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The mechanical stretching behavior of the poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) triblock copolymer (87 wt% polyethylene-co-butylene (PEB), 13 wt% polystyrene (PS)) was investigated under three different stretching modes and through in situ small-angle X-ray scattering (SAXS) analysis. The strain energy density function was investigated based on the stress and stretching ratio (λ) relationship under uniaxial, planar extension, and equi-biaxial stretching modes. As a result, the cross-effect of strain represented by the second invariants of the deformation tensor (I2) was identified, and only the Ogden model found to fit the data. In the cyclic stretching tests, SEBS exhibited smaller hysteresis during cyclic equi-biaxial stretching compared to uniaxial stretching. In other words, the Mullins effect was found to be more obvious for uniaxial stretching than equi-biaxial stretching. The λ and the stretching ratio obtained from the crystal planes by SAXS (λSAXS) were compared to investigate the relationship between the change in the microdomain structure and the macroscopic mechanical properties. Thus, affine deformation was found to occur in the smaller λ region for both uniaxial and equi-biaxial stretching and deviation from affine deformation occurred for uniaxial stretching in the larger λ region. This is because the entangled loops of PEB chains serve as cross-linking points when the films are stretched under equi-biaxial stretching. The mechanical stretching behavior of poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) was investigated under three different stretching modes and through in situ SAXS analysis. SEBS exhibited smaller hysteresis during cyclic equi-biaxial stretching than that of uniaxial stretching. SAXS measurement revealed that affine deformation occurred in the smaller stretching ratio (λ) region for both uniaxial and equi-biaxial stretching modes and deviation from affine deformation occurred for uniaxial stretching mode at the larger λ region. This is because entangled loops of poly(ethylene-co-butylene) chains serves as cross-linking points when films are stretched under equi-biaxial stretching mode.

The strength of silica-based mechanochromic nanocomposites was improved by a novel nanocomposite synthesized by grafting poly(butyl acrylate) (PBA)-b-poly(methyl methacrylate) (PMMA) from silica na...

Molecular mechanisms underlying the cononsolvency, a re-entrant coil-to-globule-to-coil conformational transition of polymer chains in mixtures of two good solvents, of poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC) in ethanol-water binary mixtures were complementarily investigated. This was accomplished by following a statistical mechanical model for competitive hydrogen bonding combined with the cooperative solvation concept as well as neutron reflectivity (NR) experiments employing contrast variation in the cononsolvents. The experimental re-entrant aggregation of the PMPC chains in ethanol-water mixed solvents, obtained on the basis of turbidity was accurately reproduced by theoretical calculations. The calculation proved the relatively strong cooperativity of ethanol and the preferential interaction of water, while the total coverage of solvents was the lowest at an ethanol volume fraction (fethanol) of 0.90. At this level, the cononsolvency was the most significant, and the collapsed PMPC chains were solvated with more water than the bulk mixed solvent. The ethanol-water cononsolvency for the PMPC brushes on a planar silicon wafer was investigated by NR experiments, and the solvent composition involved in the collapsed PMPC brush was addressed according to the contrast variation study with mixed solvents of water, deuterium oxide, ethanol-d5, and ethanol-d6. The collapsed PMPC brushes at fethanol = 0.90 contained more water than the bulk solvent. The preferential distribution of water in the collapsed PMPC brush was consistent with the simulation results. Therefore, the molecular mechanism for the cononsolvency of PMPC in ethanol-water mixed solvents based on competitive hydrogen bonding coupled with cooperative solvation was experimentally rationalized.

Nanocomposites composed of monodisperse silica nanoparticles (SiNPs) modified with an elastic comb-shaped block copolymer brush were produced for the first time. Comb-shaped polymer brushes consisting of glassy poly(methyl methacrylate) branches and a rubbery poly(butyl acrylate) backbone were grafted from 100 nm diameter SiNPs by surface-initiated atom transfer radical polymerization. The comb-shaped polymer brush-grafted SiNPs produced self-standing films with a face-centered cubic ordered lattice structure via solvent-casting. The composite films showed rubber elasticity because of the interparticle rubbery polymer brush boundary phase. The ordered lattice exhibited significant alignment and distortion in response to the macroscopic film strain, and then reproduced the initial ordered lattice after unloading.

Polythiourethane (PTU) and polyurethane (PU) elastomers were prepared from poly(oxytetramethylene) glycol, 1,4-bis(isocyanatomethyl) cyclohexane and a dithiol or diol chain extender with two methylene numbers (tetramethylene (C4) and pentamethylene (C5)). The effect of dithiol and diol and the methylene length of the chain extenders on the microphase-separated structure and mechanical properties of PTU and PU were evaluated. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction measurements revealed that the degree of ordering of hard segment chains in PTUs is lower than that for PU elastomers. However, it was revealed from the DSC, small-angle X-ray scattering and temperature dependent dynamic viscoelasticity measurements that the degree of microphase separation in the PTUs became stronger than that for the PUs. As a result, the mechanical property of PTUs is comparable with PUs. Furthermore, the glass transition temperature for the soft segment of PTU became lower than that for PU. PTU and PU exhibited a larger degree of microphase separation and mechanical property when the chain extender was composed of a tetramethylene (C4) chain compared to a pentamethylene (C5) chain. Polythiourethane (PTU) elastomers, which are obtained by the reaction between polyol, diisocyanate, and dithiol, are expected to have some properties that polyurethanes (PUs) do not have. Herein, the microphase-separated structure and mechanical properties of the 1,4-bis(isocyanatomethyl) cyclohexane-based PTUs were investigated. It was revealed from the differential scanning calorimetry, small-angle X-ray scattering and dynamic viscoelasticity measurements that the PTUs possess a stronger degree of microphase separation and lower glass transition temperature of soft segment compared to that of PUs.

