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We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-bethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of softtemplates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-bethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of softtemplates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-bethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of softtemplates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-bethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of softtemplates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

The thickness and scratch resistance of adsorbed films formed on mild steel samples (MS1020), which have been immersed in water copolymer solutions, are reported. The effects of bulk temperature and the copolymer structures, normal, poly(ethylene oxide)m-poly(propylene oxide)n-poly(ethylene oxide)m, and reverse, poly(propylene oxide)n-poly(ethylene oxide)m-poly(propylene oxide)n, are elucidated. The films' thicknesses are independent of structure but not of temperature. The adsorbed films of above cloud point solutions are thicker than below cloud point. However, nanoscratch experiments carried out to measure the scratch resistance of the films reveal that despite of thicker film formed by above cloud point solutions, it is relatively more prone to being detached than the thinner films of below cloud point solutions. The effect of extreme pressure additive, alkyl phosphate ester (APE), is also investigated suggesting the normal copolymer has comparable scratch resistance with APE when used at below the cloud point. Copyright 2016 John Wiley & Sons, Ltd.

The thickness and scratch resistance of adsorbed films formed on mild steel samples (MS1020), which have been immersed in water copolymer solutions, are reported. The effects of bulk temperature and the copolymer structures, normal, poly(ethylene oxide)m-poly(propylene oxide)n-poly(ethylene oxide)m, and reverse, poly(propylene oxide)n-poly(ethylene oxide)m-poly(propylene oxide)n, are elucidated. The films' thicknesses are independent of structure but not of temperature. The adsorbed films of above cloud point solutions are thicker than below cloud point. However, nanoscratch experiments carried out to measure the scratch resistance of the films reveal that despite of thicker film formed by above cloud point solutions, it is relatively more prone to being detached than the thinner films of below cloud point solutions. The effect of extreme pressure additive, alkyl phosphate ester (APE), is also investigated suggesting the normal copolymer has comparable scratch resistance with APE when used at below the cloud point. Copyright 2016 John Wiley & Sons, Ltd.

The thickness and scratch resistance of adsorbed films formed on mild steel samples (MS1020), which have been immersed in water copolymer solutions, are reported. The effects of bulk temperature and the copolymer structures, normal, poly(ethylene oxide)m-poly(propylene oxide)n-poly(ethylene oxide)m, and reverse, poly(propylene oxide)n-poly(ethylene oxide)m-poly(propylene oxide)n, are elucidated. The films' thicknesses are independent of structure but not of temperature. The adsorbed films of above cloud point solutions are thicker than below cloud point. However, nanoscratch experiments carried out to measure the scratch resistance of the films reveal that despite of thicker film formed by above cloud point solutions, it is relatively more prone to being detached than the thinner films of below cloud point solutions. The effect of extreme pressure additive, alkyl phosphate ester (APE), is also investigated suggesting the normal copolymer has comparable scratch resistance with APE when used at below the cloud point. Copyright 2016 John Wiley & Sons, Ltd.

The thickness and scratch resistance of adsorbed films formed on mild steel samples (MS1020), which have been immersed in water copolymer solutions, are reported. The effects of bulk temperature and the copolymer structures, normal, poly(ethylene oxide)m-poly(propylene oxide)n-poly(ethylene oxide)m, and reverse, poly(propylene oxide)n-poly(ethylene oxide)m-poly(propylene oxide)n, are elucidated. The films' thicknesses are independent of structure but not of temperature. The adsorbed films of above cloud point solutions are thicker than below cloud point. However, nanoscratch experiments carried out to measure the scratch resistance of the films reveal that despite of thicker film formed by above cloud point solutions, it is relatively more prone to being detached than the thinner films of below cloud point solutions. The effect of extreme pressure additive, alkyl phosphate ester (APE), is also investigated suggesting the normal copolymer has comparable scratch resistance with APE when used at below the cloud point. Copyright 2016 John Wiley & Sons, Ltd.

