Addition Of Triblock Copolymer Research Articles

Mechanical and viscoelastic properties of novel resin-infused thermoplastic tri-block copolymer 3D glass fabric composites

The current study investigates the mechanical and viscoelastic properties of a novel acrylic resin-infused thermoplastic (Elium®) tri-block copolymer (Nanostrength®) 3D fibre-reinforced composites (FRCs). The toughened thermoplastic resins with three different concentrations of tri-block copolymer, i.e., 10 wt%, 15 wt%, and 20 wt%, were prepared and used to fabricate thermoplastic 3D-FRCs using a vacuum-assisted resin-infusion process at room temperature. The flexural, interlaminar, and viscoelastic properties and failure modes were evaluated and compared with those of pristine thermoplastic 3D-FRCs. The addition of tri-block copolymer significantly improves the flexural strength of 3D-FRC (up to 75 % and 34 % along the warp and fill directions, respectively, at 15 wt% of tri-block copolymer) and interlaminar shear strength (up to 80 % and 111 % along the warp and fill directions, respectively, at 20 wt% of tri-block copolymer). Additionally, the residual flexure and interlaminar shear strength improved up to 35 % and 109 % at 15 wt% of tri-block copolymer. Dynamic mechanical analysis (DMA) demonstrated that the glass transition temperature and storage modulus of thermoplastic 3D-FRCs were increased up to 11 °C and 24 %, respectively at 20 wt% of tri-block copolymer, which may be due to increased physical crosslinking and the agglomeration of tri-block copolymer particles. The improved mechanical and viscoelastic properties of resin-infused thermoplastic tri-block copolymer 3D-FRCs are attributed to better interface adhesion, improved matrix toughness, and crack-bridging mechanisms induced by the tri-block copolymer. The toughened thermoplastic 3D-FRCs can be utilized in the design and development of composite structures for improved damage tolerance applications.

Cover Image, Volume 138, Issue 34

Surface engineered self-cleaning property has captured wide attention in scientific, as well as industrial arenas recently. Better protection from environmental pollutants and dirt that might adversely affect its performance is a key requirement for coatings that offer self-cleaning. The cover designed by Unnikrishnan N V and colleagues shows the development of self-cleaning microsphere coatings with a prolonged lifetime using an sol-gel assisted electro-spraying approach. In addition, high quality selfcleaning surfaces are generated by altering the type of polymers used. And modulating surfaces by addition of tri-block co-polymer is found to provide swapping of superhydrophobic nature to superhydrophilic nature. Better antibacterial and photocatalytic properties are shown by the samples. DOI: 10.1002/app.50880

Morphological Evolution of Strongly Fluorescent Water Soluble AIEEgen-Triblock Copolymer Mixed Aggregates with Shape-Dependent Cell Permeability.

Dimethyl-2,5-bis(4-methoxyphenylamino)terephthalate (DBMPT) is a water-insoluble fluorogenic molecule, which has been rendered water-soluble in physiological conditions, by the addition of triblock copolymers (TBPs), P123 (PEO19PPO69PEO19), and F127 (PEO100PPO65PEO100). DBMPT-TBP mixed aggregates, formed in the process, exhibit significant aggregation-induced enhancement of emission, with nanosecond fluorescence lifetimes. Dynamics involved in suppression of nonradiative pathways and consequent enhancement of fluorescence are followed by femtosecond transient absorption and time-resolved fluorescence spectroscopic techniques. Interestingly, shapes of the aggregates formed with the two TBPs are found to be very different, even though they differ only in the length of hydrophilic blocks. DBMPT-P123 aggregates are micrometer-sized and spherical, while DBMPT-F127 aggregates form nanorods. Evolution of their morphologies, as a function of TBP concentration, is monitored using cryo-TEM, FESEM, and fluorescence lifetime imaging microscopy. Fluorescence lifetime distribution provides useful insight into microheterogeneity in these mixed aggregates. Excellent cell permeability is observed for DBMPT-F127 nanorods, in contrast to DBMPT-P123 microspheres. These fluorescent nanorods exhibit the ability to mark lipid droplets within the cell and hence bear the promise for application in intracellular imaging.