Hard segments of polyurethanes (PUs) are generally formed from diisocyanate and diol. Diol can be replaced with triol and thiol. These chemical structures of hard segments strongly affect not only a microphase separated structure but mechanical properties of resultant PUs. In this review, we focus on the relationship between chemical structure like symmetry and bulkiness of diisocyanate and mechanical properties of PU. Then, influence of hard segment content, incorporation of 1,1,1-trimethylol propane with trifunctional groups, and alkyldithiol was reviewed mainly on trans-1,4-bis(isocyanatomethyl) cyclohexane-poly(oxytetramethylene) glycol-based PU.

It is desirable to establish a method for evaluating mechanical properties, such as modulus and strength, of micrometer and sub-micrometer thick polymer films. Bulge tests, where bulge deformation is imposed on films by the pressure of an inert gas, are suitable for satisfying this demand. However, very few studies on polymer films exist in the literature. In this study, bulge testing equipment for in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) measurements is designed and used to study the relationship between the molecular aggregation structure and the mechanical properties of a crystalline nylon 12 (Ny12) film during bulge testing. Isothermally crystallized and quenched Ny12 films exhibited stress-strain curves similar to those obtained by conventional uniaxial elongation. In situ WAXD measurements during bulge testing revealed that the lattice extension of the crystallites is clearly dependent on crystallinity. Concretely, crystallites in the isothermally crystallized film show higher elastic properties than those in the quenched one. The results of the molecular aggregation structure, including the crystal structure and the amorphous chain surrounding the crystallites, of the films during bulge deformation firstly obtained in this study must be useful for designing toughened polymer films.

Biocompatible and blood-compatible surface modification is urgently needed for stainless steel (SUS)-based human implant devices to avoid inflammation and biofouling. To this end, the use of polymeric surface modifiers, whose surface properties are specifically tailored, is a promising approach since this approach minimizes the impact on device's mechanical properties. However, adhesion between the device and surface modifier is relatively weak, since van der Waals forces are employed, leading to low device durability. To address this issue, this work functionalized poly(ɛ-caprolactone)-b-[poly(α-chloride-ɛ-caprolactone)-b-poly(2-methacryloyloxyethyl phosphorylcholine)]2 (PCL-b-(PCL-Cl-b-PMPC)2) with catechol groups via a nucleophilic substitution, whereby the catechol functionalization was optimized. The resultant surface modifier showed strong adhesion toward SUS surfaces, forming a smooth and uniform hydrophilic polymeric film that reduced SUS fouling (i.e., protein). Notably, no significant changes of adhesion between the SUS and thin films (thin film) were observed after immersion for 45 days in a pH 7.4 phosphate buffer solution. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 38–49

The effect of molecular mobility of a pre-crystallized phase on the isothermal crystallization in the microphase-separated lamellar morphology of a strongly segregated crystalline-crystalline block copolymer, poly(ethylene glycol)- block -poly(perfluorooctylethyl acrylate) (PEG- b -PFA-C 8 ), was investigated. The diblock copolymer produced a microphase-separated lamellar morphology in the melt state, and the precedent crystallization of PFA-C 8 blocks provided the lamellar confinement field. The counter PEG block crystallized within the lamellar confinement field. The molecular mobility of the pre-crystallized PFA-C 8 phase was modulated by the thermal history. The structural evolution was monitored by a complementary combination of in situ time-resolved simultaneous small-angle X-ray scattering/wide-angle X-ray diffraction measurements and thermal analyses. The degree of crystallinity and the melting temperature of the PEG crystals were associated with the molecular mobility of the pre-crystallized PFA-C 8 phase. The highly packed PFA-C 8 phase (higher-ordered phase) constrained the PEG crystallization, whereas the loosely packed PFA-C 8 phase (lower-ordered phase) caused a weak restriction in the PEG crystallization to give relatively ordered PEG crystals. Subsequent crystallization in a confinement field of crystalline-crystalline block copolymers was controlled by adjusting the molecular mobility of the pre-crystallized phase.

