Investigation of the postcure reaction and surface energy of epoxy resins using time-of-flight secondary ion mass spectrometry and contact-angle measurements

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to investigate correlations between the molecular changes and postcuring reaction on the surface of a diglycidyl ether of bisphenol A and diglycidylether of bisphenol F based epoxy resin cured with two different amine-based hardeners. The aim of this work was to present a proof of concept that ToF-SIMS has the ability to provide information regarding the reaction steps, path, and mechanism for organic reactions in general and for epoxy resin curing and postcuring reactions in particular. Contact-angle measurements were taken for the cured and postcured epoxy resins to correlate changes in the surface energy with the molecular structure of the surface. Principal components analysis (PCA) of the ToFSIMS positive spectra explained the variance in the molecular information, which was related to the resin curing and postcuring reactions with different hardeners and to the surface energy values. The first principal component captured information related to the chemical phenomena of the curing reaction path, branching, and network density based on changes in the relative ion density of the aliphatic hydrocarbon and the C₇H₇O⁺ positive ions. The second principal component captured information related to the difference in the surface energy, which was correlated to the difference in the relative intensity of the C_xH_yN_z⁺ ions of the samples. PCA of the negative spectra provided insight into the extent of consumption of the hardener molecules in the curing and postcuring reactions of both systems based on the relative ion intensity of the nitrogen-containing negative ions and showed molecular correlations with the sample surface energy.

Investigation of failure mechanisms in aged aerospace composites

The effect of isothermal ageing on two high temperature, bismaleimide composite materials, a novel CSIRO CBR 320/328 composite and a commercial CIBA GEIGY Matrimid® 5292 composite, was examined at 204 and 250 °C. Delamination is a major cause of failure in composite materials, therefore, the Mode I interlaminar fracture toughness (GIC) of both materials was measured using the double cantilever beam (DCB) test. Chemical degradation of the matrix was monitored concurrently using Fourier transform infrared (FTIR) and Raman spectroscopy. Chemical changes at the core of both of these materials were found to occur concomitantly with the observed changes in interlaminar fracture toughness. FTIR analysis of both matrix materials revealed the predominant degradation mechanism to be the oxidation of the methylene group bridging two aromatic rings common to the structure of both resins, and was substantiated by the ingrowth of a broad peak centred at 1600 cm⁻¹ . In addition to this, the pyromellitic anhydride unit present only in the CBR 320/328 composites was found to be highly resistant to the effects of ageing, whereas the saturated imide, common to the cured structures of both materials, was observed to degrade. Raman spectroscopy indicated that the predominant degradation mechanism of the composites differed at the two ageing temperatures.

固化条件对热塑增韧环氧树脂的固化动力学和相分离的影响

Thermoplastic toughened epoxy resins are widely used as matrices in modern prepreg systems.Different curing conditions play a great role in affecting the cure kinetics and phase behaviour of thermoplastic modified epoxies which further result in different mechanical properties of polymer matrix composites.Since the morphology of the cured thermoplastic/epoxy blends is directly related to the mechanical properties,it is essential to control processing conditions for obtaining desirable morphology.A polyethersulphone (PES) modified multifunctional epoxies,triglycidylaminophenol (TGAP) and tetraglycidyldiaminodiphenylmethane (TGDDM),was used for investigation.The cure kinetics and cured morphology of polymer blends heated at different heating rates and cured at different temperature were studied.It is shown that higher cure temperature and higher heating rate display similar effects in the epoxy conversion and the domain size of phase separated structure.

Structural and material properties of a rapidly cured thermoplastic-toughened epoxy system

Thermoplastic-toughened epoxy resins are widely used as matrices in modern composite prepreg systems. Rapid curing of thermoplastic-toughened epoxy matrix composites results in different mechanical properties. To investigate the structure–property relationship, we investigated a poly(ether sulfone)-modified triglycidylaminophenol/ 4,4'-diamino diphenyl sulfone system that was cured at different heating rates. An intermediate dwell was also applied during the rapid heating of the thermoplasticmodified epoxy system. We found that a higher heating rate led to a larger domain size of the phase-separated macrostructure and also facilitated more complete phase separation. The intermediate dwell helped phase separation to proceed even further, leading to an even larger domain size of the macrostructure. A carbon-fiber-reinforced polymer matrix composite prepreg based on the poly(ether sulfone)-modified multifunctional epoxy system was cured with the same schedule. The rapidly heated composite laminates exhibited higher mode I delamination fracture toughness than the slowly heated material.