Thermally mendable and improved hydrophilic bioepoxy/PEG-PPG-PEG blends for coating application

Self-healing bio-based epoxy blends of poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol), (PEG-PPG-PEG) triblock copolymer (TBCP) was prepared and investigated, with the goal of developing smart self-healing coatings that can protect metal surface from corrosion. The epoxy blends consist of low molecular weight triblock copolymer (L61) blended in different weight percentage (5, 10, 20, 30, 40 and 50 wt%) were prepared. A room temperature curing agent was selected and the thermal mending of bioepoxy coatings are investigated. At an elevated temperature (ca.140 °C–150 °C), the TBCP phase undergoes mending and migrate to the crack site, forming a thin layer of protective coating on the substrate (carbon steel). The system was transparent up to 5 wt% TBCP content and are opaque above 10 wt% TBCP concentrations. The contact angle reduced considerably from 72.5° to 25.5° due to the hydrophilic nature of TBCP. The thermal stability was increased, while the mechanical properties were decreased by the addition of TBCP.

Micro phase separated epoxy/poly(ε-caprolactone)-block-poly(dimethyl siloxane)-block-poly(ε-caprolactone)/4,4′-diaminodiphenylsulfone systems: Morphology, viscoelasticity, thermo-mechanical properties and surface hydrophobicity

Epoxy resin/4,4′-diaminodiphenylsulfone (DDS) system was modified by the incorporation of poly(ε-caprolactone)-block-poly(dimethyl siloxane)-block-poly(ε-caprolactone) (PCL–PDMS–PCL) triblock copolymer (TBCP). Morphology, viscoelasticity, thermo-mechanical and surface properties of these blends were investigated. All the blends were opaque after curing. PCL blocks of the TBCP were miscible with epoxy resin while the PDMS fraction was immiscible. However in the cured state, both PCL and PDMS blocks were phase separated from epoxy/DDS matrix. The blends exhibited matrix-droplet morphology in which TBCP phase dispersed as spherical domains in epoxy matrix. Addition of TBCP had profound impact on the cure reaction kinetics. Storage modulus and glass transition temperature (Tg) decreased while impact strength significantly increased. Incorporation of 15 phr of TBCP resulted in 80% improvement in impact strength. Further, thermal stability was unaffected while surface hydrophobicity of the blends increased.

Synthesis of mesoporous TiO2 spheres and aggregates by sol–gel method for dye-sensitized solar cells

Mesoporous microspheres of anatase TiO2 were synthesized by hydrolysis of titanium butoxide in butanol. The TiO2 micospheres were about 0.5μm in size, composed of primary nanoparticles of about 10nm, and the specific surface area increased by addition of triblock copolymer (Pluronic F127). TiO2 aggregates with irregular shape were formed by hydrothermal treatment. Before and after calcination, the crystallinity of TiO2 aggregates was high although the specific surface area decreased. The cell efficiency of TiO2 sphere electrode increased by F127 addition. Furthermore, TiO2 aggregate electrode exhibited an efficiency of 5.6%, which was much higher than those of TiO2 spheres with F127 and commercial TiO2 nanoparticles (P25) electrodes. It was confirmed that the high crystallinity of TiO2 was important to improve the photovoltaic properties as well as large surface area.

Multi-scale reinforcement of CFRPs using carbon nanofibers

In this paper, stacked-cup carbon nanofibers (CNF) were dispersed in the matrix phase of carbon-fiber-reinforced composites based on a high-performance epoxy system with and without modification by an elastomeric triblock copolymer (TCP) for increased toughness. The addition of the TCP provided an enhancement in toughness at the cost of a slight degradation in modulus and strength. The CNFs, on the other hand, provided significantly enhanced strength and stiffness in matrix-dominated configurations, including tension of quasi-isotropic composites and short beam shear strength of both quasi-isotropic and unidirectional composites. Scanning electron microscopy revealed enhanced adhesion between the matrix and carbon fibers with the addition of either TCP or CNFs. However, CNF agglomeration in the studied systems partially offset the energy dissipation processes brought about by the nanofibers, thereby limiting interlaminar fracture toughness enhancements by CNF addition. These results show good promise for CNFs as low-cost reinforcement for composites while offering insight into the codependent morphologies of multi-scale phases and their influence over bulk properties.

Interactions of Hydrophobically Modified Polyvinylamine with Pluronic Triblock Copolymer Micelles

The heats associated with the addition of triblock copolymers of ethylene oxide and propylene oxide (PEO-PPO-PEO pluronics) to solutions of linear polyvinylamine, with N-substituted pendant octyl groups (HMPVAm), were measured as functions of pH and pluronic structure. The interactions were exothermic with the overall enthalpy decreasing with increasing pH from 5 to 10. Surprisingly, the heat effect increased with increasing pluronic hydrophilicity; however, no enthalpy change was observed in the absence of micelles. The results were quantitatively modeled by assuming two competing processes-micellar dissolution and HMPVAm coating of micelles, preventing dissolution.