Polyurethane elastomers (PUEs) containing trans-1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI) have been synthesized by polymerizing 1,4-H6XDI with poly(oxytetramethylene) glycol and 1,4-butanediol. The molecular aggregation state and mechanical properties of these PUEs have been compared with those exhibited by PUE analogues made of MDI and diols. The hard segment chains in the 1,4-H6XDI-based PUEs are found to readily crystallize and form strong hydrogen bonds due to a high symmetry of 1,4-H6XDI molecule. Consequently, the 1,4-H6XDI-based PUEs exhibit well-organized hard segment domains. This leads to their generally superior mechanical properties as compared to those of the well-known MDI-based PUEs. 1,4-H6XDI’s lack of aromatic moieties is expected to greatly enhance color stability of resulting PUEs. All the above features suggest 1,4-H6XDI could replace MDI in a range of applications.

We have prepared the amidinium-carboxylate salt bridge-based supramolecular network polymers from a carboxy-terminated telechelic poly(n-butyl acrylate) and a linear polyamidine having N,N′-di-substituted acetamidine group in the main chain. FTIR measurements indicated that the salt bridge was attributed to the three-dimensional network formation. Virtually, no fluidity was observed for the blend containing equimolar amounts of the carboxyl group and the amidine group, which showed a high G′ value of about 1 MPa at −5 °C. For comparison, the supramolecular network polymers crosslinked by ammonium-carboxylate salt were prepared using a linear polyethyleneimine instead of the polyamidine. The blend with equimolar amounts of the carboxyl group and the secondary amino group showed liquid-like fluidity with a G′ value of about 0.01 MPa at −5 °C, which was attributed to the fact that a certain amount of the carboxyl group remained as its free form, as evidenced by FTIR analysis. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2148–2155

Natural rubber (NR) films from various mixing ratios of large- (LRP) and small rubber particles (SRP) were prepared through latex and solution casting methods. Film-forming behaviours of the resulting films were investigated by monitoring their surface characteristics using atomic force microscopy (AFM). When the SRP portion was higher, the surface of the latex-cast films was found to be smoother as smaller particles protruded out of the surface less than larger ones did. AFM phase micrographs revealed a hexagonal shape of packed rubber particles (RPs) of the LRP film, while the RPs in the other samples were sphere-like. After aging under ambient conditions, the packed RPs were flattened while retaining their RP boundaries, creating a supporting framework within the rubber matrix. On the contrary, when the rubber film was cast from a toluene solution, the characteristic of RP boundaries disappeared and became aggregates of the membrane components on the film surface. The latex-cast films performed much better in mechanical strength than the solution-cast films did due to the destruction of the supporting framework arisen from the non-rubber components at the RP boundaries of the solution-cast film. An inhomogeneous density distribution produced by the non-rubber aggregates in the latex-cast films was observed in small angle X-ray scattering measurements.

Dispersion of C60/silica nano-composite, prepared by inclusion of C60 into grafted polymer chains on silica, in organic solvent and poly(methyl methacrylate) (PMMA) matrix was investigated. The polymer-grafted SiO2 particles were prepared by grafting of poly(methyl methacrylate-co-2-naphthyl methacrylate) onto colloidal silica of 9.1 nm in diameter. Inclusion of C60 into the grafted polymer chains was significantly dependent on molecular weight of the polymer and independent on amounts of grafted polymer. The C60/SiO2-PMMA hybrid film, composed of 0.21% C60 and 10% SiO2, showed high transparency in visible light region.

NO2-sensing properties of porous In2O3 (pr-In2O3) powders prepared by ultrasonic-spray pyrolysis employing polymethylmethacrylate (PMMA) microspheres as a template has been investigated in this study. The PMMA microspheres were synthesized in water by ultrasonic-assisted emulsion polymerization employing methyl methacrylate monomer, sodium lauryl sulfate as a surfactant and ammonium persulfate as an initiator. The PMMA microspheres synthesized was quite uniform and the particle size was ca. 60.2 nm (measured by dynamic light scattering). The microstructure of pr-In2O3 powders prepared was largely dependent on the kind of In2O3 sources. The pr-In2O3 which was prepared from In(NO3)3 as an In 2O3 source (pr-In2O3(N)) consisted of submicron-sized spherical particles with welldeveloped spherical mesopores (several tens of nanometers in pore diameter) and each oxide wall among pores was constructed with meso-sized In2O3 particles connected continuously. On the other hand, the pr-In2O3 which was prepared from InCl3 as an In2O3 source (pr-In2 O3(Cl)) was composed of a large number of dispersed meso-sized particles and a few submicron-sized dense spherical particles. In contrast, the morphology of conventional In2O3 powder (c-In 2O3) prepared by ultrasonic-spray pyrolysis of PMMAfree In(NO3)3 aqueous solution as a reference was relatively dense and roughly spherical with a diameter of ca. 100-700 nm. The responses to 1.0 and 10ppm NO2 of pr-In2O3 sensors in air were much larger than those of a c-In2O3(N) sensor in the temperature range of less than 250°C and 300°C, respectively. In addition, the response and recovery speeds of both the pr-In2O 3 sensors were much faster than those of the c-In2O 3(N) sensor, because of the well-developed porous structure of the pr-In2O3 sensors., Sensors and Actuators B: Chemical, 187, pp.495-502; 2013