Adhesion of polymers

Most industrially applied polymer resins and composites have low surface free energy and lack polar functional groups on their surface, resulting in inherently poor adhesion properties. A strong research momentum to understand polymer adhesion in the last decade has been motivated by the growing needs of the automotive and aerospace industries for better adhesion of components and surface coatings. This paper reviews the recent research efforts on polymer adhesion with a special focus on adhesion mechanisms. It starts with an introduction to adhesion with explanatory notes on adhesion phenomena. Recent research on the adhesion mechanisms of mechanical coupling, chemical bonding and thermodynamic adhesion is then discussed. The area of adhesion promoters is reviewed with the focus on plasma and chemical treatments, along with direct methods for adhesion measurement. The topics of polymer blends and reactive polymerization are considered and the interactions with adhesion mechanisms are reported. The concluding section provides recommendations regarding future research on the contentious aspects of currently accepted adhesion mechanisms and on strategies for enhancing polymer adhesion strength.

Structure and properties of epoxy nanocomposites

This study investigated the structure-property relationships of epoxy nanocomposites when processing the materials under various conditions. A sonication technique, rapid heating rate and mechanical vibration during curing facilitated the dispersion of nanoclay in an epoxy resin. This led to the successful manufacture of fibre reinforced nanocomposites.

An investigation into transition metal ion binding properties of silk fibers and particles using radioisotopes

Silk is a structural protein fiber that is stable over a wide pH range making it attractive for use in medical and environmental applications. Variation in amino acid composition has the potential for selective binding for ions under varying conditions. Here we report on the metal ion separation potential of Mulberry and Eri silk fibers and powders over a range of pH. Highly sensitive radiotracer probes, ⁶⁴Cu²⁺, ¹⁰⁹Cd²⁺, and ⁵⁷Co²⁺ were used to study the absorption of their respective stable metal ions Cu²⁺, Cd²⁺, and Co²⁺ into and from the silk sorbents. The total amount of each metal ion absorbed and time taken to reach equilibrium occurred in the following order: Cu²⁺ > Cd²⁺ > Co ²⁺. In all cases the silk powders absorbed metal ions faster than their respective silk fibers. Intensive degumming of the fibers and powders significantly reduced the time to absorb respective metal ions and the time to reach equilibrium was reduced from hours to 5-15 min at pH 8. Once bound, 45-100% of the metal ions were released from the sorbents after exposure to pH 3 buffer for 30 min. The transition metal ion loading capacity for the silk sorbents was considerably higher than that found for commercial ion exchange resins (AG MP-50 and AG 50W-X2) under similar conditions. Interestingly, total Cu²⁺ bound was found to be higher than theoretically predicted values based on known specific Cu²⁺ binding sites (AHGGYSGY), suggesting that additional (new) sites for transition metal ion binding sites are present in silk fibers.

Characterisation of an out-of-autoclave resin film infusion process for textile composites

A new method to manufacture damage tolerant textile composites, which combines Resin Film Infusion with a fast and cost·efficient curing technology QuickstepTM, was investigated. The effect of process parameters on resin flow through carbon fibre preforms was analysed and model-based parameter optimisation resulted in considerable improvement of resin flow properties.

Rapid water quality characterization for chlorine demand and THM formation in drinking waters

The quality of drinking water generally deteriorates when it is delivered through a distribution system due to the decay of disinfectant, which subsequently allows the re-growth of microorganisms in the distribution system in addition to the formation of trihalomethane (THM). Therefore, a model which describes the changes that occur in the water quality in the distribution system is needed to determine whether to enhance the treatment processes or to improve the distribution system so that microbiological criteria are met. In this paper the chlorine decay kinetics and THM formation in treated water is modeled considering the reaction of chlorine with fast and slow reacting organic and nitrogenous compounds which are present in that water. The treated water was also passed through three types of resins to fractionate very hydrophobic acids (VHA), slightly hydrophobic acids (SHA), hydrophilic charged (CHA) and hydrophilic neutral (NEU) compounds which are present in the water. Chlorine decay tests were conducted on the effluents emerging from the resins to evaluate the chlorine demand and THM formation potential of those organic fractions. The model shows that the CHA presented in the waters has a very high THM formation potential (around 62% of the THM produced). VHA, NEU and CHA contributed to chlorine demand in the water.

