流变-导电同步测试法研究炭黑填充高密度聚乙烯的等温结晶行为

采用流变-导电同步测试法,研究炭黑(CB)填充高密度聚乙烯(HDPE)在124.3～125.3℃范围的等温结晶行为,发现应变、频率与预降温速率均显著影响等温结晶过程中动态流变与导电行为.动态储能模量(G')与电阻均在结晶过程中发生显著变化.其中,CB粒子在熔体中发生扩散,造成原有逾渗网络结构破坏,导致复合体系电阻在结晶诱导期内增大.随结晶度增加,G'在结晶诱导期附近开始显著增大,其临界时间对应1%～2%相对结晶度;同时,CB粒子在无定形区相互聚集而形成渗流网络结构,使得复合体系电阻显著降低.电阻的变化被认为与CB粒子在熔体中的迁移以及在HDPE晶体生长过程中的聚集行为有关,且比依时性动态流变行为更敏感.     

Crystallization of polyethylene at elevated pressures

The crystallization from the melt of three sharp polyethylene fractions has been studied at 5 kbar. It has been shown that the thickness of so-called extended-chain lamellae is a function of time, temperature, and molecular weight. There is by no means just the fully extended molecular configuration present. Crystallization is qualitatively similar to that of chain-folded crystals at 1 bar, giving an optimum lamellar thickness which increases with time and decreasing supercooling. Fractional crystallization is widespread and is a major cause of disparate lamellar thickness. Isothermal thickening of lamellae during crystallization has been established directly. Morphological detail suggests further that layers can increase their thickness tenfold over their initial size.     

Static ultrasonic oscillations induced degradation and its effect on the linear rheological behavior of novel propylene based plastomer melts

The ultrasonic degradation of novel propylene based plastomer (DP) melts with different melt viscosities was conducted in a “static” ultrasonic device where the samples were taken from various distances from the tip of an ultrasonic probe. The effects of ultrasonic time, oscillation temperature, ultrasonic intensity and the distance from the ultrasonic probe tip on the degradation behavior of DP melts as well as the ultrasonic degradation effect on the linear rheological behavior of DP melts were studied. The results show that the increase of initial melt viscosity of DP (higher molecular weight) has greater impact on the ultrasonic degradation of DP melt. The molecular weight and intrinsic viscosity of DP decrease with the increase of ultrasonic oscillation time and they approach to a limiting value. The molecular weight distribution of DP increases after ultrasonic degradation. Decreasing oscillation temperature and distance from probe tip and increasing ultrasonic intensity lead to an increase in the degradation of DP melt. The linear rheological behavior measurements of the samples obtained near the ultrasonic probe tip show that ultrasonic oscillations decrease the complex viscosity, zero shear viscosity, viscoelastic moduli, cross modulus, relaxation time and the slope of log G′ − log G″ for DP melts.     

Effect of melt viscosity on the crystallization kinetics of pre-sheared metallocene polyethylene melts

This work aims to verify the impossibility mentioned in the literature of saturating the crystallization kinetics of pre-sheared metallocene polyethylene melts. Similarly to results reported for other materials, and contrary to other published works, an acceleration of crystallization kinetics with the increase of shear strain and its saturation at large strain values was found. Similar strain values, with the same temperature variation, were evaluated with independent experiments using different devices, which allowed us to identify the steady state as the melt state responsible for the saturation of crystallization kinetics. Since this is a partially disentangled melt state, with viscosity lower than that of fully entangled (relaxed) melts, we assign the acceleration of crystallization kinetics by application of shear, and its saturation, mainly to the facilitated diffusion of chain segments to the lamellae growth front. This conclusion is supported additionally with the experimental results of other authors.     

Nucleation and size distribution of nucleus during induction period of polyethylene crystallization

The crystallization process from supercooled melt results in the formation of nanosize nuclei in the earlier stage (induction period) through subsequent attachment or detachment of repeating unit to nuclei. The size distribution of nucleus f(N(j),t) in the induction period of nucleation process from the melts has not been experimentally confirmed yet by direct observation. The reason is that the number density of nuclei nu is too small to be detected experimentally. In our previous work, we showed the direct evidence of nucleation experimentally by means of small angle x-ray scattering (SAXS) technique. Further we have succeeded to observe the nucleation and f(N(j),t) of polymer crystallization from the melts by SAXS using synchrotron radiation. We increased nu by adding a nucleating agent to a polymer (polyethylene). The time evolution of f(N(j),t) was observed for the first time.     

