Instantaneous strain recovery elasticity and endothermic heat change in nylon-6 monofilaments and silicone rubbers

The instantaneous elastic moduli for a nylon-6 monofilament were derived on strain recoveries right after creep, stress relaxation, and rapid elongation,E _c ,E _s andE _e , respectively. It was found that during strain recoveryE _s (>E _e ) andE _e increase monotonically with increasing load,m ₁, on the sample. The extrapolated value of E_s atm ₁=0 g is almost equal to Young's modulus, 4.06 GPa. The value ofE _c also increased with increasingm ₁, and atm ₁=600 g (1.93 t cm^–2) reached about 14 GPa. The endothermic heat change right after creep, stress relaxation or rapid elongation,Q, was negligibly small. For comparison,E _s ,E _c andQ were also investigated for silicone rubber. It was found thatE _s (53.8 M Pa at the draw ratioD=1.2) decreased abruptly atD=1.3. In the range ofD=1.4–1.9,E _s was only 22.6 MPa. In the case of stress relaxation,Q increased with increasingD from 4 J mol^–1 (atD=1.2) to 56 J mol^–1 (atD=1.9). FurthermoreE _c (5.58 MPa atm ₁=133.8 g (429.4 kg cm^–2)) increased gradually with increasing m₁ and attained 16.6 MPa atm ₁=548.4 g (1.76 t cm^–2). In the case of creep,Q was in the range of 0–11.5 J mol^–1 and larger when larger loads,m ₂ were removed during the later stages of creep.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe author wishes to thank Mr. Keizi Igarashi and Mr. Tetsuya Yasui for helping in the experiments.     

Excess thermodynamic properties of binary mixtures of N,N-dimethylacetamide with water or water-d2 at temperatures from 277.13 K to 318.15 K

Densities of binary mixtures of N,N-dimethylacetamide (DMA) with water (H₂O) or water-d₂ (D₂O) were measured at the temperatures from T=277.13 K to T=318.15 K by means of a vibrating-tube densimeter. The excess molar volumes V_m^E, calculated from the density data, are negative for the (H₂O + DMA) and (D₂O + DMA) mixtures over the entire range of composition and temperature. The V_m^E curves exhibit a minimum at x(DMA)≅0.4. At each temperature, this minimum is slightly deeper for the (D₂O + DMA) mixtures than for the corresponding (H₂O + DMA) mixtures. The difference between D₂O and H₂O systems becomes smaller when the temperature increases. The V_m^E results were correlated using a modified Redlich–Kister expansion. The partial molar volume of DMA plotted against x(DMA) goes through a sharp minimum in the water-rich region around x(DMA)≅0.08. This minimum is more pronounced the lower the temperature and is deeper in D₂O than in H₂O at each temperature. Again, the difference becomes smaller as the temperature increases. The excess expansion factor α^E plotted against x(DMA) exhibit a maximum in the water rich region of the mole fraction scale. At each temperature, this maximum is higher for the (D₂O + DMA) mixtures than for the corresponding (H₂O + DMA) mixtures, and the difference becomes smaller as the temperature increases. At its maximum, α^E can be even more than 25 per cent of total value of the cubic expansion coefficient α in the (H₂O + DMA) and (D₂O + DMA) mixtures.     

Effect of thermal history on the mechanical properties of three polypropylene impact-copolymers

