Effective volume changes during fatigue and fracture of polyacetal

Conventional tensile dilatometry techniques are extended to cyclic fatigue applications to study volume changes that occur during controlled-load cyclic fatigue of polyacetal. During fatigue, in-situ measures of the irreversible and elastic volume change are monitored together with dynamic viscoelastic parameters (E′, E″, and Tan δ), and changes in the energy densities (strain energy, potential energy, and irreversible work). The results show that the effective irreversible volume of the polyacetal gradually increases over a wide range of applied cyclic stress. However, at high stress levels and/or frequencies (i.e., low-cycle, thermally dominated regime), the effective Poisson's ratio of the polyacetal increases as it softens (evidenced by the dynamic viscoelastic data). Conversely, at lower stress levels, the Poisson's ratio continually decreases coincident with decreases in the loss modulus (E″) and the irreversible work density. These results are indicative of entirely different mechanisms governing the low-cycle (high stress level) and high-cycle (low stress) regimes. Also, comparisons between tensile and fatigue dilatometry studies show that the dilational-strain response of samples fatigued at high stress levels are similar to data obtained from monotonic tensile dilatometry. However, the dilationstrain response of samples fatigued at lower stress levels are distinctly different from low-cycle fatigue and tensile dilatometry.     

The influence of temperature and absorbed water on the fatigue crack propagation in nylon-6,6

The effect of absorbed water on the fatigue crack propagation (FCP) of nylon-6,6 was investigated over a range of test temperatures and is correlated with dynamic mechanical properties. Both the storage modulus, a measure of specimen stiffness, and the loss compliance, a measure of energy dissipation and hysteretic heating, influence FCP response. At a given temperature, fatigue resistance is greatest for a given water content corresponding to an optimum combination of storage modulus, E′, and loss compliance, D″. The use of an empirical shift parameter to normalize the temperature dependence of the FCP behaviour of nylon with various water contents is discussed.     

Viscoelastic properties of polyamic acid solutions—precursors of polyimides

The rheology of polyamic acid (PAA) solutions, precursors of polyimides used in microelectronic device applications, has been investigated by dynamic (oscillatory) shear flow measurements. Frequency dependent storage and loss moduli and dynamic viscosity were measured in the frequency range 10^?1 to 10³ rad/s at 23°C. The storage modulus G′ (ω) and loss modulus G″ (ω) exhibited quadratic and linear dependence in frequency at low frequencies respectively, the viscoelastic fluid behavior commonly predicted for polymer solutions from many molecular theories. At high frequencies both dynamic moduli become proportional to ω^2/3. The results show that PAA solutions are very high loss viscoelastic fluids, judging from the loss tangent values which far exceed unity. It is suggested that dynamic viscoelastic properties could be used to monitor the degree of imidization since there is a gradual change from viscoelastic fluids to soft viscoelastic solids to hard viscoelastic solids as PAA is converted to polyimides. Onset of non-Newtonian flow as shown on the frequency dependent dynamic viscosity was in the range 30 to 200 rad/s. The viscoelastic constants, zero-shear rate viscosity η_o and steady-state compliance J_e⁰, where also determined from the dynamic data and compared to previous steady shear flow results.     

Dynamic mechanical analysis of ethylene–propylene–diene monomer rubber and styrene–butadiene rubber blends

The effects of blend ratio, crosslinking systems, and fillers on the viscoelastic response of ethylene–propylene–diene monomer (EPDM)/styrene–butadiene rubber (SBR) blends were studied as functions of frequency, temperature, and cure systems. The storage modulus decreased with increasing SBR content. The loss modulus and loss tangent results showed that the EPDM/SBR blend vulcanizate containing 80 wt % EPDM had the highest compatibility. Among the different cure systems studied, the dicumyl peroxide cured blends exhibited the highest storage modulus. The reinforcing fillers were found to reduce the loss tangent peak height. The blend containing 40 wt % EPDM showed partial miscibility. The dispersed EPDM phase suppressed the glass‐transition temperature of the matrix phase. The dynamic mechanical response of rubbery region was dominated by SBR in the EPDM–SBR blend. The morphology of the blend was studied by means of scanning electron microscopy. The blend containing 80 wt % EPDM had small domains of SBR particles dispersed uniformly throughout the EPDM matrix, which helped to toughen the matrix and prevent crack propagation; this led to enhanced blend compatibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of short chain branching on the viscoelastic behavior during fatigue fracture of medium density ethylene copolymers