Enthalpy relaxation in the cooling/heating cycles of polypropylene/organosilica nanocomposites: I: Non-isothermal crystallization

Non-isothermal crystallization of the neat isotactic polypropylene homopolymer (PP-0) and of a series of nanocomposites (PNC) containing up to 4.68 vol.% of organosilica was studied in the standard DSC mode during constant-rate cooling from the melt state.Analysis of the nucleation parameters derived from cooling rate dependencies of the temperatures for the onset of crystallization exotherms revealed a slight but systematic increase of the nucleation barrier for lamellar crystallization of PP in the PNC concomitant to stronger restrictions to transport of PP segments across the melt/lamellar crystal interface. The overall crystallization rate data for the PNC were consistent with the assumption of two separate contributions from the initial (unconstrained), and the subsequent (constrained) growth mechanisms, respectively.The obtained results were considered as evidence for the coexistence in undercooled PP melts of the PNC of initial crystal nucleation and growth sites characteristic for the neat PP-0, and the basically different sites (presumably, PP chains anchored by both ends to the surfaces of two adjacent nanoparticles).     

Reversible and irreversible crystallization in high-density polyethylene at low temperature

Reversible and irreversible crystallization and melting of high-density polyethylene at low temperature has been re-evaluated and is discussed in terms of the concept of the specific reversibility of a crystal. The concept of the specific reversibility links reversible and irreversible melting of a specific crystal such that reversible melting occurs only at slightly lower temperature than irreversible melting. In this study evidence for irreversible crystallization at low temperature in high-density polyethylene is provided, non-avoidable by primary crystallization and extended annealing at high temperature. The simultaneously observed reversible crystallization and melting at low temperature can be attributed to lateral-crystal-surface activity in addition to the well-established reversible fold-surface melting, dominant at high temperature, and evidenced by small-angle X-ray data available in the literature. This revised version was published online in August 2006 with corrections to the Cover Date.     

Crystallization of polymers under high tension: A dendrite model

The crystallization of highly oriented homopolymer melts (or glasses) is modeled. It is shown that in such cases heat flow controls the kinetics and microstructure of the transforming material. The situation is modeled similarly to the growth of a thermal dendrite, with the inclusion of large and variable concentrations of defects in the fibrillar crystals. Expressions relating the undercooling, growth velocity, filament tip radius, and defect concentration to a normalized tensile force are derived. Example predictions for the case of isotactic polystyrene are given.     

Extended-chain crystals. I. General crystallization conditions and review of pressure crystallization of polyethylene

This is the first paper of a series of reports concerning extended-chain crystals of flexible, linear high polymers. The general conditions for crystal growth are discussed. Polymer crystallization is described as a two-step process: nucleation of each crystallizing molecule to a folded-chain conformation, followed by an increase in fold length in a solid-state reorganization step. This reorganization step is enhanced in the case of polyethylene by crystallization at high temperature under elevated pressure. Mechanical deformation during crystallization is also able to produce extended-chain crystals. The most promising method, however, is crystallization during polymerization. Previous work on crystallization of polyethylene under elevated pressure is critically reviewed.     

Transitions in trans-1,4-polyisoprene

The melting transitions of both crystalline forms of trans-1,4-polyisoprene, as detected by differential thermal analysis, have been identified by attendant studies with optical microscopy and x-ray diffraction. The lower-melting (LM) form melts initially at a temperature which depends upon the crystallization temperature but which, under our experimental conditions, is between 45 and 53°C. If recrystallization is allowed to occur, the apparent final melting point, which depends upon the recrystallization temperature, is about 58°C. The initial melting point of the higher-melting (HM) form, also crystallization temperature-dependent, is upwards of 57°C. Under the most easily accessible experimental conditions, it may be obscured by the final melting of the LM-form. The apparent final melting point of the HM form is approximately 66°C. Conversion of the LM form into the HM form occurs only by fusion and crystallization. No evidence of a solid-solid transition was found. The rate of conversion is governed principally by the rate of nucleation at the conversion temperature. If fusion of the LM form is incomplete, recrystallization of the LM form takes place instead of conversion to the HM form.     

