Toughening epoxy thermosets with block ionomers : the role of phase domain size

Herein we report a novel approach to toughen epoxy thermosets using a block ionomer, i.e., sulfonated polystyrene-block-poly(ethylene-co-butylene)-block- polystyrene (SSEBS). SSEBS was synthesized by sulfonation of SEBS with 67 wt % polystyrene (PS). Phase morphology of the epoxy/SSEBS blends can be controlled at either nanometer or micrometer scale by simply adjusting the sulfonation degree of SSEBS. It has been found that there exists a critical degree of sulfonation (10.8 mol %) forming nanostructures in these epoxy/SSEBS blends. Above this critical value, macrophase separation can be avoided and only microphase separation occurs, yielding transparent nanostructured blends. All epoxy/SSEBS blends display increased fracture toughness compared to neat epoxy. But the toughening efficiency varies with the phase domain size, and their correlation has been established over a broad range of length scales from nanometers to a few micrometers. In the nanostructured blends with SSEBS of high sulfonation degrees, the fracture toughness decreases with decreasing size of the phase domains. In the macrophase-separated blends, only a slight improvement in toughness can be obtained with SSEBS of low sulfonation degrees. The epoxy blend with submicrometer phase domains in the range 0.05-1.0 μm containing SSEBS of a moderate degree of sulfonation (5.8 mol %) displays the maximum toughness. This study has clearly clarified the role of phase domain size on toughening efficiency in epoxy thermosets.

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.

Electrospun single-walled carbon nanotube/polyvinyl alcohol composite nanofibers : structure-property relationships

Polyvinyl alcohol (PVA) nanofibers and single-walled carbon nanotube (SWNT)/PVA composite nanofibers have been produced by electrospinning. An apparent increase in the PVA crystallinity with a concomitant change in its main crystalline phase and a reduction in the crystalline domain size were observed in the SWNT/PVA composite nanofibers, indicating the occurrence of a SWNT-induced nucleation crystallization of the PVA phase. Both the pure PVA and SWNT/PVA composite nanofibers were subjected to the following post-electrospinning treatments: (i) soaking in methanol to increase the PVA crystallinity, and (ii) cross-linking with glutaric dialdehyde to control the PVA morphology. Effects of the PVA morphology on the tensile properties of the resultant electrospun nanofibers were examined. Dynamic mechanical thermal analyses of both pure PVA and SWNT/PVA composite electrospun nanofibers indicated that SWNT–polymer interaction facilitated the formation of crystalline domains, which can be further enhanced by soaking the nanofiber in methanol and/or cross-linking the polymer with glutaric dialdehyde.

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.

Study on thermoplastic-modified multifunctional epoxies : influence of heating rate on cure behaviour and phase separation

The effect of heating rate on the cure behaviour and phase separation of thermoplastic-modified epoxy systems was investigated. Polyethersulphone (PES) modified multifunctional epoxies, triglycidyl-aminophenol (TGAP) and tetraglycidyldiaminodiphenylmethane (TGDDM), as well T300/914 prepreg were used. It was shown that heating rate had a significant influence on the cure kinetics and phase structures of investigated systems. Greater heating rate causes higher epoxy conversion. The domain size of the macrophases formed from phase separation increases with the increase of heating rate. A more complete phase separation is achieved by fast heated thermoplastic-modified epoxy blends.

In situ synchrotron SAXS study of polymerizable microemulsions

We present for the first time a real-time small-angle X-ray scattering (SAXS) study of the structural transition of fluid microemulsion to solid polymerized material in a silicone polymerizable microemulsion system. A reactive methacrylate-terminated siloxane macromonomer (MTSM, Mn ∼ 1000 g/mol) was synthesized and used for microemulsion formulations comprising MTSM (oil phase), water, and a mixture of nonionic surfactant (Teric G9A8) with isopropanol. In situ synchrotron SAXS was used to investigate time-dependent nanostructure evolution during the polymerization reaction, which was directly initiated by X-ray radiation. The SAXS data were analyzed using both the Teubner-Strey model and the core-shell model. The results obtained by the Teubner-Strey model showed that the domain size (d) decreased while the correlation length (ξ) increased upon polymerization. The analysis in terms of the core-shell model displayed that adding water to the precursor microemulsion caused the water droplets to start swelling, which resulted in the discontinuity of water in oil microemulsion. There exhibited large differences in morphologies of polymerized materials from the microemulsion formulations with different water and surfactant contents. The core and shell sizes of water droplets decreased during the course of polymerization when there was 15 wt % or more water in the microemulsion formulation; the polymerized material thus exhibited increasingly discrete granular morphology. When there was 10 wt % or less water content in the precursor microemulsion, the rearrangement of water domains could be minimized during the course of polymerization and transparent polymerized material was obtained.