The effect of thermal history on static mechanical properties and impact fracture behavior of three reactor polypropylene impact-copolymers (ICPPs) was investigated for three ICPPs prepared using commercial Innovene^®, Unipol^® and Spheripol^® polymerization technologies. Multiple extrusion employing a co-rotating twin-screw extruder resulted in a significant reduction of the molecular weight of the PP homopolymer phase evidenced by the increasing melt flow index (MFI). Neither cross-linking of the ethylene-propylene rubber (EPR) phase nor EPR particle coarsening was detected for any of the ICPPs after 5 consecutive extrusions. Decreasing molecular weight of the PP homopolymer phase caused change in the crystalline morphology of injection molded specimens due to the change in crystallization kinetics and reduction of the number of tie molecules, however, the overall degree of crystallinity did not change, significantly. The static tensile mechanical properties (E, σ_y, ?_b), critical strain energy release rate, G_c, and the Charpy notched impact strength, a_k, decreased with increasing MFI in a monotonous manner for all the ICPPs investigated. Despite significant differences between the absolute values of the mechanical properties for the three ICPPs, the MFI dependence of the σ_y and G_c relative to that for the unaffected ICPP fell on a single master curve for all of them. High-speed digital camera, used to follow the fracture process during the instrumented impact test, revealed no significant change of the small scale yielding fracture process with increasing MFI. This was in an agreement with the negligible change in the size of the crack tip plastic zone, R_p, predicted using simple mixed mode fracture model. The plane strain value of the critical strain energy release rate, G_1c, calculated from the measured G_c for the INN (2.4 kJ/m²), UNI (2.8 kJ/m²) and SPH (3.5 kJ/m²) using a simple LEFM model did not exhibit significant dependence on the number of extruder passes. The observed differences between the three ICPPs were ascribed to the significantly larger EPR content in UNI compared to the other two ICPPs and significantly larger content of isotactic PP homopolymer in the INN compared to the remaining two ICPPs.     

Tensile properties of semi-crystalline thermoplastic polymers: Effects of temperature and strain rates

This work deals with the study of temperature and time dependency of tensile properties of a PA 12-based polymer. The range of variation of parameters in experiments was linked to in-service conditions of components manufactured with this material (temperature interval from ?25 °C to 50 °C and average strain-rate magnitudes from 0.00028 s^?1 to 9.4 s^?1). For tests with different temperatures and low speed, an electro-mechanical machine, Zwick Z250, equipped with an incremental extensometer was used. To study the effect of strain rate at medium speeds, a servo-hydraulic system, Schenk PC63M, equipped with a strain-gauge extensometer was used, while at high speeds a servo-hydraulic machine, Instron VHS 160/20, equipped with a high-speed camera for strain evaluation by digital image correlation was employed. The changes of the rate of deformation with strain as well as elastic modulus variation with strain were studied. An increase in the elastic modulus and yield strength was observed with a drop in temperature and an increase in the strain-rate, temperature having a stronger influence on the variation of mechanical properties. The collected data was assembled in an elasto-plastic material model for finite-element simulations capable of rendering temperature- and strain-rate-dependency. The model was implemented in the commercial software Abaqus, yielding accurate results for all tests.     

High-pressure Raman scattering of MgMoO4

In this paper, we present results of high-pressure Raman scattering studies in β-MgMoO₄ from atmospheric to 8.5 GPa. The experiments were carried out using methanol–ethanol as pressure medium. By analyzing the pressure dependence of the Raman data (change in the number of lattice modes, splitting of bands and wavenumber discontinuities) we were able to observe a phase transition undergone by the β-MgMoO₄ at 1.4 GPa, which is only completed at ∼5 GPa. The transition was observed to be irreversible and the modifications in the Raman spectra were attributed to the changes in coordination of Mo ions from tetrahedral to octahedral. The transition possibly changes the original C2/m symmetry to C2/m or to P2/c. Implication on the phase transition for similar molybdate structures, such as α-MnMoO₄, is also highlighted.     

The disproportionation reaction phase transition,mechanical, and lattice dynamical properties of the lanthanum dihydrides under high pressure: A first principles study