Electrospinning of nanofibres with parallel line surface texture for improvement of nerve cell growth

Nanofibres having a parallel line surface texture were electrospun from cellulose acetate butyrate solutions using a solvent mixture of acetone and N,N'-dimethylacetamide. The formation mechanism of the unusual surface feature was explored and attributed to the formation of voids on the jet surface at the early stage of electrospinning and subsequent elongation and solidification of the voids into a line surface structure. The fast evaporation of a highly volatile solvent, acetone, from the polymer solution was found to play a key role in the formation of surface voids, while the high viscosity of the residual solution after the solvent evaporation ensured the line surface to be maintained after the solidification. Based on this principle, nanofibres having a similar surface texture were also electrospun successfully from other polymers, such as cellulose acetate, polyvinylidene fluoride, poly(methyl methacrylate), polystyrene and poly(vinylidene fluoride-co-hexafluoropropene), either from the same or from different solvent systems. Polarized Fourier transform infrared spectroscopy was used to measure the polymer molecular orientation within nanofibres. Schwann cells were grown on both aligned and randomly oriented nanofibre mats. The parallel line surface texture assisted in the growth of Schwann cells especially at the early stage of cell culture regardless of the fibre orientation. In contrast, the molecular orientation within nanofibres showed little impact on the cell growth.

On toughening of epoxies and their carbon fibre-reinforced composites

Compared to the neat matrix material, FRC has highly favorable mechanical properties, and their strength-to-weight ratios are superior. In addition, FRCs have potential for use in many applications in dentistry and are expected to gain increasing applications in the future. This book includes both review and research papers in different FRC areas from contributors around the world.

Qualitative spectroscopic characterization of the matrix-silane coupling agent interface across metal fibre reinforced ion exchange resin composite membranes

The characterization of novel metal reinforced electro-dialysis ion exchange membranes, for water desalination, by attenuated total reflectance Fourier transform infrared spectroscopy mapping is presented in this paper. The surface of the porous stainless steel fibre meshes was treated in order to enhance the amount of surface oxide groups and increase the material hydrophilicity. Then, the metal membranes were functionalized through a sol-gel reaction with silane coupling agents to enhance the affinity with the ion exchange resins and avoid premature metal oxidation due to redox reactions at the metal-polymer interface. Polished cross sections of the composite membranes embedded into an epoxy resin revealed interfaces between metallic frameworks and the silane layer at the interface with the ion exchange material. The morphology of the metal-polymer interface was investigated with scanning electron microscopy and Fourier transform infrared micro-spectroscopy. Fourier transform infrared mapping of the interfaces was performed using the attenuated total reflectance mode on the polished cross-sections at the Australian Synchrotron. The nature of the interface between the metal framework and the ion exchange resin was shown to be homogeneous and the coating thickness was found to be around 1 μm determined by Fourier transform infrared micro-spectroscopy mapping. The impact of the coating on the properties of the membranes and their potential for water desalination by electro-dialysis are also discussed.

Oil-spill cleanup: the influence of acetylated curaua fibers on the oil-removal capability of magnetic composites

A magnetic resin based on cardanol, furfural, and curaua fibers was prepared and characterized. The material could be used in oil-spill cleanup processes, because of its aromatic/aliphatic balance. The resin was prepared through bulk polycondensation of cardanol and furfural in the presence of curaua fibers and maghemite nanoparticles. Hydrophobicity of the curaua fibers was improved by acetylation, increasing the oil-absorbing capability of the composites. The obtained magnetic composites were studied by Fourier-transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. Degree of cure, magnetic force, and oil-removal capability tests were also performed. The results show that the composites possess an elevated cure degree in addition to a considerable magnetic force. The materials exhibit a good oil removal capability in the presence of a magnetic field, which is improved by the use of acetylated curaua. In the best case, the composite filled with maghemite and curaua can remove 12 parts of oil from water.

A novel approach to the functionalisation of pristine carbon fibre using azomethine 1,3-dipolar cycloaddition

We demonstrate the utilisation of an azomethine 1,3-dipolar cycloaddition reaction with carbon fibre to graft complex molecules onto the fibre surface. In an effort to enhance the interfacial interaction of the fibre to the matrix, the functionalised fibres possessed a pendant amine that is able to interact with epoxy resins. Functionalisation was supported by X-ray photoelectron spectroscopy and the grafting process had no detrimental effects on tensile strength compared with the control (untreated) fibres. Also, microscopic roughness (as determined by atomic force microscopy) and fibre topography were unchanged after the described treatment process. This methodology complements existing methodology aimed at enhancing the surface of carbon fibres for advanced material applications while not compromising the desirable strength profile. Single-fibre fragmentation tests show a statistically significant decrease in fragment length compared with the control fibres in addition to transverse cracking within the curing resin, both of which indicate an enhanced interaction between fibre and resin.