Structure and thickness optimization of active layer in nanoscale organic solar cells

 This paper presents the development of a two-dimensional model of multilayer bulk heterojunction organic nanoscale solar cells, consisting of the thickness of active layer and morphology of the device. The proposed model is utilized to optimize the device parameters in order to achieve the best performance using particle swarm optimization algorithm. The organic solar cells under research are from poly (3-hexylthiophene) and [6,6]-phenyl C61-butyric acid methyl ester type which are modelled to be investigated for performance enhancement. A three-dimensional fitness function is proposed involving domain size and active layer thickness as variables. The best results out of 20 runs of optimization show that the optimized value for domain size is 17 nm, while the short-circuit current vs. voltage characteristic shows a very good agreement with the experimental results obtained by previous researchers. © 2014 Springer Science+Business Media New York

Duolayers at the air/water interface: improved lifetime through ionic interactions

Ionic interactions to stabilize Langmuir films at the air/water interface have been used to develop improved duolayer films. Two-component mixtures of octadecanoic (stearic) acid and poly(diallyldimethylammonium chloride) (polyDADMAC) with different ratios were prepared and applied to the water surface. Surface pressure isotherm cycles demonstrated a significant improvement in film stability with the inclusion of the polymer. Viscoelastic properties were measured using canal viscometry and oscillating barriers, with both methods showing that the optimum ratio for improved properties was four octadecanoic acid molecules to one DADMAC unit (1:0.25). At this ratio it is expected multiple strong ionic interactions are formed along each polymer chain. Brewster angle microscopy showed decreased domain size with increased ratios of polyDADMAC, indicating that the polymer is interspersed across the surface. This new method to stabilize and increase the viscoelastic properties of charged monolayer films, using a premixed composition, will have application in areas such as water evaporation mitigation, optical devices, and foaming.

Intersectoral size differences and migration: Kuznets revisited

The empirical evidence on the Kuznets hypothesis ranges from positive or negative support to insignificant relationships. Most studies typically try this hypothesis in domains different than the one conceived by Kuznets, which pertains to the industrialization-led urbanization (i.e., significant rural-urban migration) phase of societies. In this paper, we offer a specific channel on Kuznets' hypothesis in his suggested domain. First, we establish theoretically that intersectoral urban-rural size differences result in an intersectoral income inequality, increasing the national inequality. This, in turn, prompts an intersectoral migration, which works as an equilibriating mechanism in the economy, decreasing the inequality in due course. We then successfully test the predictions of the model. The theoretical predictions yield a recursive triangular system, in which we test, i) how the sectoral size differences influence the agricultural income, ii) how a change in agricultural income acts on migration, and iii) what happens to the income distribution as a result of migration. We find a very strong support for the theoretical predictions and the Kuznets hypothesis in its own domain.

Ligand-enhanced expression and in-cell assay of human peroxisome proliferator-activated receptor alpha ligand binding domain

A human peroxisome proliferator-activated receptor alpha ligand binding domain (PPARαLBD)-maltose binding protein fusion construct was expressed in Escherichia coli. A codon optimized DNA sequence encoding human PPARαLBD (aa196–468) was synthesized and ligated into the pDEST17 E. coli expression vector downstream of a MBP solubility fusion tag and an intermittent TEV protease cleavage site. Following auto-induction at 28 °C, PPARαLBD protein was purified to electrophoretic homogeneity by a nickel affinity chromatographic step, on-column TEV protease cleavage followed by Sephacryl S200 size exclusion chromatography. The recombinant protein displayed cross-reactivity with goat anti-(human PPARα) polyclonal antibody and was identified as human PPARα by trypic peptide mass finger-printing. The addition of a PPARα specific ligand (fenofibric acid, GW7647 or GW590735) to the growth media significantly stabilized the PPARαLBD structure and enhanced the expression of soluble protein. In-cell ligand binding was examined by monitoring the enhancement of PPARαLBD expression as a function of the concentration of ligand in the growth media. The efficient expression and in-cell assay of the reported PPARαLBD construct make it amenable to high through-put screening assays in drug discovery programs.