The pressure-induced disproportionation reaction phase transition, mechanical, and dynamical properties of LaH₂ with fluorite structure under high pressure are investigated by performing first-principles calculations using the projector augmented wave (PAW) method. The phase transition of 2LaH₂ → LaH + LaH₃ obtained from the usual condition of equal enthalpies occurs at the pressure of 10.38 GPa for Perdew–Wang (PW91) functional and 6.05 GPa for Ceperly–Adler (CA) functional, respectively. The result shows that the PW91 functional calculations agree excellently with the experimental finding of 11 GPa of synchrotron radiation (SR) X-ray diffraction (XRD) of Machida et al. and 10 GPa of their PBE functional theoretical result. Three independent single-crystal elastic constants, polycrystalline bulk modulus, shear modulus, Young's modulus, elastic anisotropy, Poisson's ratio, the brittle/ductile characteristics and elastic wave velocities over different directions dependences on pressure are also successfully obtained. Especially, the phonon dispersion curves and corresponding phonon density of states of LaH₂ under high pressure are determined systematically using a linear-response approach to density functional perturbation theory (DFPT). Our results demonstrate that LaH₂ in fluorite phase can be stable energetically up to 10.38 GPa, stabilized mechanically up to 17.98 GPa, and stabilized dynamically up to 29 GPa, so it may remain a metastable phase above 10.38 GPa up to 29 GPa, these calculated results accord with the recent X-Ray diffraction experimental finding and theoretical predictions of Machida et al.     

Influence of strain rate on the compressive yield stress of CMDB propellant at low,intermediate and high strain rates

The mechanical properties of composite modified double base (CMDB) propellant significantly depend on the strain rate. In particular, the yield stress increases dramatically at higher strain rates. To study this behaviour, low, intermediate and high strain rate compression testing (1.7 × 10⁻⁴ to 4 × 10³ s⁻¹) of CMDB propellant at room temperature was conducted by using a universal testing machine, a hydraulic testing machine and a split Hopkinson pressure bar (SHPB) system, respectively. The yield stress was observed to increase bilinearly with the logarithm of strain rate, with a sharp increase in slope at a strain rate of 5 × 10¹ s⁻¹, which was supported by dynamic mechanical analysis (DMA) testing. The Ree-Eyring model, involving two rate-activated processes, was employed to predict the yield behaviour of CMDB propellant over a wide range of strain rates. The predictions are in excellent agreement with the experimental data.     

Direct fracture toughness determination of a ductile epoxy polymer from digital image correlation measurements on a single edge notched bending sample

This work presents a combined experimental and numerical study on the fracture toughness behaviour of a ductile epoxy resin system. Quasi-static fracture tests using single edge notched bending (SENB) specimens were conducted under room temperature conditions. In addition, the digital image correlation technique was employed to experimentally map the full-field displacements and strains around the notch and crack tip, allowing direct calculation of the J-integral fracture toughness. The magnitude of fracture toughness was found to be 1.52 ± 0.03 kJ/m², showing good consistency with the results measured according to the standard analytical formulations. A numerical model of the single edge notch bending specimen was built to compute the local strain field around the crack tip, together with the fracture toughness parameter. Good agreement was confirmed for both the experimental J-integral fracture toughness and the local surface strains around the crack-tip from the digital image correlation based optical technique, compared to the results obtained by numerical simulation. The fracture surfaces of the samples were examined using an optical microscope to analyze the failed surface morphology and the corresponding failure mechanisms.     

High-pressure Raman spectra of racemate dl-alanine crystals

Raman spectroscopy investigations of dl-alanine crystal under high pressures have been carried out up to 18.0 GPa. For instance, around 1.0 GPa and between 1.7 and 2.3 GPa changes in the Raman profile were observed and associated to conformational changes of the molecules in the unit cell or to a phase transition accompanied to slight conformational change of the molecule through CH and CH₃ groups. Moreover, between 6.0 and 7.3 GPa, the appearance of a new low energy lattice modes and to the splitting of a band assigned to the stretching vibration of the CCH₃ moiety were related to a second phase transition. Finally, changes in lattice modes, red shift of the band associated to CCH₃ stretching and increasing of line-width of the band associated to the wagging of CO₂, between 11.6 and 13.2 GPa, are ascribed to a third phase transition. On release of pressure the original phase was obtained again.     

