Glass transition and free volume behaviour of poly(acrylonitrile)/LiCF3SO3 polymer-in-salt electrolytes compared to poly(ether urethane)/LiClO4 solid polymer electrolytes

Measurements of the glass transition temperature (T_g) and free volume behaviour of poly(acrylonitrile) (PAN) and PAN/lithium triflate (LiTf), with varying salt composition from 10 to 66 wt% LiTf, were made by positron annihilation lifetime spectroscopy (PALS). Addition of salt from 10 to 45 wt% LiTf resulted in an increase in the mean free volume cavity size at room temperature (r.t.) as measured by the orthoPositronium (oPs) pickoff lifetime, τ₃, with little change in relative concentration of free volume sites as measured by oPs pickoff intensity, I₃. The region from 45 to 66 wt% salt displayed no variation in relative free volume cavity size and concentration. This salt concentration range (45 wt%<[LiTf]<66 wt%) corresponds to a region of high ionic conductivity of order 10⁻⁵ to 10⁻⁶ S cm⁻¹ at T_g as measured by PALS. A percolation phenomenon is postulated to describe conduction in this composition region. Salt addition was shown to lower the T_g as measured by PALS; T_g was 115°C for PAN and 85°C for PAN/66 wt% LiTf. The T_g and free volume behaviour of this polymer-in-salt electrolyte (PISE) was compared to a poly(ether urethane)/LiClO₄ where the polymer is the major component, i.e. traditional solid polymer electrolyte (SPE). In contrast to the PISE, the T_g of the SPE was shown to increase with increasing salt concentration from 5.3 to 15.9 wt%. The relative free volume cavity size and concentration at r.t. were shown to decrease with increasing salt concentration. Ionic conductivity in this SPE was of order 10⁻⁵ S cm⁻¹ at r.t., which is over 60°C above T_g, 10⁻⁸ S cm⁻¹ at 25°C above T_g, and conductivity was not measurable at T_g.

Effect of relaxation on pressure sensitivity index in a Zr-based metallic glass

Shear-banding features of as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass were investigated through Rockwell indentation tests. Isothermal annealing of the as-cast samples was conducted at temperatures below its glass transition temperature, Tg. The exothermal enthalpy during continuous heating below Tg decreases with increasing annealing temperature, indicating the gradual reduction of free-volume upon annealing. The observation on the morphology of shear-banding pattern around the indents implies a reduced shear bands activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of Rockwell indent decrease from 88° for the as-cast sample to 79° for the sample annealed at 633 K for 1 h, indicating a pressure sensitive plasticity. By Mohr–Coulomb criterion, the pressure sensitive index can be obtained on the basis of the measured 2θ, which increases with increasing annealing temperature, indicating an increase of “atomistic friction” due to the reduction of the free volume upon annealing.

Indentation study on the pressure sensitivity of a ZR-based bulk metallic glass

Spherical indentation test was conducted on as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass, and the evolution of the morphology of the deformation zone of indents upon annealing was investigated. The DSC traces of the as-cast and annealed samples show that the enthalpy change at the glass transition, ΔH, decreases with the increasing of annealing temperature, indicating the reduction of the free volume upon annealing. The morphology of the indents implies a reduced shear band activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of spherical indent in the as-cast and the annealed samples were measured to be in the range of 88-79°, which decrease with the increasing of annealing temperature, indicating pressure sensitive plasticity in the as-cast and annealed samples. By Mohr–Coulomb criterion, the pressure sensitive index, α, can be obtained on the basis of the measured 2θ. The sensitivity index increases with increasing temperature, implying an increase of 'atomistic friction' due to the reduction of the free volume upon annealing.

Effects of quenching rate on amorphous structures of Cu46Zr54 metallic glass

Metallic glass shows some superior properties different from crystalline, but the nature of amorphous structure and structural change during glass transition have not been completely understood yet. Molecular dynamics simulation provides intuitive insight into the microstructure and properties at atomistic level. Before probing into the microstructures of metallic glass with molecular dynamics (MD) simulation, it is important to obtain amorphous state first. In the current work, we reproduce the process of manufacturing metallic glass in laboratory including the melting, equilibrating and quenching procedure with molecular dynamics simulations. The structure changing at melting point and glass transition temperature are investigated with the different cooling processing. The partial radial distribution function (PRDF) is applied as a criterion to judge the final amorphous state obtained considering the quenching at different cooling rates and the effects of cooling rate on the formation of amorphous structures are further discussed.