Temperature evolution for small particles formed during electrocrystallization

It is shown, by analyzing heat balance of a cluster formed during electrochemical crystallization, that the cluster temperature passes through maximum and can achieve the melting point in the crystallization initial stage. This allows preparing amorphous deposits.     

Extensional flow-induced crystallization of a polyethylene melt

Measurements of flow-induced orientation and crystallization have been made on a high-density polyethylene melt (HDPE) undergoing a planar extensional flow in a four-roll mill. The HDPE was suspended as a cylindrical droplet at the flow stagnation point in a linear low density polyethylene (LLDPE) carrier phase. Deformation and crystallization of the HDPE droplet phase were monitored using video imaging in conjunction with measurement of the birefringence and dichroism to quantify the in-situ transformation kinetics. Planar deformation rates along the symmetry axis of the molten HDPE phase were on the order of 0.03 s^?1. Measurements of the initial transformation rate following flow cessation at 131.5°C and 133.2°C show a dependence on initial amorphous phase orientation and the total Hencky strain achieved during flow. The flow-induced crystallization rate is enhanced over the quiescent transformation rate by orders of magnitude, however, the dependence on temperature is less dramatic than expected for a nucleation-controlled growth mechanism. Analysis demonstrates that the melting point elevation model cannot account either qualitatively or quantitatively for the phenomena observed, suggesting that alternative explanations for the strong orientation dependence of the transformation rate are needed.     

Crystallinity and the effect of ionizing radiation in polyethylene. IV. Effect of segregation of low molecular weight chains on determination of main-chain scission in linear polyethylene

Different single crystal preparations of polyethylene with (unfractionated) and without (partially fractionated) low molecular weight chains were irradiated at room temperature. G(crosslink) was determined from the gel point. It is shown that in addition to the molecular weight and molecular weight distribution of polymers, G(crosslink) is determined by three more parameters: thickness of crystalline core, amount of amorphous surface layer, and degree of interlamellar contact. Unlike unfractionated polyethylene, partially fractionated polyethylene showed almost 100% gel at about 250 Mrad. To obtain the same amount of gel, unfractionated polyethylene required a much higher dose than that required by partially fractionated polyethylene. Molecular weight distribution of sol fractions of unfractionated and partially fractionated polyethylene was studied by gel permeation chromatography (GPC) and the solubility data analyzed by Charlesby–Pinner plots. It has been shown that the unattainability of 100% gel from unfractionated polyethylene is due to segregation of low molecular weight chains during crystallization which need very high doses for complete gelation.     

Electron microscope study of low molecular weight fractions of linear polyethylene

Electron microscope studies are reported for crystals of linear polyethylene formed in dilute solution from very sharp low molecular weight fractions. Emphasis is placed on molecular weights in the range of 1.1 × 10³ to 15.1 × 10³. The dependence of the crystal habit on the crystallization temperature is very similar to that which has been found for the higher molecular weight species. However, the demarcation temperature for the crystallization of the different morphological forms is very molecular weight-dependent. The conditions under which interfacial dislocation networks form can be clearly defined. The molecular weight must be less than 3000, so that these structures are restricted to very small chain lengths. However, not all crystallization conditions within this allowable molecular weight range yield such dislocations. The formation of interfacial dislocation networks are shown to occur only under very special circumstances. Their occurrence clearly cannot be offered as evidence, as has been done in the past, for a regular, chain-folded interfacial structure.     

Thermolysis of polyethylene hydroperoxides in the melt. Part 9: Re-examination of the experimental kinetics of hydroperoxide decomposition

The experimental kinetics of decomposition of polyethylene hydroperoxides in the melt is re-examined. It is found that the rates determined are more accurate if only the “free” hydroperoxides are taken into account instead of the total hydroperoxides that include also the “associated” hydroperoxides. Then, decomposition of polyethylene hydroperoxides in the melt can be attributed unambiguously to a first-order reaction that is valid in the whole time range of the thermolysis experiments. Nevertheless, the first-order rate constant determined this way increases with the initial hydroperoxide concentration. This constitutes a significant difference with the first-order rate constants that are valid in low molecular mass chemistry and are independent of the initial concentration of the reacting species. It has already been concluded previously that this experimental first-order rate cannot be attributed to true monomolecular hydroperoxide decomposition. Hence, another or other reactions must be envisaged for the interpretation of the specific first-order decomposition of the hydroperoxides in polyethylene melts.     