Properties and consolidation of nanocrystalline 3Cu–Al2O3 composite by rapid sintering

Nanopowders of Cu and Al₂O₃ were synthesized from 3CuO and 2Al powders by high-energy ball milling. Nanocrystalline Al₂O₃ reinforced composite was consolidated by pulsed-current activated sintering method within 2 min from mechanically synthesized powders of Al₂O₃ and Cu. The relative density of the composite was 96%. The average hardness and fracture toughness values obtained were 540 kg/mm² and 6.3 MPa m^1/2, respectively.

     

Volumetric study of (2-methoxyethanol + tetrahydrofuran + cyclohexane) at T=298.15 K

The excess molar volumes V_m^E at T=298.15 have been determined in the whole composition domain for (2-methoxyethanol + tetrahydrofuran + cyclohexane) and for the parent binary mixtures. Data on V_m^E are also reported for (2-ethoxyethanol + cyclohexane). All binaries showed positive V_m^E values, small for (methoxyethanol + tetrahydrofuran) and large for the other ones. The ternary V_m^E surface is always positive and exhibits a smooth trend with a maximum corresponding to the binary (2-methoxyethanol + cyclohexane). The capabilities of various models of either predicting or reproducing the ternary data have been compared. The behaviour of V_m^E and of the excess apparent molar volume of the components is discussed in both binary and ternary mixtures. The results suggest that hydrogen bonding decreases with alcohol dilution and increases with the tetrahydrofuran content in the ternary solutions.     

Self‐reinforced polypropylene composites based on low‐cost commercial woven and non‐woven fabrics

In the present paper, different self‐reinforced polypropylene (PP) composites based on low‐cost commercial woven (w) and non‐woven (nw) fabrics were obtained. Hot compaction (HC) and film stacking (FS) followed by compression molding were used to prepared the composites. The fracture and failure behavior of the different materials was determined under different testing conditions through quasi‐static uniaxial tensile tests, Izod impact experiments and by means of fracture mechanics tests on mode I double‐edge deeply notched tensile specimens. In the case of the composite obtained by film stacking + compression molding (rPP/nw/w‐FS) and the hot‐compacted composite (nw/w‐HC) containing simultaneously woven and non‐woven fabrics, the acoustic emission technique was applied in situ in the tensile tests to determine their consolidation quality and to identify the failure mechanisms responsible for their fracture behavior. It was observed that both composites exhibited relatively similar high consolidation quality. However, the hot‐compacted composite presented a more uniform distribution of failure mechanisms (debonding and fiber fracture) than the film‐stacked composite. The hot‐compacted composite containing both types of reinforcements exhibited the best combination of mechanical (tensile, impact, and fracture) properties. Therefore, this composite appeared as the most promising for structural applications among the different composites investigated.     

In situ measurement of biaxial modulus of Si anode for Li-ion batteries

We report in situ measurement of biaxial moduli of a Si thin-film electrode as a function of its lithium concentration. During lithiation, biaxial compressive stress is induced in the Si film and it undergoes plastic flow. At any state-of-charge (SOC), a relatively small delithiation–relithiation sequence unloads and reloads the film elastically. From the stress and strain changes during a delithiation–relithiation cycle, the biaxial modulus of the film is calculated. Stress change is obtained by measuring the change in substrate curvature using a Multi-beam Optical Sensor; the elastic strain change is obtained from the change in SOC. By repeating these measurements at several different values of SOC, the biaxial modulus was seen to decrease from ca. 70 GPa for Li_0.32Si to ca. 35 GPa for Li_3.0Si. Such a significant reduction in elastic modulus has important implications for modeling stress evolution and mechanical degradation in Si-based anodes.     