ABA-type triblock copolymers (PEOxz-PTHF-PEOxz) composed of poly(tetrahydrofuran) (PTHF) and poly(2-ethyl-2-oxazoline) (PEOxz) were synthesized by cationic sequential polymerization. Differential scanning calorimetry and wide-angle X-ray diffraction analyses revealed that PEOxz-PTHF-PEOxzs produced a microphase separation structure, which consisted of a partially crystallized amorphous PTHF phase containing PEOxz chains on both ends. Tensile testing showed that PEOxz-PTHF-PEOxz exhibited tough mechanical properties that differed from those of the brittle PTHF homopolymer. Thus, it was suggested that the amorphous PTHF/PEOxz phase played a role in physically cross-linking the moieties via entanglement, resulting in a PEOxz-PTHF-PEOxz material with tough mechanical properties and the ability to be cold-drawn., Polymer Journal, 45(11), pp.1115-1119; 2013

Dispersion of fullerene, C 60, by addition of polymethacrylate dispersant in methyl methacrylate (MMA) and incorporation of C 60 into poly(methyl methacrylate) (PMMA) were investigated. Copolymers synthesized by radical copolymerization of MMA and 2-naphthyl methacrylate (NMA), poly(MMA-co-NMA), effectively dispersed C 60 in MMA to form clusters of 20 nm. In these cases, addition of minimal 110 naphthyl groups per unit C 60 molecule afforded to give clusters with minimum of 20 nm sizes. Furthermore, block copolymers, poly(MMA-b-NMA) with MMA/NMA mole ratio from 12:1 to 20:1, also efficiently dispersed C 60 to give formation of clusters of 20 nm size by addition of minimal 40 naphthyl groups per unit C 60 molecule, which was corresponding to approximate nine layers of naphthyl group in block copolymer adsorbed on the surface of the cluster. Hybrid films of C 60/PMMA, prepared by casting of C 60-dispersed solution containing PMMA, exhibited absorbance at 400 nm linearly increased with C 60 content., Colloid and Polymer Science, 290(12), pp.1221-1226; 2012

Mechanical properties of thermoplastic polyurethane elastomers based on either polyether or polycarbonate (PC)-glycols, 4,4'-dipheylmethane diisocyanate (1,1'-methylenebis(4-isocyanatobenzene)), 1,4-butanediol, were controlled by restriction of crystallization of polymer glycols. For the polyether glycol based-polyurethane elastomers (PUEs), poly(oxytetramethylene) glycol (PTMG), and PTMG incorporating dimethyl groups (PTG-X) and methyl side groups (PTG-L) were employed as a polymer glycol. For the PC-glycol, the randomly copolymerized PC-glycols with hexamethylene (C₆) and tetramethylene (C₄) units between carbonate groups with various composition ratios (C₄/C₆ = 0/100, 50/50, 70/30 and 90/10) were employed. The degree of microphase separation and mechanical properties of both the PUEs were investigated using differential scanning calorimetry, dynamic viscoelastic property measurements and tensile testing. Mechanical properties could be controlled by changing the molar ratio of two different monomer components.

A series of eight aliphatic polycarbonate (PC) glycols with various methylene numbers (HO−[(CH2)mOC(═O)O]n−(CH2)m−OH, m = 3, 4, 5, 6, 7, 8, 9, and 10) were employed as a soft segment for a synthesi...

Highly hydrophilic polyurethane elastomers (PUEs) were synthesized from 1,2-bis(isocyanate) ethoxyethane (TEGDI), poly(ethylene oxide-co-propylene oxide) copolyol (EOPO) and 1,4-butane diol/1,1,1-trimethylol propane (75/25) (wt/wt) by a prepolymer method. 4,4′-Diphenylmethane diisocyanate (MDI)-based PUEs were synthesized as a control as well. Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) measurements revealed that the degree of microphase separation of the TEGDI-based PUEs was much weaker than for the MDI-based PUEs. Young's modulus and elongation at break of the TEGDI-based PUEs were quite lower and larger than for the MDI-based PUEs, respectively. This is due to quite weak cohesion force of the hard segment chains in the TEGDI-based PUEs. The degree of swelling of the TEGDI-based PUEs was five times larger than for the MDI-based one. This is associated with the hydrophilic nature of TEGDI and weak cohesion force in the TEGDI-based PUEs., Polymer, 50(15), pp.3693-3697; 2009

The microphase-separated structure of polyurethane bulk and thin films were investigated using atomic force microscopy (AFM). The polyurethane (PUs) were synthesized with poly(oxytetramethylene) glycol (PTMG), 4,4′-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD) by a prepolymer method. The hard segment contents were 34 and 45wt%. Polarized optical microscopy (POM) revealed that the 34wt% PUE is homogeneous at a macroscopic level, while the 45wt% one is macrophase-separated into two phases. One phase forms spherulites of ca. 2–5 μm in diameter. AFM observation for the 34wt% PUE showed the microphase-separated structure, consisting of hard segment domains and a soft segment matrix. In contrast, for the 45 wt% PUE, a lot of the hard segment domains were observed in the spherulite region, indicating that spherulites include much amount of hard segment component, in contrast, outside of spherulite exhibited similar structure to that of 34 wt% one. For the PU bulk, the different microphase-separated structure in the inside and outside of spherulite was successfully observed for the first time. Also, the microphase-separated structure of PU films was investigated as a function of the film thickness. The PU films exhibited similar microphase-separated structure. For the thicker film (∼200nm), the interdomain spacing almost corresponded to bulk one. On the other hand, that for the film thickness below 7nm dramatically decreased. This seems to be simply related to a decreasing space. We obtained the experimental data, which the phase-separated domain size of multiblock copolymer decreased with decreasing film thickness.