Absolute integrated SAXS measurements during the crystallization of linear polyethylene

Absolute intensity measurements of a dynamic small-angle x-ray scattering from a linear polyethylene were carried out during polymer crystallization from melt in a temperature range of 113.5° to 124.5°C. The mean-square modulation of the electron density over the irradiated volume was evaluated and the feasibility of dynamic experimentation for crystallization kinetic analysis was established. The results provide an absolute value of mass density of the amorphous phase of a semicrystalline polymer at the crystallization temperature.     

Use of SAXS and linear correlation functions for the determination of the crystallinity and morphology of semi‐crystalline polymers. Application to linear polyethylene

The use of correlation functions to obtain the morphological parameters of crystalline‐amorphous two‐phase lamellar systems is critically reviewed and extended. It is shown that processing of the experimental SAXS‐patterns only significantly affects the curvature of the autocorrelation triangle and that the parameters of the corresponding ideal two‐phase structure can be determined independently of the data processing procedure. The methods to be used depend on the normalization of the correlation function. The validity of the formulation is illustrated for a sample of linear polyethylene, cooled and heated at 10°C per min. Crystallite thickening during crystallization and surface melting during heating are observed. The overall crystallinity and the fraction of semi‐crystalline stacks during crystallization and melting are determined quantitatively as a function of temperature using the total scattering power of the corresponding ideal two‐phase structure, correlation functions, and a scaling procedure. Absolute intensities are not required. The SAXS results are confirmed by independent techniques (DSC, WAXD, and SALLS). During crystallization, amorphous regions are present outside the semi‐crystalline regions because growing spherulites do not fill space completely. During melting, larger amorphous regions develop in the spherulites because of the complete melting of stacks. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1715–1738, 1999     

NMR study of polyethylene crystallization kinetics under high pressure

Crystallization of polyethylene under hydrostatic pressures of 1–4.5 kbar is directly observed using pulsed proton NMR. The rate of growth of extended-chain polyethylene crystals is measured over this pressure range and to a maximum temperature of 227°C. The observed crystallization isotherms are superimposable on a log time scale; this implies a consistent mechanism for extended-chain growth over this pressure range. Avrami coefficients for high-pressure extended-chain crystallization are determined to be 1.3–1.7. A decrease of crystal nucleus surface free energies with increasing pressure is indicated. Findings are consistent with Wunderlich's model of initial folded-chain crystallization followed immediately by chain extension. Future applications of this NMR technique are briefly considered.     

Crystallization and melting of fractions of branched polyethylene

Effects of the molecular weight on the crystallization behaviour of branched polyethylene become observable if isothermal crystallization is studied at temperatures near to the melting end. Crystallinities decrease with decreasing molecular weight. Thicknesses of lamellae grown during isothermal crystallization are independent of the molecular weight. They depend only on temperature. Compared to the effect of the branches polydispersity gives only a minor contribution to the broadening of the crystallization and melting range of low density polyethylene.     

New concept of solute distribution around a diffusive crystal-solution interface of a binary Lennard-Jones mixture from the viewpoint of molecular dynamics

Directional crystallization from a binary mixture was performed by pseudo-NpT ensemble molecular dynamics. The initial crystal phase having a face-centered-cubic (fcc) structure grew toward the whole cell according to the temperature gradient in the universal cell. The growing crystal phase was not planar even though the solute molecules grew in two-dimensional coordinates because the solvent molecules disturbed the crystallization of the solute molecules at the diffusive crystal-solution interface. This represented the essential phenomenon of solute distribution during crystallization. Consequently, the growing crystal phase still contained solvent molecules having a liquid structure. The time change of the solute composition in the early phase of crystal growth showed an increase in solute composition as the time step proceeded. The resulting solute composition in this early phase was considered at different temperature gradients in the universal cell and it increased as the temperature of the initial crystal-solution interface increased. A new distribution coefficient model was proposed as a function of the difference between the local solute composition and bulk solute composition in the solution around the crystal-solution interface. The impurity-solvent distribution coefficient could be represented by the new model for faster growth of the lower temperature's initial interface. As regards a better distribution coefficient, there was found to be a very dilute solution phase over the crystal phase. The new variable "distribution rate" instead of the ambiguous variable "growth rate" was considered as a function of temperature gradient in the universal cell.