A method to determine viscoelastic changes in medium density polyethylene (MDPE) pipe specimens associated with the crack tip during fatigue crack initiation (FCI) and propagation (FCP) experiments is described. The load-displacement curves are analyzed to obtain the phase angle, δ. Changes in δ are related to the number of cycles of crack initiation of three different MDPE copolymers: hexene (H), butene (B), and methyl pentene (MP) copolymers. These changes are related to craze formation and growth at the notch tip, leading to crack initiation and to the irreversible work, W_i, expended on them. Within a given material, step wise increments in δ distinguish the onset of crack initiation and the brittle-to-ductile transition in crack growth. The magnitudes of tan δ and W_i are noted to be in quantitative agreement with the resistance of the three copolymers to FCI and brittle propagation that rank in the order: isobutyl (MP) > ethyl (B) > butyl (H). Similar crystallinity of the three copolymers insinuates a hypothesis that variance in the nature of chain entanglements associated with the respective branch type might be accountable for the observed differences in viscoelastic character. The final stage of failure by ductile tearing is dominated by large scale plastic flow that seemingly overshadows the material differences governing time dependent brittle fracture.     

Viscoelastic properties of a gum vulcanizate at large static deformations

The loss tangent corresponding to small sinusoidal oscillations superposed on a large static deformation is found to decrease with increasing static deformation ratio for a natural rubber gum vulcanizate. Further, the response functions of the stress–relaxation and the incremental stress–relaxation vs. time and the storage modulus vs. frequency are found not to be separable functions of time and strain effects. These findings are shown to indicate that the elastic contribution to the viscoelastic response of this elastomer increases more rapidly with the static deformation than does the relaxation contribution. The loss modulus, however, is found to be a separable function of time and strain effects. Hence, only one relaxation function is needed in the viscoelastic constitutive theory applied to this elastomer. The finite linear viscoelasticity theory as modified by Morman has a form which can account for these results. Predictions of the incremental stress–relaxation function from dynamic data are within 1% of experimental values.     

Dynamic stress‐stiffening of carbon black‐filled vulcanizates

Dynamic stress‐stiffening was investigated under relatively low deformation for the vulcanizates reinforced with carbon black. When dynamic strain sweep with fixed strain amplitude was imposed on samples, storage modulus and loss modulus were significantly increased and loss tangent and loss compliance remained unchanged. It was found that stress‐stiffening effect showed a strong dependence on aging time, frequency, as well as oscillatory strain magnitude. At 60°C, the strain‐aged vulcanizate produced a significant stress‐stiffening effect whereas the material hardening was not observed at 0°C. The increased Payne effect after cyclic deformations can be destroyed partially by dynamic strain sweeps. These features are quite different from the Mullins effect and dynamic stress‐softening effect in filled rubbers. We interpreted this character of filled vulcanizates in much developed carbon black agglomerates and other possible superstructures. The results provide new insight into understanding the relationship between the rolling resistance of tires and lab‐tested dynamic property. POLYM. ENG. SCI., 59:1743–1752, 2019. © 2019 Society of Plastics Engineers     

Effects of Time and Temperature on the Viscoelastic Properties of Chinese Fir Wood

The effects of time and temperature on dynamic viscoelastic properties of Chinese fir (Cunninghamia lanceolata [Lamb.] Hook) were investigated using dynamic mechanical analysis in this study. The isothermal tests were applied to the small clear specimens with a moisture content of about 0.6% at constant temperatures ranging from 25 to 200°C for 550 min at atmospheric pressure. Changes in storage modulus and loss tangent with heating time were examined. The results indicated that heating time mainly resulted in thermal softening, thermal degradation of wood, and the reduction of wood stiffness. At more than 60°C, the reduction in storage modulus was accelerated generally as the wood was subjected to a higher temperature or longer heating time. At constant temperatures of 140 and 160°C, a relaxation phenomenon was observed with a slight change in weight, which could be attributed to the relocation of lignin molecules. At the temperature range of 140 to 180°C, the higher the heating temperatures, the earlier the tanδ peak appeared. It is suggested that the wood thermal softening occurs at higher temperatures with shorter heating times or at lower temperatures with longer heating times. At temperatures of 180 and 200°C, the loss of amorphous polysaccharides due to thermal degradation is considered to be the main factor affecting wood viscoelasticity.     