Photocatalytic Properties of Mesoporous TiO<sub>2</sub> Films Derived from Evaporation-Induced Self-Assembly Method

Hexagonal and cubic mesoporous TiO2 films were prepared by using triblock copolymer-templated sol-gel method via evaporation-induced self-assembly (EISA) process. The mesophase of TiO2 film was controlled by spin-speed during the spin-coating process. The hexagonal mesoporous structure was formed at a high spin-speed around 2000 rpm, whereas the cubic mesostructure was formed at a low spin-speed around 600 rpm. XRD and TEM results indicate that those mesostructures are highly organized with a pore diameter of 7 nm. The prepared cubic and hexagonal mesoporous films were tested as photocatalysts for the decomposition of 2-propanol in gas phase. Both films presented considerably higher photocatalytic activity than a nonporous TiO2 films prepared by a typical sol-gel process without addition of triblock copolymer. Notably, we found that the cubic mesoporous films showed a relatively higher photocatalytic activity than the hexagonal mesostructured film. We believe this is due to the orientation of pore channels open on the surface of mesoporous films.

Compatibilising action of random and triblock copolymers of poly(styrene–butadiene) in polystyrene/polybutadiene blends: A study by electron microscopy, solid state NMR spectroscopy and mechanical measurements

Scanning electron microscopy, solid-state proton NMR spectroscopy and static mechanical analysis have been performed in order to evaluate the compatibilising action of random copolymers of polystyrene and polybutadiene and triblock copolymers of poly(styrene–butadiene–styrene) in incompatible polystyrene/polybutadiene (PS/PB) blends. Scanning electron microscopic examination of the cryofractured and etched surfaces showed high degree of compatibilising action of the triblock copolymers as evidenced by the very sharp decrease of the domain size of the dispersed phase followed by an increase at higher concentrations. This is a clear indication of interfacial saturation. These results were in agreement with the theoretical predictions of Noolandi and Hong. The random copolymer was not effective in compatibilising the system. Solid-state proton NMR experiments were performed on the uncompatibilised and compatibilised blends. The proton spin–lattice relaxation times in the laboratory frame, T 1( H), and in the rotating frame, T 1 ρ ( H), and spin–spin relaxation times, T 2( H), were carefully measured for the systems. Significant changes were observed for the systems compatibilised with triblock copolymers due to the preferential localisation of the copolymers at the PS/PB interface. However, the random copolymer did not have any compositional drift and is not an effective interface modifier in agreement with microscopy study. The static mechanical properties of the blends have also been analysed. The addition of triblock copolymers increased the mechanical properties of the blends. Finally, attempts have been made to correlate the NMR results with the microstructure and mechanical properties of the blends.

Fracture and yielding behaviors of polystyrene/ethylene‐propylene rubber blends: Effects of interfacial agents

AbstractThe aim of this work is to investigate the effects of two triblock copolymers, used as coupling agents, on fracture and yielding behaviors of a blend of 80 volume % of polystyrene (PS) and 20 volume %of ethylene‐propylene rubber (EPR), over a large range of loading rates and temperatures. For this purpose, blends containing different concentrations of two triiblock copolymers were studied at various test conditions. The focus was put on the time‐temperature dependence of fracture performance of the blends. Addition of triblock copolymer makes the PS/EPR blend more ductile. The time‐temperature dependence of the brittle‐ductile transition in fracture performance of the blend is controlled by an energy activation process. The interfacial agent lowers the temperature at brittle‐ductile transition and reduces the energy barrier controlling the fracture process. This effect, however, is much more pronounced for the lower molecular weight interfacial agent. The correlation between temperature, loading rate and yield stress of the blends seems to be controlled by a molecular relaxation process according to the Ree‐Eyring theory. This model, based on the assumption of two relaxation processes (α and β) acting in parallel, allows prediction of yield stress at various loading rates and temperatures. Addition of the interfacial agents results in a reduction of the activation energy and an increase in the activation volume V* for both the α and β processes. Furthermore, the similarity of the value of the activation energy ΔHβ in the β yielding process and the energy barrier ΔH controlling the brittle‐ductile transition in fracture seems to suggest that a similar secondary relaxation mechanism controls the yielding and the fracture behavior of the blend.