High Performance Polyamide 6 Fibers Using Polycarbonate Based Thermoplastic Polyurethane Thin Film Coatings- a Novel Method

The effect of side methyl and dimethyl groups of the soft segment component on the microphase-separated structure and mechanical properties of polyurethane elastomers (PUEs) was investigated. Poly(oxytetramethylene) glycol (PTMG), and PTMG incorporating dimethyl groups (PTG-X) and methyl side groups (PTG-L) were used as a polymer glycol, which forms a soft segment in the PUEs. The PUEs were synthesized with 4,4′-dipheylmethane diisocyanate [1,1′-methylenebis(4-isocyanatobenzene)], 1,4-butane diol, and 1,1,1-trimethylol propane by a prepolymer method. The degree of microphase separation of the PUEs became weaker with increasing side group content in polymer glycols. Dynamic viscoelastic properties measurement showed reorganized-crystallization and melting of the soft segment for the PUEs based on PTMG, PTG-L, and PTG-X with a lower content of the side groups, but not for a PTG-L and PTG-X with higher content of the side groups. Tensile testing revealed that increasing methyl group concentration made the PUEs soften and weaken. The PTMG-based PUEs obviously exhibited strain-induced crystallization of the soft segment chains during elongation process. In contrast, for the PTG-L and PTG-X-based PUEs, crystallinity decreased with increasing side group content, and the PUEs with PTG-L and PTG-X with highest methyl group content did not crystallize even at a large strain. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2054–2063, 2008

Norbornane diisocyanate (NBDI: 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane) is a new commercialized diisocyanate. NBDI-based polyurethane elastomers (PUEs) were prepared from poly(oxytetramethylene) glycol (PTMG), NBDI and 1,4-butanediol (BD) by a prepolymer method. Microphase-separated structure and mechanical properties of the NBDI-based PUEs were compared with general aliphatic and cycloaliphatic diisocyanate-based PUEs. The diisocyanates used were isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI). Regular polyurethanes were also prepared as hard segment models from each isocyanate and BD to understand the feature of each hard segment chain. The HDI-based PUE showed the largest Young's modulus and tensile strength in the four PUEs due to the ability of crystallization of the hard segment component and the strongest microphase separation. HMDI has both properties of aliphatic and cycloaliphatic diisocyanates because of its high symmetrical chemical structure compared with NBDI and IPDI. On the other hand, the NBDI- and IPDI-based PUEs have an inclination to phase mixing, leading to decreased Young's modulus and tensile strength. The NBDI-based PUE exhibited better thermal properties at high temperatures due to stiff structure of NBDI.

Biogels and bio-hybrid gels were prepared from myofibril of fish and their properties were evaluated. The muscular protein used was extracted from fish meat. After washing and centrifugal separation, the muscular protein was mixed with 3 wt % of NaCl and the gels were prepared by heating the mixtures from 50 to 90 °C. The bio-hybrid gels were prepared from fish protein gel and poly(vinyl alcohol). Tensile tests revealed that the tensile strength, strain at break and Young’s modulus of heated hybrid gels prepared at 50, 80 and 90 °C increased with increasing preparation temperature. This can be explained by the difference in crosslinking density. Also, the heated gels showed a good response to electric field in acid and alkaline solutions. Young modulus, tensile strength and elongation at break of the bio-hybrid gels increased with an increasing PVA content. Bending of hybrid gels in solutions of various pH under the electric stimulus was observed. The largest bending angle was 20–30 °C at pH=1.2.

A diisocyanate baring ether bonds, 1,2-bis(isocyanate)ethoxyethane (TEGDI), was used for the preparation of polyurethane elastomers (PUEs). The PUEs were synthesized with either TEGDI or HDI, poly(oxytetramethylene) glycol (PTMG), and curing agents by a prepolymer method. 1,6-Hexamethylene diisocyanate (HDI) was also used as a control diisocyanate. The TEGDI-based PUEs exhibited highly softened property on account of flexibility of TEGDI itself and weaker phase separation. Another TEGDI-based PUEs were prepared with either poly(oxypropylene) glycol (PPG) or poly(caprolactone) glycol (PCL). Microphase-separated structure of these TEGDI-based PUEs are quite different from those with general diisocyanates and the PUEs were made be greatly softened.