Simultaneous measurement of resistance and viscoelastic responses of carbon black‐filled high‐density polyethylene subjected to dynamic torsion

The conduction and viscoelastic responses to temperature are measured simultaneously for carbon black (CB) filled high‐density polyethylene (HDPE) subjected to dynamic torsion. PTC/NTC transition was correlated with the loss tangent peak and the quasi modulus plateau, which was ascribed to the filler network. The bond‐bending model of elastic percolation networks was used to reveal the structural mechanisms for the cyclic resistance changes at different temperatures. The resistance changes at lower temperatures depended on the deformation of the polymer matrix, while the changes in melting state were mainly attributed to the rearrangement of the CB network. A simple scaling law is derived to relate resistance and dynamic storage modulus in the melting region. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dynamic viscoelastic properties of CaCO3 filled,closed cell microcellular copoly (ethylene/octene) vulcanisates Effect of blowing agent,temperature, and strain

Abstract

Dynamic mechanical analysis of precipitate CaCO₃ filled, closed cell microcellular ethylene–octene copolymer vulcanisates has been studied as a function of temperature and double strain amplitude. Experiments were carried out over the temperature range – 100 to 100°C. Strain dependent isothermal dynamic mechanical analysis was performed for double strain amplitude 0·09–5%. The log of storage modulus bears a simple relationship with the log of density for both solid and closed cell microcellular rubber. The slope of the line is found to be temperature dependent. The relative storage modulus decreases with decreasing relative density. The eect of blowing agent and filler loading on storage modulus and loss tangent were also studied. Cole–Cole plots of microcellular vulcanisates show a circular arc relationship with density. Plots of loss tangent against storage modulus were found to exhibit a linear relationship. Hysteresis and strain work also bear a linear relationship.     

Dynamic properties of crosslinked epoxy resin at large cyclic and static deformation

Measurement of dynamic properties of crosslinked epoxy resin have been performed under torsional cyclic deformation with different amplitudes and frequencies and with extensional creep under different loads. It is found in both cases that the dynamic modulus decreases above a certain critical value of deformation. Truncation of the glassy state region and shifting of the transition zone to lower temperatures and higher frequencies have been observed as effects of large amplitude deformation. The maximum reduction in the modulus value and the minimum in the critical amplitude both occur in the region of T_g Shear fatigue of the material has been observed in the glassy state with a frequency- and temperature-dependent fatigue life. It is found that the loss modulus under extensional creep depends upon the values of the deformation and stress whereas the storage modulus depends solely upon the deformation. The ratio of energy expended during static and cyclic deformations is shown to depend only upon the extensional deformation.     

Dynamic mechanical behavior of flexible graphite made from exfoliated graphite

The low-frequency dynamic mechanical properties of low density flexible graphite (0.027–0.089 g/cm³, obtained by compressing exfoliated graphite at 0.3–1.7 MPa without a binder) are different in flexure and compression. The storage and loss moduli and the loss tangent are higher under flexure than compression. Under flexure, the storage modulus is essentially unaffected by increasing the static strain while the loss tangent and loss modulus decrease. Under compression, both storage and loss moduli increase with increasing static strain, while the loss tangent slightly decreases. The storage and loss moduli are higher and the loss tangent is lower for out-of-plane compression than for in-plane compression. The storage and loss moduli increase with increasing fabrication pressure, while the loss tangent decreases. Energy dissipation is much more effective under flexure than compression. Flexure appears to provide more sliding of the graphite layers than compression. For the highest energy dissipation under flexure, a low static strain is recommended; for high energy dissipation under compression, a high static strain is recommended.     