Effects of quenching rate on amorphous structures of Cu46Zr54 metallic glass

Metallic glass shows some superior properties different from crystalline, but the nature of amorphous structure and structural change during glass transition have not been completely understood yet. Molecular dynamics simulation provides intuitive insight into the microstructure and properties at atomistic level. Before probing into the microstructures of metallic glass with molecular dynamics (MD) simulation, it is important to obtain amorphous state first. In the current work, we reproduce the process of manufacturing metallic glass in laboratory including the melting, equilibrating and quenching procedure with molecular dynamics simulations. The structure changing at melting point and glass transition temperature are investigated with the different cooling processing. The partial radial distribution function (PRDF) is applied as a criterion to judge the final amorphous state obtained considering the quenching at different cooling rates and the effects of cooling rate on the formation of amorphous structures are further discussed.

Rapid composite tube manufacture utilizing the quickstep™ process

In this study, a novel method for manufacturing composite tubes utilizing the Quickstep^TM process has been developed. Tubes manufactured from `quick-cure' Toray G83C prepreg have demonstrated highly repeatable axial crush behavior with an average specific energy absorption (SEA) of 86 kJ/kg. The cure cycle is optimized by comparing the results from compression, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), and porosity testing. The tube lay-up is optimized using compression and porosity test results. The effect of changes in fiber-orientation on SEA is also investigated. Process development has resulted in a robust manufacturing method capable of producing fully cured, high performance composite tubes with a cure cycle of 7 min. This corresponds to a 95% reduction in time compared to an equivalent autoclave cycle.

Miscibility, crystallization κinetics and real-time small-Angle x-ray scattering investigation of the semicrystalline morphology in thermosetting polymer blends of epoxy resin and poly(ethylene oxide)

Thermosetting polymer blends of poly(ethylene oxide) (PEO) and bisphenol-A-type epoxy resin (ER) were prepared using 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) as curing agent. The miscibility and crystallization behavior of MCDEA-cured ER/PEO blends were investigated by differential scanning calorimetry (DSC). The existence of a single composition-dependent glass transition temperature (Tg) indicates that PEO is completely miscible with MCDEA-cured ER in the melt and in the amorphous state over the entire composition range. Fourier-transform infrared (FTIR) investigations indicated hydrogen-bonding interaction between the hydroxyl groups of MCDEA-cured ER and the ether oxygens of PEO in the blends, which is an important driving force for the miscibility of the blends. The average strength of the hydrogen bond in the cured ER/PEO blends is higher than in the pure MCDEA-cured ER. Crystallization kinetics of PEO from the melt is strongly influenced by the blend composition and the crystallization temperature. At high conversion, the time dependence of the relative degree of crystallinity deviated from the Avrami equation. The addition of a non-crystallizable ER component into PEO causes a depression of both the overall crystallization rate and the melting temperature. The surface free energy of folding σe displays a minimum with variation of composition. The spherulitic morphology of PEO in the ER/PEO blends exhibits typical characteristics of miscible crystalline/amorphous blends, and the PEO spherulites in the blends are always completely volume-filling. Real-time small-angle X-ray scattering (SAXS) experiments reveal that the long period L increases drastically with increasing ER content at the same temperatures. The amorphous cured ER component segregates interlamellarly during the crystallization process of PEO because of the low chain mobility of the cured ER. A model describing the semicrystalline morphology of MCDEA-cured ER/PEO blends is proposed based on the SAXS results. The semicrystalline morphology is a stack of crystalline lamellae; the amorphous fraction of PEO, the branched ER chains and imperfect ER network are located between PEO lamellae.

Dymanic mechanical analysis of polyvinylalcohol/silica nanocomposite

Polyvinylalcohol/Silica (PVA/SiO₂) nanocomposites with different SiO₂ contents are synthesized by employing a novel self-assembly monolayer (SAM) technique. The influence of the silica on dynamic mechanical properties of the nanocomposites is investigated by conducting dynamic mechanical analysis (DMA) and quasi-thermal mechanical analysis (Q-TMA). It is found that the storage modulus (E′), loss factor (tga), glass transition temperature (T_g), and activation energy (E_a) of prepared nanocomposites all show a strong dependence on the SiO₂ content. The Q-TMA results indicate that under a constant force, the elasticity of nanocomposites decreases with SiO₂ content, and the softening temperature moves to a higher temperature when more SiO₂ is added.