This paper investigates the adsorption behavior of triblock copolymer Poly (propylene oxide)-poly (ethylene oxide)-poly (propylene oxide), PPO-PEO-PPO on silicon and iron surfaces by using the contact angle goniometer, spectroscopic ellipsometer and atomic force microscopy (AFM). After adsorption, the decrease of water contact angle was observed on each surface; and a larger reduction of water contact angle occurred on the surface covered by the copolymer film with longer and higher weight percent of hydrophilic PEO block. This means that the PEO block may be on the top of the adsorbed copolymer film. The film thickness measurement shows that the copolymer with longer and higher weight percent of PPO block forms a thicker film on the hydrophobic surface, which suggests that the hydrophobic PPO block of the copolymer in the aqueous solution plays the main role during the adsorption of PPO-PEO-PPO onto the hydrophobic surface. It has been found from the AFM results that the roughness of the surface decreased after adsorption and the smoother topography was observed on the surface adsorbed by a thicker adsorbed film.

The fabrication of mesoporous core-shell and hollow spheres with ordered mesostructures and tunable large pore sizes is highly desirable for fundamental research and practical applications. A direct triblock-copolymer-templating coating approach has been provided for the synthesis of carbon sphere@mesoporous silica core-shell (CS@SBA-15) and hollow structures in an acidic medium at room temperature. These CS@SBA-15 core-shell structures possess large mesopores (6.3-8.4 nm), high surface areas (318.1-438.4 m2 g-1) and large pore volumes (0.31-0.36 cm3 g-1). The corresponding hollow mesoporous silica spheres (HMSS) with controllable mesopores (6.0-8.2 nm), high surface areas (239.9-326.5 m2 g-1) and pore volumes (0.37-0.62 cm3 g-1) can be obtained after the removal of the carbon sphere cores through calcination at 700 degrees C in air. The current research results provide an effective methodology for the synthesis of other mesoporous silica core-shell structures with large pore sizes and multilayer core-shells, and even nanorattle structures.

The fabrication of mesoporous core-shell and hollow spheres with ordered mesostructures and tunable large pore sizes is highly desirable for fundamental research and practical applications. A direct triblock-copolymer-templating coating approach has been provided for the synthesis of carbon sphere@mesoporous silica core-shell (CS@SBA-15) and hollow structures in an acidic medium at room temperature. These CS@SBA-15 core-shell structures possess large mesopores (6.3-8.4 nm), high surface areas (318.1-438.4 m2 g-1) and large pore volumes (0.31-0.36 cm3 g-1). The corresponding hollow mesoporous silica spheres (HMSS) with controllable mesopores (6.0-8.2 nm), high surface areas (239.9-326.5 m2 g-1) and pore volumes (0.37-0.62 cm3 g-1) can be obtained after the removal of the carbon sphere cores through calcination at 700 degrees C in air. The current research results provide an effective methodology for the synthesis of other mesoporous silica core-shell structures with large pore sizes and multilayer core-shells, and even nanorattle structures.

peer-reviewed, TEM analysis of mesoporous materials is generally undertaken to give qualitative results. Accurate quantitative analysis is demonstrated in this study. A systematic image analysis of a powder form of a hexagonal mesoporous material known as KIT-6 is conducted using a transmission electron microscope (TEM). Three types of image contrast typically appear in this material (a hexagonal honeycomb structure, wide and narrow parallel lines). The honeycomb face is used to characterise this material in terms of a conventional 2-D hexagonal structure and the d-spacings for the (100) and (110) planes are experimentally measured in varying focus conditions. A tilting experiment is conducted to determine how the angle of tilt affects the line spacing and their visibility. Tilting has very little effect on the line spacing, whereas it affects the visibility of both the wide and narrow lines by limiting an angle range of visibility. The hexagonal lattice structure parameter determined by TEM method is found to be similar to 7% lower than that calculated by low-angle X-ray diffraction. Thus we conclude that TEM data can be used to determine the geometry and dimensions of hexagonal mesoporous silica materials, with a small error in the hexagonal lattice parameter., Accepted, peer-reviewed