Effect of side methyl and dimethyl groups of soft segment component on polyurethane elastomers (PUEs) was investigated with and without elongation. The polymer glycols used were poly(oxytetramethylene) glycol (PTMG), PTMG with dimethyl groups (PTG-X) and methyl groups (PTG-L). Phase separation of the PUEs became weaker with an increasing methyl group content. Tensile test revealed that the increasing methyl group concentration made the PUEs be soften and weaken. The PTMG based PUEs obviously exhibited elongation-induced crystallization during elongation process. In contrast, for the PTG-L and PTG-X based PUEs, crystallinity decreased with an increasing side methyl group content, and the PUEs with PTG-L and PTG-X with highest methyl group content did not crystallize. We succeeded the control of the crystallization behavior of elastomers under an elongation by the introduction of side methyl groups.

Randomly copolymerized poly(carbonate) glycols were employed as starting materials for the synthesis of polyurethane elastomers (PUEs). The poly(carbonate) glycols had hexamethylene (C 6 ) and tetramethylene (C 4 ) units between carbonate groups in various composition ratios (C 4 /C 6 = 0/100, 50/50, 70/30, and 90/10), and the number-average molecular weights of these poly(carbonate) glycols were 1000 and 2000. The PUEs were synthesized with these poly(carbonate) glycols, 4,4'-diphenylmethane diisocyanate, and 1,4-butanediol by a prepolymer method. Differential scanning calorimetry measurements revealed that the difference between the glass-transition temperature of the soft segment in the PUEs and the glass-transition temperature of the original glycol polymer decreased and the melting point of the hard-segment domain increased with an increasing C 4 composition ratio. The microphase separation of the poly(carbonate) glycol-based PUEs likely became stronger with an increasing C 4 composition ratio. Young's modulus of these PUEs increased with an increasing C 4 composition ratio. This was due to increases in the degree of microphase separation and stiffness of the soft segment with an increase in the C 4 composition ratio. The molecular weight of poly(carbonate) glycol also influenced the microphase-separated structure and mechanical properties of the PUEs. The addition of different methylene chain units to poly(carbonate) glycol was quite effective in controlling the microphase-separated structure and mechanical properties of the PUEs.

Well-defined poly(methyl methacrylate) (PMMA) brush layers were prepared onto silicon wafers by surface-initiated atom transfer radical polymerization using 2-(4-chlorosulfonylphenyl)-ethyltrichlorosilane as an initiator. Based on molecular weight and layer thickness measurements, it was deduced that the apparent graft density was 0.6–0.8 chains nm-2 depending on the polymerization time and that the conformation of tethered chains was highly extended. Surface relaxation behavior of the PMMA brush layer and the spin-coated PMMA film was examined by lateral force microscopy. The αa- and β-relaxation processes were discernibly observed at both surfaces. Although surface molecular motion of the brush layer and the spin-coated film was markedly different from the bulk one, both were hardly distinguishable in terms of relaxation phenomena.

The n -octadecyltrichlorosilane (OTS, CH 3 (CH 2 ) 17 SiCl 3 ), 18-nonadecenyltrichlorosilane (NTS, CH 2 CH(CH 2 ) 17 SiCl 3 ), [2-(perfluorooctyl)ethyl]trichlorosilane (FOETS, CF 3 (CF 2 ) 7 CH 2 CH 2 SiCl 3 ) monolayers, and their mixed monolayers were used as model surfaces for the study of protein adsorption mechanism. Surface plasmon resonance (SPR) spectroscopy was applied to analyze the protein adsorption behavior onto the monolayer surfaces. The surfaces after exposure of these monolayers to bovine serum albumin (BSA) and γ-globulin(IgG) solutions were observed with atomic force microscope(AFM). AFM observation revealed that the charged protein either below or above pI was preferentially adsorbed onto the FOETS phase of the phase-separated (OTS/FOETS) mixed monolayer. in situ AFM observation of monolayer surfaces in BSA solution also revealed the preferential adsorption of BSA onto the hydrophobic FOETS surface. SPR clarified that the amount of adsorbed protein in the charged state was lower than that in the neutral state. Adhesion force was not detected in the force–distance curve measurement between negatively-charged HOOC(CH 2 ) 9 SH chemisorbed cantilever tip and the OTS phase in the presence of adsorbed BSA on FOETS phase of mixed monolayer. These results indicate that the preferential adsorption of protein onto the FOETS phase for the mixed monolayer systems at either below or above pI is due to, (1) the minimization of interfacial free energy between the monolayer surface and the buffer solution; and (2) the electrostatic repulsion among protein molecules bearing charges.

A novel and convenient method to prepare organosilane monolayers was proposed. Pure water was put onto a cleaned silicon wafer and then a toluene solution of n-trichloro(octadecyl)silane (OTS) was spread on it. X-ray photoelectron spectroscopy and atomic force microscopic observation revealed that an OTS monolayer was successfully formed on the solid substrate after the water was evaporated. The static water contact angle of the silicon wafer covered with the OTS monolayer was 105°. Molecular aggregation states of the OTS monolayer were examined by electron diffraction, Fourier transform infrared spectroscopic, X-ray reflectivity, and grazing incidence X-ray diffraction measurements. The prepared OTS monolayer was in a two-dimensional hexagonal crystalline state at 293 K and alkyl chains of the OTS molecules were oriented normal to the surface. Also, the alkyl chains in the monolayer were highly ordered, although the experimental procedure for the monolayer preparation was quite simple. The development of...