Thermodynamics of mixtures with strongly negative deviations from Raoult’s law: Part 6. Excess molar volumes at 298.15 K for 1-alkanols + dibutylamine systems. Characterization in terms of the ERAS model

Excess molar volumes, V_m^E, at 298.15 K and atmospheric pressure over the entire composition range for binary mixtures of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol and 1-octanol with dibutylamine are reported. They are calculated from densities measured with a vibrating-tube densimeter. All the excess volumes are large and negative over the whole mole fraction range, indicating strong interactions between unlike molecules, which are more important for the systems involving methanol or ethanol, characterized by the most negative V_m^E. For the other mixtures, V_m^E at equimolar composition, is approximately constant. The V_m^E curves are nearly symmetrical. The V_m^E and excess molar enthalpies (H_m^E) of the mixtures studied are consistently described by the ERAS model. The ERAS parameters confirm that the strongest interactions between unlike molecules are encountered in the methanol+dibutylamine system.     

Mechanical properties of the novel organometallic polymer poly(ferrocenyldimethylsilane)

A study of the mechanical properties of poly(ferrocenyldimethylsilane) [Fe(η‐C₅H₄)₂SiMe₂]_n, 3 , a novel organometallic polymer, has been performed on thin films of this material. The Young's modulus and Poisson's ratio of film samples (15 × 1 × 1 mm) of 3 were measured in quasi‐static tension using a video extensometer. For 3 , the values of the Young's moduli (E) and Poisson's ratios (ν) were similar between axes in the plane and independent of the splicing direction used during sample preparation. The mean and standard deviation of the Young's modulus and Poisson's ratio were 0.78 ± 0.08 GPa and 0.37 ± 0.06 GPa, respectively. Thermomechanical analysis of 3 revealed a steady decrease of E from a room temperature value of approximately 0.70 GPa. Additionally, it was found that at 150 °C, 3 was unable to support even small stresses, consistent with the onset of a melt transition (ca. 135 °C). A mathematical model based on molecular geometry is developed to describe the results. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2280–2288, 2005     

Carbon based Si- and Cr-containing thin films: Chemical and nanomechanical properties

Si- and Cr-containing C films were deposited by magnetron sputtering combined with CVD onto silicon wafers. The composition and chemical structure were characterized by X-ray Photoelectron Spectroscopy (XPS) and nanomechanical properties by depth-sensing hardness and scratch techniques.The incorporated Si and Cr are preferentially bonded to carbon, in accordance with simplified thermodynamic calculations and as manifested by the XPS chemical shifts. At relatively high Cr- and low Si-content silicides (Cr_xSi) may also form as indicated by X-ray induced Auger electron spectroscopy. The chromium content in the C–Si–Cr films varied between 1 and 55 at% while the silicon content in the same films between 25 and 0 at%. For comparison two-component films of Si–C and Cr–C were also deposited with Si-content up to 42 at% and Cr-content up to 55 at% by varying the input power of the magnetrons.The nanohardness (H) and reduced modulus (E) were higher for all the films than that of the silicon substrate being 10 GPa, 127 GPa, respectively. Interestingly, the H and E of the three-component CrSiC films were almost invariant of the changes of the components' concentration within the indicated range and varied between 13–16 GPa and 120–140 GPa. H and E values for the two-component Cr–C films were much higher, reaching about 22 GPa and 170 GPa, respectively.     

The Dynamic Impact Experiments Under Active Confining Pressure and the Constitutive Equation of PP/PA Blends at Multi-Axial Compressive Stress State

Summary : A special active hydraulic confining pressure installation matched with Φ14.5 mm SHPB apparatus was developed. A series of active confining pressure impact experiments for PP/PA blends are performed in this special SHPB system under two kinds of axial strain rate: 8.0*10², 1.4*10³ s⁻¹ and the active confining pressure of 0 MPa, 4 MPa, 8 MPa, 12 MPa, 15 MPa, 20 MPa. The axial strain-time profile, the axial stress-time profile and the hoop strain-time profile of the specimen are recorded online respectively. According to the equilibrium equation, the complete state of principal stress and principal strain of PP/PA blends under multi-axial stress state is analyzed. The experimental results reveal that the axial stress-strain curves all are related to the confining pressure and the strain rate. It can also be seen that under a constant effective strain rate the effective stress- effective strain curves at different confining pressures are coincident basically. This manifests that under a certain effective strain rate there is only one unique effective stress- effective strain curve. The multi-axial constitutive equation for PP/PA blends is suggested finally as: where σ_conf is the confining pressure value. For 113 PP/PA blends, E = 2.98 GPa, α = −31.15 GPa, β = 93.31 GPa, θ₂ = 8.54 µS, E₂ = 0.82 GPa.     

