacrylate) (PMMA) has been studied. The structural levels of deformation have been determined from the creep rate oscillation periods (deformation jumps) measured by the interferometric method. Special attention is given to a new method of data processing, which enables one to reveal previously undetectable nanoscale deformation jumps. By the example of PMMA specimens preliminarily exposed to γ radiation with doses D=55–330 kGy and unexposed specimens, the presence of nanoscale deformation jumps with the values dependent on the dose D and time of creep has been shown. The obtained results confirm the existence of 10–20-nm domains in amorphous polymers and make it possible to study the multilevel organization of the deformation process, starting from the nanoscale.     

Jumpwise deformation of polymethyl methacrylate in the microplasticity region

The deformation rate with a step of 325 nm has been measured under uniaxial compression at the initial stage of creep and shape recovery of a polymethyl methacrylate (PMMA) sample after unloading. The effect of low γ-ray doses and magnetic fields on the deformation has been studied. It has been shown that a weak pre-exposure of the PMMA sample structure to radiation and magnetic fields can cause a slight hardening in the microplasticity region. The deformation jump sizes have been determined on micro- and nanoscales. The effect of irradiation and magnetic fields manifests itself as redistributed contributions of various jumps to the deformation.     

Jumplike deformation of γ-irradiated polymethyl methacrylate

Nonuniformity of the microdeformation rate and the parameters of microdeformation jumps were studied in the creep regime for a polymethyl methacrylate irradiated by various dozes of the Co-60 γ radiation. The creep rate during compression of the polymethyl methacrylate was measured by an interferogram on 300-nm deformation increments. It is shown that the periods L of rate oscillations (jumps of deformation) on three scale levels are dependent on the irradiation doze and are also changed after prolonged exposure of samples in air. In the doze range 0 to 330 kGy, both a decrease and an increase in L are observed, which corresponds to the unstable kinetics of radiation chemical processes. The deformation jumps permit estimates of the radiation effect on various structural levels. It is concluded that the effect of radiation on coarser microstructural formations is the largest.

     

Structural micromechanics of oriented polymers

To clarify whether the interfibrillar slippage occurs on plastic deformation of oriented polymers, flow creep of ultrahigh molecular weight polyethylene (UHMW PE) samples with various connectedness of microfibrils has been studied in a dead load mode at room temperature. The flow creep rate of melt-crystallized and gel-cast UHMW PE films drawn to various draw ratios, as well as of modified gel-crystallized samples (cross-linked/grafted or washed free of low molecular weight fraction) has been measured with the help of a unique laser interferometric technique (Doppler creep rate meter). The technique allows one to measure creep rates for deformation increments as small as 0.3 μ within an accuracy 1%. The interferometric technique enabled us to observe an extremely high variability of flow creep rate. It was recognized that the creep process accelerates or slows from time to time. A length of a loaded sample increased by multiple consecutive deformation jumps (or steps). The size distribution of the steps appeared to be controlled by the structure of interfibrillar regions. The influence of the latter on the variability of creep rate confirms a hypothesis that suggests a contribution of interfibrillar slippage to plastic deformation of oriented polymers. The observed phenomenon has been attributed to stick-slip motion of microfibrils and their aggregates sliding on each other under the action of applied stress. It was found that the creep rate decreases with increasing interfibrillar interaction.     

Serrated creep of zinc single crystals under compression in a magnetic field

The compressive creep rate of zinc single crystals was measured for sample deformation increments of 150 nm, which permits the measurement of deformation jumps larger than 300 nm. A weak magnetic field B = 0.2 T is shown to increase the average creep rate and decrease the height and sharpness of submicron-sized deformation jumps. Preliminary holding of a sample in a magnetic field also influences the creep rate and the characteristics of deformation jumps. The data are explained in terms of a model relating the effect of a magnetic field to the destruction of barriers to dislocation motion.     

Universality and scaling of unstable plastic flow

The statistics of the jumplike plastic deformation of a Cu–Be alloy under the conditions of a low-temperature unstable plastic flow is studied experimentally. At a high strain rate, the parameters of the load jumps are found to be related by power laws, which corresponds to a scale-invariant behavior. A comparison with the data obtained for another mechanism of plastic instability, namely, the Portevin–Le Chatelier effect, points to the existence of universal laws governing the dynamics of a dislocation ensemble in the conditions of plastic instability.     

Multilevel character of deformation of polymers

The inhomogeneity in the creep rate of polymers on different scales of deformation has been studied by laser interferometry. The main results have been obtained for the amorphous-crystalline polymer polytetrafluoroethylene. The deformation characteristics are the oscillation periods of the rate (jumps of deformation), oscillation amplitudes of the rate, and the scatter of these quantities. Application of computer methods for processing of the results has made it possible to determine the difference and similarity between jumpwise deformations on different structural levels, including the nanolevel. For a more distinct separation of deformation levels, the measurements have been made in a magnetic field and outside the magnetic field. Deformation jumps have been found on five levels: from 4 nm to more than 10 μm. Introduction of a sample into a magnetic field changes the characteristics of jumps; in this case, the scatter in the values of jumps always increases, whereas their average value varies differently on different scale levels. The measurement of the parameters of deformation jumps on different scales allows one to study the laws of the development of the deformation process and the evolution of structural inhomogeneities.     

Step deformation of solid amorphous polymers

The variation of step deformation kinetics in solids is studied as a function of morphological factors. Oscillations of creep rate at micrometer increments of the amount of deformation, which reflect the step nature of the process, are investigated from an interferogram. It is shown that the plasticization of polymethyl methacrylate by dibutyl phthalate blurs the steps, while their height varies insignificantly. The results are explained using the concept of the netlike structure of amorphous polymers. The data obtained confirm the universal nature of jumps as a mode of evolution of deformation in various solids. The jumps reflect the cooperative nature of motion of kinetic units, and the regular variation of the characteristics of the jumps lends support to the definition of creep as a process of structural self-organization.     