The n-octadecyltrichlorosilane (OTS, CH 3 (CH 2 ) 17 SiCl 3 ), 18-nonadecenyltrichlorosilane (NTS, CH 2 =CH(CH 2 ) 17 SiCl 3 ), [2-(perfluorooctyl)ethyl] trichlorosilane (FOETS, CF 3 (CF 2 ) 7 CH 2 CH 2 SiCl 3 ) monolayers, and their mixed monolayers were used as the model substrates for the study of protein adsorption mechanism. Surface plasmon resonance (SPR) spectroscopy was applied to analyze the protein adsorption behavior onto the surface of the monolayers. Atomic force microscope (AFM) was used to observe the monolayer surfaces after exposure of these monolayers to bovine serum albumin (BSA) and γ-globulin(IgG) solution. AFM observation revealed that the charged protein either below or above the isoelectric point was preferentially adsorbed onto the FOETS phase of the (OTS/FOETS) mixed monolayer. SPR revealed that the amount of adsorbed protein in the charged state was lower than that in the neutral state. These results indicate that the preferential adsorption of protein onto the FOETS phase for the mixed monolayer systems at either below or above pI is due to (1) the minimization of interfacial free energy between the monolayer surface and the buffer solution, and (2) the electrostatic repulsion among protein molecules bearing charges.

Alkyltrichlorosilanes, [2‐(perfluorooctyl)ethyl]trichlorosilane (FOETS) and their mixed monolayers were polymerized on the water subphase and were subsequently immobilized onto the silicon wafer surface by covalent bonding. Atomic force microscopic (AFM) observation of the [n‐octadecyltrichlorosilane(OTS)/FOETS] mixed monolayer revealed that the crystalline OTS formed circular domains of ∼1–2 μm in diameter that were surrounded by an amorphous FOETS matrix. Lateral force microscopic (LFM) and scanning viscoelasticity microscopic (SVM) observations of the (OTS/FOETS) mixed monolayer could also distinguish the difference in the physical and mechanical properties between domain and matrix. The (alkylsilane/FOETS) mixed monolayers with a shorter alkyl chain such as n‐dodecyltrichlorosilane (DDTS) did not show the phase‐separated structure maybe due to the lack in crystallinity of DDTS component. AFM observation of the [crystalline fatty acid (nonreactive)/FOETS (reactive)] mixed monolayer also revealed the phase‐separated structure. The crystalline fatty acid domains in the mixed monolayer were extracted by solvent and then, the monolayer of FOETS with the holes of ∼1–2 μm in diameter, that is, the (Si/FOETS) monolayer was finally obtained. The Si phase of (Si/FOETS) was backfilled with the another organosilane by chemisorption. Then, the [(3‐mercaptopropyl) trimethoxysilane (MTS)/FOETS] mixed monolayer was newly obtained by the chemisorption of MTS. The absorption of bovine serum albumin (BSA) onto mixed monolayers was studied by exposure of the mixed monolayers to a BSA solution. BSA was preferentially adsorbed onto the MTS part due to a specific reaction between disulfide bond (–S–S–) in BSA and SH groups in MTS. On the other hand, in the case of (OTS/FOETS) mixed monolayer, BSA adsorbed preferentially onto the FOETS matrix in order to minimize the interfacial free energy in the aqueous environment.

(Alkylsilane/fluoroalkylsilane) mixed monolayers were immobilized covalently on a silicon wafer surface with stable surface structure. Atomic force microscopic observation of the n-octadecyltrichlorosilane (OTS)/[2-(perfluorooctyl)ethyl]trichlorosilane (FOETS) mixed monolayer revealed that the crystalline OTS circular domains of ca. 1–2μm in diameter were surrounded by a sealike amorphous FOETS matrix, even though the molar fraction of OTS was above 75%. Also, the phaseseparated monolayer can be prepared from FOETS, and a non-polymerizable and crystallizable amphiphile such as lignoceric acid (LA). The phase separation of the (alkylsilane/fluoroalkylsilane) mixed monolayer might be attributed to both faster spreading of FOETS molecules on the water surface and the crystallizable characteristics of alkylsilane molecules. The mixed monolayer of crystalline alkylsilane (OTS) and amorphous alkylsilane (n-dodecyltrichlorosilane, DDTS) formed a phase-separated structure on the water surface because of the crystallizable characteristics of OTS. Lateral force microscopic (LFM) observation revealed that the order of the magnitude of lateral force generated against the silicon nitride tip was: n-triacontyltrichlorosilane (TATS) domain with longer alkyl chain > amorphous FOETS matrix > crystalline OTS domain. On the other hand, scanning viscoelasticity microscopic observation revealed that the order of the magnitude of modulus was: Si substrate > crystalline OTS domain > amorphous FOETS matrix.

Surface structure and dynamics in three different polymeric ultrathin systems, such as organosilane monolayers, poly(methyl methacrylate) (PMMA) brushes and poly(amido amine) dendrimer monolayers are discussed.