Application of model-free and multivariate non-linear regression methods for evaluation of the thermo-oxidative endurance of a recent manufactured parchment

The thermo-oxidative degradation of a parchment recent manufactured from a goat skin has been investigated by TG/DTG, DSC simultaneous analysis performed in static air atmosphere, at six heating rates in the range 3–15 K min⁻¹. At the progressive heating in air atmosphere, the investigated material exhibits three main successive processes occurring with formation of volatile products, namely the dehydration followed by two thermo-oxidative processes. The processing of the non-isothermal data corresponding to the first process of thermo-oxidation was performed by using Netzsch Thermokinetics—a Software Module for Kinetic Analysis. The dependence of activation energy, evaluated by isoconversional methods suggested by Friedman, and Ozawa, Flynn and Wall, on the conversion degree and the relative high standard deviations of this quantity show that the investigated process is a complex one. The mechanism and the corresponding kinetic parameters were determined by Multivariate Non-linear Regression program. Three mechanisms, one consisting in four successive steps and two others in five successive steps, exhibit the best F-test Fit Quality for TG curves. It was also used the previously suggested criterion, according to which the most probable process mechanism correspond to the best agreement between E _FR  = E _FR (α) (E _FR is the activation energy evaluated by isoconversional method suggested by Friedman; α is the conversion degree) obtained from non-isothermal experimental data and activation energy values, E _iso , obtained by applying the differential method to isothermal data simulated using non-isothermal kinetic parameters. According to this last criterion, the most probable mechanism of parchment oxidation consists in four successive steps. The contribution of the thermo-oxidation process in the parchment damage by natural aging is discussed.     

Study into melting-crystallization of silver thiogallate by the statistical thermal analysis method

The influence of heat treatment of a liquid phase on “melting-crystallization” processes of silver thiogallate (AgGaS₂) having chalcopyrite structure I [`4]2\textd \bar{4}2{\text{d}} , has been studied by the method of statistical thermal analysis (STA). It is shown that the melting temperature of solid phase (T _m) increases non-monotonic from 970 °C due to rise in the preliminary melt overheating, and T _m reaches asymptotically 1010 °C. The equilibrium melting-crystallization temperature ( T_\textm^\texto T_{\text{m}}^{\text{o}} ) has been defined as 989.2 °C. It is also found an extreme dependence of the melt supercooling on its overheating. The two curves of irregular dependence of nucleation rate on melt supercooling have been plotted at different melt overheating.     

Compressive response of composite ceramic particle-reinforced polyurethane foam

Quasi-static and dynamic compressive tests are undertaken on the polyurethane (PU) foam and fumed silica reinforced polyurethane (PU/SiO₂) foam experimentally. The ceramic microspheres with varying mass fractions are adopted to mix with the PU/SiO₂ foam to fabricate the composite particle-reinforced foams. The effects of strain rate and particle mass fraction are discussed to identify and quantify the compressive response, energy-absorbing characteristic, and the associated mechanisms of the composite foams. The results show the initial collapse strength and plateau stress of the foams are improved significantly by reinforcing with the ceramic microsphere within 60 wt% at quasi-static compression. The rate sensitivity is observed on all the foams, but in different patterns due to the influence of ceramic microsphere. The compressive response affected by ceramic microsphere can be attributed to the particle cluster effect and stress wave propagation. Together with the deformation, the compressive characteristic experiences non-monotonic change from the low to high strain rates. The specific energy absorption (SEA) of the foam with 41 wt% ceramic microsphere show the largest magnitude at quasi-static compression. With the increasing strain rate, the ceramic reinforced foam exhibits superior energy absorption efficiency at high strain rates to that of the pure foams.