Characterization of melded carbon fibre/epoxy laminates

‘Melding’ is a novel in situ method for joining thermosetting composite structures, without the need of adhesives. Laminate joining is achieved using uncrosslinked resin matrix of the pre-preg. This study used Hexply914C pre-preg material to characterize melded CFRP structures produced using the melding method. A designated area of a laminate was maintained at temperatures below 40 °C retaining uncured (B-staged) material, while the remainder of the laminate was cured at 175 °C. After a 2.5 h cure cycle, the cured region showed a high degree of cure (0.88) and glass transition temperature (176 °C). The uncured area of the same laminate was cured in a second stage, simulating an in situ melded joint. By controlling the temperature and duration of the intermediate dwell and affecting minimum viscosity values prior to final cure, low values of porosity (<0.5%) were achieved. The mechanical properties of the resulting joint were consistent throughout the melded laminate. Flexural strength (1600 MPa), flexural modulus (100–105 MPa) and short beam strength (105–115 MPa) values observed where equivalent or greater than those found in the recommended autoclave cured control specimens. After the entire laminate was post cured, glass transition temperatures of 230 °C (peak tan δ) were observed in all areas of the laminate.

Manufacturing process effects on the mode I interlaminar fracture toughness and nanocreep properties of CFRP

Quickstep ™ is a fluid filled floating mould technology which was recently developed by an Australian company of the same name. The Quickstep and conventional autoclave manufacture of composites were compared by investigating the mode I interlaminar fracture toughness and nanocreep propeties of HexPly914 carbon epoxy composites. It was found that composites cured using the Quickstep technology had significantly higher fracture toughness (1.8 times) than the composites cured via autoclave for this system. DMTA (dynamic mechanical thermal analysis) results showed a higher Tg (glass transition temperature) for the material manufactured by the Quickstep than that cured by the autoclave. FTIR (Fourier transform infrared spectroscopy) spectra did not indicate any difference in cure chemistry between the two processes. Nanocreep experiments were performed to explore the viscoelastic properties of the epoxy matrix of composites. The KelvinVoigt three-element model was applied to analyse the indentation creep behaviour of both composites.

Photodarkening of amorphous selenium under high pressure

The photodarkening phenomena of amorphous Se have been studied by the optical absorption coefficient, sound velocity and attenuation measurements. The light illumination at low temperatures induces the photodarkening, and the photodarkened state is completely recovered by annealing near 306 K corresponding to the glass transition temperature. The photodarkening is enhanced by application of pressure. The sound velocity decreases and the sound attenuation increases by the illumination at low temperature. These suggest that a structural disorder increases in the photodarkened state. Three stages are observed for the recovery process of the photodarkened specimen. The photodarkening and the recovery process are discussed on the basis of VAP (valence alternative pair) model.

Quickstep

Quickstep✹ is a novel technology for composite materials manufacturing. Characterisation of carbon fibre reinforced polymer composites cured both conventionally and with the low cost Quickstep process revealed a higher glass transition temperature, enhanced fracture toughness and better impact resistance for the Quickstep composite laminates.

Fracture behaviour of a rapidly cured polyethersulfone toughened carbon fibre/epoxy composite

An out-of-autoclave rapid heating/low pressure technique has been used to cure polyethersulfone (PES) toughened HexPly 8552. Mode I and mode II tests were conducted to evaluate the fracture toughness of the composites and the effectiveness of cure was determined through thermal analysis. When compared to the autoclave process, the out-of-autoclave process resulted in a 52% reduction in processing time, without any sacrifice to the matrix intrinsic properties. Thermal analysis indicated an 8 °C improvement in glass transition temperature (T_g) as a result of an increased degree of cure. The out-of-autoclave process did lack in the ability to facilitate the removal of porosity which affected the fracture toughness results. The porosity is believed to have increased the mode I propagation fracture toughness. However its effect on mode II was quite deleterious, shown by scanning electron microscopy (SEM). This study managed to identify a number of key parameters associated with the out-of-autoclave process essential for further optimisation.

The effect of solvent uptake on the relaxation behaviour, morphology and mechanical properties of a poly(ether ether ketone)/poly(etherimide) blend

The effects of solvent uptake on the relaxation behaviour, morphology and mechanical properties of poly(ether ether ketone) (PEEK), poly(etherimide) (PEI) and a 50/50 PEEK/PEI blend have been investigated. Amorphous films were immersed in acetone at 25°C, 35°C and 45°C until equilibrium uptake was achieved. The films were then examined by wide angle X-ray scattering (WAXS), differential scanning calorimetry (d.s.c.), dynamic mechanical relaxation spectroscopy and mechanical testing. WAXS and d.s.c. revealed that the degree of solvent induced crystallinity in PEEK is constant with immersion temperature, whereas the degree of induced crystallinity in the 50/50 blend is strongly temperature dependent. The dynamic mechanical studies confirmed that a significant decrease in glass transition temperature results from the plasticizing effect of the solvent and that solvent and thermally crystallized samples have different relaxation characteristics. Mechanical property tests showed that the yield stress and tensile strength of the blend are dominated by PEEK and the degree of crystallinity, while the modulus is more sensitive to the extent of plasticization.