A mixed (n-octadecyltrichlorosilane (OTS)/[2-(perfluorooctyl)ethyl]trichlorosilane (FOETS)) monolayer was prepared on the water subphase and was subsequently immobilized onto the silicon wafer surface by chemical bonds. Atomic force microscopic (AFM) observation of the mixed (OTS/FOETS) monolayer revealed the formation of a phase-separated structure. In situ AFM observation of the adsorption behavior of bovine serum albumin (BSA) onto the mixed (OTS/FOETS) monolayers, successfully showed the adsorption behavior of BSA onto the phase-separated surface. It also revealed that in the case of pH 7.5, BSA was preferentially adsorbed onto the lower surface free energy FOETS phase of the mixed (OTS/FOETS) monolayer. On the other hand, BSA was adsorbed homogeneously onto the OTS and FOETS phases at the isoelectric point of BSA (pI 4.7). These results indicate that the preferential adsorption of BSA onto the FOETS phase in the mixed (OTS/FOETS) monolayer system may be due to: (1) the minimization of interfacial free energy between a monolayer surface and an aqueous solution; and (2) the electrostatic repulsion among BSA molecules bearing negative charges.

Octadecyltrichlorosilane (OTS) and [2-(perfluorooctyl)ethyl]trichlorosilane (FOETS) monolayers and their mixed monolayer were polymerized on a water subphase and subsequently immobilized onto a silicon wafer surface by covalent bonding. Atomic force microscopic (AFM) observation of the mixed (OTS/FOETS) monolayer revealed the formation of a phase-separated structure. Protein-adsorption behavior onto the monolayers was investigated in situ on the basis of an attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopic flow cell method and the morphology of the monolayer surface-adsorbed bovine serum albumin (BSA) was observed by AFM. Protein adsorption behavior observed by ATR-FT-IR flow cell method revealed that the amount of BSA adsorption onto the OTS and FOETS monolayers increased remarkably at an initial experimental stage and attained a steady state within a few minutes at pH 7.5. The amount of steady state adsorption was c. 0.18-0.2 microgcm(-2). AFM observation of the monolayer after exposure to BSA solution suggested that BSA adsorbed in the end-on adsorption state on OTS monolayer and side-on one in the FOETS monolayer, respectively. However, in the case of the mixed (OTS/FOETS) monolayer, ATR-FT-IR flow cell experiment revealed that the amount of steady state adsorption of BSA was suppressed. Also, AFM observation revealed that at pH 7.5, BSA preferentially adsorbed onto the FOETS phase of the mixed (OTS/FOETS) monolayer, which had a higher interfacial free energy against water. On the other hand, BSA adsorbed homogeneously onto the OTS and FOETS phases at the isoelectric point of BSA (pH 4.7). These results indicate that the preferential adsorption of BSA onto the FOETS phase in the mixed (OTS/FOETS) monolayer system is due to: (1) the minimization of the interfacial free energy between a monolayer surface and an aqueous solution; and (2) the electrostatic repulsion between BSA molecules bearing negative charges.

Chemically cross-linked polyurethanes (PUs) were synthesized with two different cross-linking densities and dangling chain concentrations to understand the difference between the molecular mobility of the bulk and free surface based on dynamic viscoelastic properties, lateral force microscopy (LFM) and scanning viscoelasticity microscopy (SVM) measurements. The PUs were synthesized from poly(oxypropylene) triol (PPT; Mn = 3000) and tolylene-2,4-diisocyanate (TDI) with a formulation ratio (= [NCO]/[OH]) of 0.85 and 1.20. The former PU has a lightly cross-linked structure with dangling chains, and the latter one has a densely cross-linked structure with allophanate groups and without dangling chains. The α-relaxation process, associated with glass transition of the PPT chains for the bulk and surface, was observed for both PUs in dynamic viscoelastic properties and lateral force microscopy measurements, respectively. The temperature region, at which the α-relaxation process was observed, for the surface was lower and broader in comparison with bulk and the trend was more obvious for the PU with dangling chains. These results can be explained well with the existence of dangling chains and their segregation at the top surface because of lower conformational entropy.

Measurements are presented how chain and microphase-separated structures of ultrathin polyurethane (PU) films are controlled by the thickness. The film thickness is varied by a solution concentration for spin coating. The systems are PUs prepared from commercial raw materials. Fourier-transform infrared spectroscopic measurement revealed that the degree of hydrogen bonding among hard segment chains decreased and increased with decreasing film thickness for strong and weak microphase separation systems, respectively. The microphase-separated structure, which is formed from hard segment domains and a surrounding soft segment matrix, were observed by atomic force microscopy. The size of hard segment domains decreased with decreasing film thickness, and possibility of specific orientation of the hard segment chains was exhibited for both systems. These results are due to decreasing space for the formation of the microphase-separated structure., IUMRS-ICA 2008 Symposium Sessions X and Y. Soft Matter Science, 9-13 December, Nagoya, Japan, Journal of Physics: Conference Series, 184(1), 012028; 2009