Anti-corrosive,weatherproof and self-healing polyurethane developed from hydrogenated hydroxyl-terminated polybutadiene toward surface-protective applications

Self-healing polyurethane (PU) faces aging deterioration due to active dynamic bonds, which remain a challenging predicament for practical use. In this work, a novel strategy is developed to address this predicament by leveraging the hydrophobicity and gas barrier of hydrogenated hydroxyl-terminated polybutadiene (HHPB). The dynamic oxime-carbamate bonds derived from 2, 4-pentanedione dioxime (PDO) enable the elastomer to exhibit surface self-repairability upon applied mild heat and achieve ~99.5% mechanical self-healing efficiency. The mechanical properties remained nearly intact after 30-d exposure to thermal oxidation, xenon lamp, acids, bases, and salts. Gas permeability, positron annihilation lifetime spectroscopy (PALS), and contact angle measurements reveal the pivotal role of gas barrier, free volume, and hydrophobicity in blocking undesirable molecules and ions which effectively protects the elastomer from deterioration. HHPB-PU also exhibits excellent adhesion to steel substrate. The shear strength achieves (3.02 ± 0.42) MPa after heating at 80 °C for 4 h, and (3.06 ± 0.2) MPa after heating at 130 °C for 0.5 h. Regarding its outstanding anti-corrosive and weatherproof performances, this self-healable elastomer is a promising candidate in surface-protective applications.     

In vitro degradation of poly(ester-urethanes) for biomedical applications

Degradation studies on a series of polyesterurethanes having different compositions of hard and soft blocks have been performed utilizing an accelerated test method. Degradation was followed by titrimetry, mass loss, mechanical properties and infrared spectroscopy. As the number of methylene groups present within the polyester moiety was increased, the resistance to degradation also increased. The presence of an aromatic component in the hard block reduced the rate of hydrolysis but the degradation in mechanical properties was accelerated.     

Graphene foam/carbon nanotube/poly(dimethyl siloxane) composites for exceptional microwave shielding

Highly porous poly(dimethyl siloxane) (PDMS) composites containing cellular-structured microscale graphene foams (GFs) and conductive nanoscale carbon nanotubes (CNTs) are fabricated. The unique three-dimensional, multi-scale hybrid composites with inherent percolation and a high porosity of 90.8% present a remarkable electromagnetic interference shielding effectiveness (EMI SE) of ∼75 dB, a 200% enhancement against 25 dB of the composites made from GFs alone with the same graphene content and porosity. The corresponding specific EMI SE measured against the composite density is 833 dB cm³/g. These values are among the highest for all carbon filler/polymer composites reported thus far. Significant synergy arises from the hybrid reinforcement structure of the composites: the GFs drive the incident microwaves to be attenuated by dissipation of the currents induced by electromagnetic fields, while the CNTs greatly enhance the dissipation of surface currents by expanding the conductive networks and introducing numerous interfaces with the matrix.     

Block copolymers of L-lactide and poly(ethylene glycol) for biomedical applications

Poly (L-lactide)-poly (oxyethylene)-poly (L-lactide) block copolymers obtained in bulk, by a ring opening mechanism, from poly (ethylene glycol)s (PEG)s and L-lactide (LA), at 120–140°C, in the absence of added catalysts are described. By using PEGs with different molecular masses, 3000 and 35000, respectively, and varying the initial molar ratio LA to PEG, two series of copolymers with different molecular masses, relative length of blocks and hydrophilicity were obtained. Physico-chemical characterization of the copolymers had been previously performed. The morphological characteristics of the copolymers were investigated by means of X-ray diffractometry, optical and scanning electron microscopy. The biological properties of the materials were determined by evaluating their cytotoxicity, cytocompatibility, hemocompatibility and degradability using different standard tests. The results obtained indicate that the block copolymers synthesized may be useful for biomedical applications, in particular as resorbable drug vehicles. The materials are brittle and their mechanical properties are not appropriate for implant devices.     