Thermoplastic elastomer/carbon nanotube composites are studied for sensor applications due to their excellent mechanical and electrical properties. Piezoresisitive properties of tri-block copolymer styrene-butadiene-styrene (SBS)/carbon nanotubes (CNT) prepared by solution casting have been investigated. The initial elastic modulus of the SBS/CNT composites increases with increasing the CNT filler content present in the samples, without losing the high deformation capability of the polymer matrix (∼1500%). Furthermore, above the percolation threshold these materials are unique for the development of large deformation sensors due to the strong piezoresistive response. Piezoresistive properties evaluated by uniaxial stretching in tensile mode and 4-point bending showed gauge factors up to 120. The linearity obtained between strain and electrical resistance makes these composites interesting for large strain piezoresistive sensors applications.

The controlled synthesis of ordered anionic surfactant templated mesoporous silica with cubic Ia3d̅ structure (AMS-6) is reported via prolonged periods of hydrothermal treatment (HT). The cubic Ia3d̅ mesophase transforms to hexagonal p6mm after 8 days of HT at 100 °C. Surprisingly, the hexagonal phase is stable only for a limited period after which a reversal to the cubic Ia3d̅ mesostructure is observed. Characterization methods such as powder X-ray diffraction (XRD), electron microscopy (SEM, TEM), N2-isotherms, magic-angle spinning (MAS) 29Si NMR spectroscopy, and thermogravimetric analysis (TGA) have been employed to follow structural and textural changes of the materials prepared. Data show that the resultant mesostructure and its textural properties are highly dependent on the period of HT with less unit-cell shrinkage on calcination after extensive HT. Furthermore, evidence of two different solid−solid phase mechanisms during HT is presented. The initial transition is consistent with a restructuring of the surfactant packing and a depletion of the organic moieties from the organo-silica wall as evident from 29Si NMR spectroscopy. The return to the bicontinuous cubic phase is driven by changes in charge matching at the organic−inorganic interface as a result of increases in the polymerization of the silica wall. The textural properties, and in particular the presence or absence of surface porosity, has been controlled through variations in hydrothermal treatment. These are associated with specific growth directions of cubic AMS-6 crystals. The synthetic method described allows us to easily prepare phase pure and intermediate mesostructured nanoparticles.

The emerging need for new synthetic materials for soft tissue engineering applications encourages the search for innovative polymers having interesting properties. Ring-opening polymerization of lactones and lactides initiated by tin alkoxides has received particular attention due to the versatility of the method for building up well-defined biodegradable structures. The controlled reactions together with a careful choice of comonomers and copolymer composition make it possible to create materials with desired molecular architecture and properties.The aim of the work described in this thesis was to design aliphatic bioresorbable copolymers with new structures and controlled properties for potential application in soft tissue engineering. The first part of the work was focused on the surface properties of the materials synthesized for biomedical application. Solution-cast film triblock copolymers of L-lactide (LLA) and 1,5-dioxepan-2-one (DXO), subjected to thermal treatment have been studied. The effects of molecular weight, polymer composition, cooling rate, and casting solution concentration on the nanostructure surface morphology and topography have been investigated by atomic force microscopy (AFM). The surface characterization of the annealed triblock copolymers revealed well-defined fiber features formed as a result of a melt-induced micro-phase separation during crystallization. The dimensions and shape of the formations could be related to the copolymer composition and annealing conditions, and this makes it possible to create controlled and well-defined surface structure. The results of cell adhesion studies on annealed triblock copolymers indicate that these materials favor fibroblast growth and spreading, which makes them promising candidates for applications as bioresorbable membranes.In the next stage of the work, linear and network copolymers of ε-caprolactone (CL) and DXO with a controlled composition and controlled hydrophilicity have been synthesize, QC 20100629