Rheological behavior and network dynamics of silica filled vinyl‐terminated polydimethylsiloxane suspensions

Present article reports the rheological properties and network dynamics of fumed silica filled vinyl‐terminated polydimethylsiloxane suspensions. The results reveal that as filler loading increases, the span of the linear viscoelastic region with constant dynamic storage modulus is narrowed with increase in strain amplitude while the relaxation time of the compounds get shifted to longer time scales. The dynamics of filler‐network indicated significant Payne effect due to fumed silica incorporation into the PDMS matrix. Further, strain‐induced agglomeration of fumed silica particles, characterized by a peak in the dynamic loss modulus curve could also be observed. High loss‐tangent was observed for lower contents of filler in the suspension, an effect with an apparent relationship to the loosely formed filler‐network. The formation of a saturated network structure of fumed silica particles was evident from the dynamic modulus and complex viscosity data, that remained unaffected with frequency till a critical amount of fumed silica loading. Han plots (storage modulus versus loss modulus) revealed the microstructural changes for various filled systems that was attributed to build‐up of the filler‐network causing an apparent evolution of yielding phenomenon. Van Gurp‐Palmen plots (complex modulus versus phase lag) showed that flow behavior of the filled PDMS suspensions resembled to that of typical viscous fluids. POLYM. ENG. SCI., 57:973–981, 2017. © 2016 Society of Plastics Engineers     

Experimental and numerical prediction of effect of frequency on bending fatigue performance of polyamide 66/hectorite nanocomposite

An increased use of thermoplastics in components and structures that are subjected to cyclic loads necessitates a specific attention to variables that affect the hysteretic heating. Hysteretic heating effect in polyamide 66/hectorite nanocomposite has been investigated under bending strain control mode using a custom-built bending fatigue test setup in a laboratory environment. Dynamic mechanical analysis (DMA) results revealed a considerable rise in loss modulus with a decrease in frequency from 1 to 0.1?Hz irrespective of the temperature of the specimen. Alternatively, a reduction in fatigue test frequency from 2 to 0.5?Hz resulted in a significant decrease in cyclic softening. Fatigue behaviour predicted from DMA results using coupled structural/thermal finite element analysis is fairly in agreement with the experimental one. An accelerated crack initiation at decreased specimen temperature and high cyclic steady state stress reduced the fatigue life at 0.5?Hz compared with 2?Hz.     

Viscoelastic sol–gel state of the chitosan and alginate solution mixture

The rheological behavior of chitosan/alginate solutions was investigated in relation to gelation and polyelectrolyte complex (PEC) formation. Before mixing, the chitosan and the alginate solutions were both homogeneous fluids. However, heterogeneity developed after mixing, accompanied by a serious increase of viscosity. To determine the sol–gel state of the solutions, the viscoelastic variables, such as the dynamic storage modulus (G′) and loss modulus (G″), the loss tangent, and the viscoelastic exponents for G′ and G″, were obtained. Depending on the concentration, the chitosan/alginate solutions revealed unexpected rheological behavior. At a polymer concentration of 1.0 wt %, the chitosan/alginate solution was in a viscoelastic gel state, whereas, at higher concentrations, viscoelastic sol properties were dominant. A viscoelastic gel state for the chitosan/alginate solution was induced based on the weak formation of fiber‐shaped precipitates of a PEC at a low polymer concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1408–1414, 2007     

Dynamic mechanical properties of highly loaded ferrite-filled thermoplastic elastomer

The dynamic mechanical properties in terms of the storage modulus E′, loss modulus E″, and the loss tangent δ has been studied for highly filled magnetic polymer composites. The effect of surface treatment on the relaxation spectra has been clearly elucidated and quantitative values indicating the extent of polymer–filler interactions have been given. Various models have been tested for describing the viscoelastic behavior of such highly filled systems. The Wiechert model using a single-arm with a Cole–Cole parameter has been shown to effectively fit the Argand diagram in the case of the present highly filled systems.     