Interpenetrating polymer networks based on polyol modified castor oil polyurethane and poly(2-hydroxyethylmethacrylate): Synthesis, chemical, mechanical and thermal properties

Interpenetrating polymer networks (IPNs) of glycerol modified castor oil polyurethane (GC-PU) and poly[2-hydroxyethylmethacrylate] (PHEMA) were synthesized using benzoyl peroxide as initiator and N,N-methylenebis acrylamide as crosslinker. GC-PU/PHEMA interpenetrating polymer networks were obtained by transfer moulding. These were characterized with respect to their resistance to chemical reagents and mechanical properties such as tensile strength, per cent elongation and shore A hardness. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were undertaken for thermal characterization. The changes in NCO/OH ratio and GC-PU/PHEMA composition on the properties of the IPNs were studied.     

Macroporous interpenetrating cryogel network of poly(acrylonitrile) and gelatin for biomedical applications

Cryogels are supermacroporous gel network formed by cryogelation of appropriate monomers or polymeric precursors at subzero temperature. The beneficial feature of this system is a unique combination of high porosity with adequate mechanical strength and osmotic stability, due to which they are being envisaged as potential scaffold material for various biomedical applications. One of the important aspect of cryogel is simple approach by which they can be synthesized and use of aqueous solvent for their synthesis which make them suitable for different biological applications. Various modifications of the cryogels have been sought which involves coupling of various ligands to its surfaces, grafting of polymer chain to cryogel surface or interpenetrating networks of two or more polymers to form a cryogel which provides diversity of its applications. In the following work we have synthesized full interpenetrating network of polyacrylonitrile (PAN)-gelatin with varied gelatin concentration. The PAN-gelatin cryogel interpenetrating network is macroporous in nature and has high percentage swelling equilibrium in the range of 862-1,200 with a flow rate greater than 10 ml/min, which characterizes the interconnectivity of pores and convective flow within the network. PAN-gelatin interpenetrating cryogel network has good mechanical stability as determined by Young's modulus which varies from 123 kPa to 819 kPa depending upon the polymer concentration. Moreover they are shown to be biocompatible and support cell growth within the scaffolds.     

Macroporous interpenetrating cryogel network of poly(acrylonitrile) and gelatin for biomedical applications

Cryogels are supermacroporous gel network formed by cryogelation of appropriate monomers or polymeric precursors at subzero temperature. The beneficial feature of this system is a unique combination of high porosity with adequate mechanical strength and osmotic stability, due to which they are being envisaged as potential scaffold material for various biomedical applications. One of the important aspect of cryogel is simple approach by which they can be synthesized and use of aqueous solvent for their synthesis which make them suitable for different biological applications. Various modifications of the cryogels have been sought which involves coupling of various ligands to its surfaces, grafting of polymer chain to cryogel surface or interpenetrating networks of two or more polymers to form a cryogel which provides diversity of its applications. In the following work we have synthesized full interpenetrating network of polyacrylonitrile (PAN)-gelatin with varied gelatin concentration. The PAN-gelatin cryogel interpenetrating network is macroporous in nature and has high percentage swelling equlibirium in the range of 862–1,200 with a flow rate greater than 10 ml/min, which characterizes the interconnectivity of pores and convective flow within the network. PAN-gelatin interpenetrating cryogel network has good mechanical stability as determined by Young’s modulus which varies from 123 kPa to 819 kPa depending upon the polymer concentration. Moreover they are shown to be biocompatible and support cell growth within the scaffolds.     

Effects of surface-functionalized multi-walled carbon nanotubes on the properties of poly(dimethyl siloxane) nanocomposites

The effects of surface-functionalized multi-walled carbon nanotubes (MWNTs) on the properties of poly(dimethyl siloxane) (PDMS) nanocomposites are investigated in the present study. The surface functionalization of MWNTs is carried out by diphenyl-carbinol functionalization followed by reaction with multifunctional silane, 3-aminopropyltriethoxisilane. Fourier transform infrared spectroscopy (FT-IR) and energy dispersion spectroscopy (EDS) analysis are used to confirm the presence of diphenyl-carbinol and silane on the surface of the MWNTs. The effects of the MWNTs’ surface treatment on the thermal and electrical properties of poly(dimethyl siloxane)-based (PDMS) nanocomposites are also studied. The results show that the grafting of silane molecules onto diphenyl-carbinol-functionalized MWNTs (SD-MWNTs) improves the dispersion of MWNTs in PDMS; this subsequently enhances the thermal conductivity and dynamic mechanical properties as compared to those containing unmodified (U-MWNTs) and diphenyl-carbinol-functionalized MWNTs (D-MWNTs). The electrical conductivity of the nanocomposites is shown to decrease due to the wrapping of MWNTs with non-electrical-conducting organic materials.     