QC 20100602

Synthetic and degradable polymers are an attractive choicein many areas, since it is possible to control the way in whichthey are manufactured; more specifically, pathways tomanipulate the architecture, the mechanical properties and thedegradation times have been identified. In this work,L-lactide, 1,5-dioxepan-2-one and ε-caprolactone were usedas monomers to synthesize polymers with different architecturesby ring-opening polymerization. By using novel initiators,triblock copolymers, functionalized linear macromonomers andstar-shaped aliphatic polyesters with well-defined structureshave been synthesized. To synthesize triblock copolymers,cyclic germanium initiators were studied. The polymerizationproceeded in a controlled manner although the reaction rateswere low. To introduce functionality into the polymer backbone,functionalized cyclic tin alkoxides were prepared and used asinitiators. During the insertion-coordination polymerization,the initiator fragment consisting mainly of a double bond wasincorporated into the polymer backbone. The double bond wasalso successfully epoxidized and this gave unique possibilitiesof synthesizing graft polymers with precise spacing. Themacromonomer technique is a very effective method for producingwell-defined graft polymers. Spirocyclic tin initiators weresynthesized and used to construct star-shaped polymers. Thestar-shaped polymers were subsequently crosslinked in apolycondensation reaction. These crosslinked structures swelledin water, and swelling tests showed that by changing thestructure of the hydrogel network, the degree of swelling canbe altered. A first evaluation of the surface characteristicsof the linear triblock copolymers was also performed. AFManalysis of the heat-treated surfaces revealed nanometer-scalefibers and tests showed that keratinocytes were able to growand proliferate on these surfaces., QC 20100602

Synthetic and degradable polymers are an attractive choicein many areas, since it is possible to control the way in whichthey are manufactured; more specifically, pathways tomanipulate the architecture, the mechanical properties and thedegradation times have been identified. In this work,L-lactide, 1,5-dioxepan-2-one and ε-caprolactone were usedas monomers to synthesize polymers with different architecturesby ring-opening polymerization. By using novel initiators,triblock copolymers, functionalized linear macromonomers andstar-shaped aliphatic polyesters with well-defined structureshave been synthesized. To synthesize triblock copolymers,cyclic germanium initiators were studied. The polymerizationproceeded in a controlled manner although the reaction rateswere low. To introduce functionality into the polymer backbone,functionalized cyclic tin alkoxides were prepared and used asinitiators. During the insertion-coordination polymerization,the initiator fragment consisting mainly of a double bond wasincorporated into the polymer backbone. The double bond wasalso successfully epoxidized and this gave unique possibilitiesof synthesizing graft polymers with precise spacing. Themacromonomer technique is a very effective method for producingwell-defined graft polymers. Spirocyclic tin initiators weresynthesized and used to construct star-shaped polymers. Thestar-shaped polymers were subsequently crosslinked in apolycondensation reaction. These crosslinked structures swelledin water, and swelling tests showed that by changing thestructure of the hydrogel network, the degree of swelling canbe altered. A first evaluation of the surface characteristicsof the linear triblock copolymers was also performed. AFManalysis of the heat-treated surfaces revealed nanometer-scalefibers and tests showed that keratinocytes were able to growand proliferate on these surfaces., QC 20100602

QC 20100602

NR 20140805

Three types of block copolymers were used to prepare block copolymer ionomers: (1) a triblock copolymer of styrene and ethylene-co-butylene (SEBS) obtained commercially and diblock and triblock copolymers of styrene and ethylene-co-propylene (SEP and SEPS) that were synthesized by anionic polymerization of styrene and isoprene followed by hydrogenation of the polyisoprene block. The styrene content of the SEBS was 30% (wt); the styrene content of the SEP and SEPS was varied from 10-50% to obtain spherical, cylindrical or lamellar microstructures. The styrene blocks were sulfonated to 0-18 mol% with acetyl sulfate, and the free acid derivative and the Na(+) and Zn(2+) salts were prepared. The block copolymer ionomers exhibited two different levels of microphase separation: (1) a block microstructure with a characteristic dimension of the order of 10-20 nm and an ionic microstructure of the order of 2A nm that was located within the styrene block microdomains. The effects of sulfonation, nature of the cation, temperature and sample preparation on the different microstructures and the properties of the polymers were studied by dynamic mechanical analysis, transmission electron microscopy, and small angle x-ray scattering. The effect of adding homopolymers that are miscible with the ionic phase was also studied. jg