Strength and microplasticity of biocarbons prepared by carbonization in the presence of a catalyst

The microdeformation has been investigated under uniaxial compression of beech-derived biocarbons partially graphitized during carbonization in the presence of a Ni- or Fe-containing catalyst. The strength and ultimate fracture strain have been determined at different temperatures of carbonization of the samples in the absence or in the presence of a catalyst. It has been shown using high-precision interferometry that the deformation of biocarbon samples under uniaxial loading occurs through jumps (in magnitude and rate of deformation) with axial displacements in the nanometer and micrometer ranges. The use of a catalyst leads to a decrease in the size of nanometer-scale jumps and in the number of micrometer-scale jumps. The standard deviations of the strain rate on loading steps from the smooth average dependence of the strain rate on the displacement have been calculated for micrometer-scale jumps. A similar characteristic for nanometer- scale jumps has been determined from the distortion of the shape of beats in the primary interferogram. It has been shown that the variation in the standard deviation of the strain rate with a change in the carbonization temperature is similar to the corresponding dependence of the ultimate fracture strain.     

Relationship of Processing Conditions to Structure and Properties in PMDA‐ODA Polyimide

A combined wide angle X‐ray diffraction (WAXD)/small‐angle X‐ray scattering (SAXS)/scanning electron microscopy (SEM)/density study of structure and morphology was carried out for a large series of pyromellitic dianhydride‐oxydianiline (PMDA‐ODA) polyimide (PI) samples processed using different powder metallurgy techniques. Using a combined DSC/creep rate spectroscopy (CRS)/long‐term creep resistance (LTCR) approach, their molecular dynamics, thermal and elastic properties, and creep resistance in the temperature range from 20 to 470°C were also studied. Both a choice of the method of formation of fine PI particles and the order of applying high pressure relative to high temperature to form the monolithic samples led to the observation of significant property differences. Relationships between the processing conditions, structure, and properties were determined. As a result, the conditions for optimizing certain PMDA‐ODA polyimide properties, especially creep resistance and elastic properties at extreme temperatures, were determined.     

Plastic deformation macrolocalization during serrated creep of an aluminum-magnesium Al-6 wt % Mg alloy

The nonlinear dynamics of the space-time structure of macrolocalized deformation is studied by a set of high-speed in situ methods under the conditions of serrated creep in an aluminum-magnesium Al-6 wt % Mg alloy at room temperature. Macroscopic deformation jumps with an amplitude of several percent are detected in the creep curve of this alloy. It is found that a complex space-time structure of macrolocalized deformation bands moving in a correlated manner forms spontaneously in the material during the development of a deformation jump. The difference between the observed picture of deformation bands and the well-known Portevin-Le Chatelier classification of deformation bands is discussed.     

Regularities in the variation of the rate of stepped creep in polyethylene with different supermolecular structure

The study of stepped creep, previously discovered with micron-size deformation increments (ɛ) of polymers, in the form of a variation of the rate near the average value is continued. A scheme based on a laser interferometer was used to record the creep; this made it possible to perform precise measurements. Attention was focused on the degree of scatter of the rate h in the process of deformation of polyethylene fibers. It is shown that the creep rate of textured fibers is extremely nonuniform and pulsates continuously, forming beats of different periods, i.e., deformation jumps of different height. The ratio of h of the highest to the lowest rate for arbitrarily chosen small increments of the deformation has a maximum near the start of the “flow” stage and prior to fracture. The h-ɛ curve shifts along the deformation scale as the polymer structure changes, but the form of the curve and the overall level of h change very little. It is also established that the value of h for identical deformations is higher in more highly oriented polymers, and the value of h is higher in cross-linked structures than in unmodified structures. It is proposed that h reflects not only the deformation heterogeneity, but also influences crack formation during the creep process. Fiz. Tverd. Tela (St. Petersburg) 39, 580–585 (March 1997)     

Emission of negative and positive ions at rupture of polymers

The emission of negative and positive ions at rupture of polymers has been recorded under high vacuum. The time characteristics of the emission have been investigated with a time resolution up to 1 μs by varying the sizes and the tension rate of poly(ethylene terephthalate), poly(caprolactam), poly(vinylidene fluoride), polyimide, and poly(tetrafluoroethylene) specimens. The kinetics of emission at the last stages of the tension is associated with the specific features of the intergrowth of the main crack in polymers of different types. Possible mechanisms of ion emission have been discussed.     

A facile method for preparing highly conductive and reflective surface-silvered polyimide films

A novel method was developed for the preparation of reflective and electrically conductive surface-silvered polyimide (PI) films. The polyimide films were functionalized with poly(dopamine), simply by dipping the PI films into aqueous dopamine solution and mildly stirring at room temperature. Electroless plating of silver was readily carried out on the poly(dopamine) deposited PI (PI-DOPA) surface. The surface compositions of the modified PI films were studied by X-ray photoelectron spectroscopy (XPS). XPS results show that the PI-DOPA surfaces were successfully deposited with ploy(dopamine) and were ready for electroless deposition of silver. The poly(dopamine) layer was used not only as the chemi-sorption sites for silver particles during the electroless plating of silver, but also as an adhesion promotion layer for the electrolessly deposited silver. The as-prepared silvered PI films show high conductivity and reflectivity, with a surface resistance of 1.5 Ω and a reflectivity of 95%, respectively.