聚合物熔体动态黏弹特性微尺度效应实验研究

针对聚合物熔体在微流道内,因拉伸/压缩作用导致的黏弹特性受物理尺度影响的问题,通过动态剪切流动实验系统研究了四种聚合物材料的黏弹特性,以及黏弹特性随物理尺度的变化规律。结果表明,在角频率1~100 rad/s的范围内,聚酰胺、聚氨酯、聚乳酸均表现出耗能模量大于储能模量的黏性占优特征,聚丙烯在高频区时表现出弹性占优特征。储能模量与耗能模量均随着物理特征尺度的减小而降低。物理特征尺度从1000 μm减小到250 μm的变化过程中,聚氨酯、聚酰胺和聚丙烯三种熔体的弹性效应对微尺度变化的敏感性比黏性效应强烈,储能模量变化率与耗能模量变化率的差值分别为5.8%、4.2%和2.6%。聚乳酸熔体的黏性效应对微尺度变化的敏感性与弹性效应基本一致,其储能模量变化率与耗能模量变化率的差值为-0.3%。材料分子链特征的差异导致储能模量与耗能模量随物理特征尺度减小的变化率不同。熔体黏弹特性对微尺度变化敏感性的强弱依次为聚氨酯、聚酰胺、聚丙烯和聚乳酸,其黏弹性特征参量的变化率分别为28.6%、22.6%、20.6%和19.45%。     

Fatigue failure mechanisms in polymer composites

Axial fatigue of two, commercial, talc-filled polypropylenes was studied. A significant result of our investigation was the identification and characterization of the failure mechanisms and the effects of frequency and hysteretic heating. Frequency was found to be important to the fatigue response of the polymers. At low frequency, fatigue failure appeared to be a process of crack initiation and growth with very little dissipative heating. At high frequency, the fatigue process was dominated by dissipative heating resulting in significant creep and modulus loss, and failure was much accelerated and due mainly to material softening and melting. Correlation of temperature rise with on-line energy loss in selected experiments enabled us to extract information from the fatigue process. The results provided some quantitative understanding of the different fatigue failure mechanisms at low and high frequencies.     

Investigation on the dynamic melt rheological properties of polypropylene/wood flour composites

The rheological behavior of polypropylene/wood flour (WF) composite was investigated at constant temperature over a wide range of frequencies using a mechanical compact rheometer operated in the dynamic mode. The effect of WF content, particle size, and coupling agent on melt rheological properties were investigated. The melt rheological data in terms of complex viscosity (η*), storage modulus (G′), loss modulus (G″), and loss tangent (tan δ) were studied and compared for different samples. It was found that complex viscosity increases with increasing wood content and coupling agent. Compatibilization using coupling agent increased both storage modulus and loss modulus, but the variation of storage modulus is more. By increasing wood content storage modulus increases. Complex viscosity, storage modulus, and loss modulus showed a minimum value by increasing of wood particle size. Tan δ decreases with increasing of wood content. Cole–Cole plot indicated that relaxation process changes with addition WF, coupling agent, and using different mesh size of wood. The Han plots revealed the sensitivity of rheological properties with composition at constant temperature. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Dynamic rheological properties for HDPE/CB composite melts

A study on the dynamic viscoelastic properties of carbon black (CB)‐filled high‐density polyethylene (HDPE) in the molten state was carried out. When the temperature was above 180°C in an air atmosphere, the storage modulus G′, loss modulus G″, and loss tangent δ showed particular characteristics. In the low‐frequency region, the modulus increased with increase of the testing time while the tan δ obviously decreased. Also, the higher the temperature, the more notable was the change. We can detect these changes from the deviation of G′ (G″) against ω plots from the linearity and the appearance of a characteristic plateau phenomenon. The width and height of the modulus plateau increased with increase of the temperature. When temperature was below 180°C, the testing time and the temperature had no effect on the viscoelastic parameters of HDPE. However, if we used 99% nitrogen gas as the atmosphere, substituting for air, the viscoelastic parameters revealed an undiscernible change, different from that in an air atmosphere. No changes were found under the protection of the antioxidant B215. This phenomenon indicated that HDPE can be oxidized at a temperature higher than 180°C. Nitrogen gas and an antioxidant agent can prevent HDPE from crosslinking. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2160–2167, 2003