Polyurethane/poly(hydroxyethyl methacrylate) semi-interpenetrating polymer networks for biomedical applications

The thermodynamic miscibility, morphology, phase distribution, mechanical properties, surface properties, water sorption, bacterial adhesion and cytotoxicity of semi-interpenetrating polymer networks (semi-IPNs) based on crosslinked polyurethane (PU) and poly(hydroxyethylmethacrylate) (PHEMA) were studied to give an insight into their structure and properties. The free energies of mixing of the two polymers in semi-IPNs have been determined and it was shown that the values are positive and depend on the amount of PHEMA. This demonstrates that the components are immiscible, the extent of which is dependent upon variations in composition. The morphology of the semi-IPNs was analyzed with scanning electron microscopy and tapping mode atomic force microscopy (TMAFM). The micrographs of the semi-IPNs and TMAFM phase images indicated that distinct phase separation at the nanometer scale is observed. The mechanical properties reflect the changes in structure of semi-IPNs with composition. The stress at break increases from 3.4 MPa to 23.9 MPa, and the Young’s modulus from 12.7 MPa up to 658.5 MPa with increasing amounts of PHEMA, but strain at break has a maximum at 40.4% PHEMA. The bacterial adhesion and cytotoxicity data suggest that semi-IPNs with PHEMA content above 22% may be used for biomedical material applications.     

氨基硅油改性聚丁二烯聚氨酯脲的合成与性能

过量的甲苯二异氰酸酯（TDI0加入氨乙基氨丙基聚二甲基硅氧烷（AEAPS）,端羟基聚丁二烯（HTPB）中制成预聚体,以3,3′－二氯－4,4′二苯基甲烷二胺（MOCA）为固化剂,合成了一系列不同含量的硅氧烷改性聚丁二烯聚氨酯脲,通过接触角,表面光电子能谱（ESCA）测试,应用应变,动态力学热分析,结果表明,氨基硅油在聚氨酯脲表面明显富集,聚丁二烯聚氨酯脲的力学性能改变不大。     

含亚苯基甲基苯基硅树脂的合成及表征

以甲基、苯基氯硅烷和1,4-二(羟基二甲基硅基)苯为原料,采用水解-缩聚法合成了主链含亚苯基的甲基苯基有机硅树脂,并对其结构和性能进行了研究。红外光谱(FT-IR)和核磁共振(29Si NMR)分析表明,亚苯基被成功引入到硅树脂主链中。差式量热扫描(DSC)分析表明硅树脂为均聚物。热失重(TG)结果表明,在N2氛中,硅树脂在450℃失重约1%,优于普通甲基苯基硅树脂。硅树脂的清漆涂层在300℃下使用时,附着力、抗冲击、柔韧性能仍保持良好。电化学阻抗分析(EIS)结果表明,硅树脂的清漆涂层常温固化后、经300℃的高温烘烤后都具有优良的耐腐蚀性能。     

Silicone-modified cellulose. Crosslinking of cellulose acetate with poly[dimethyl(methyl-H)siloxane] by Pt-catalyzed dehydrogenative coupling

Cellulose acetate was reacted in different ratios with poly[dimethyl(methyl-H)siloxane] containing 25 mol% Si–H side groups along the chain. A dehydrocoupling reaction between Si–H and C–OH groups occurred in presence of Karstedt’s catalyst, leading to the formation of Si–O–C bond, as proved by FTIR spectra, thus crosslinking the cellulose derivative. The networks were processed as films by casting before the end of the reaction and were investigated by different techniques to emphasize the morphology, thermal, dielectric and surface properties developed in correlation with the ratio between the two involved components (cellulose and siloxane derivatives). A decrease of the dielectric constant values of cellulose acetate was noticed throughout the studied frequency and temperature range as a result of crosslinking.     

Anti-microbial and anti-corrosive poly (ester amide urethane) siloxane modified ZnO hybrid coatings from Thevetia peruviana seed oil

The utilization of renewable resources for the development of organic coatings is a viable means of creating alternatives to petroleum-based chemicals which are not eco-friendly. This paper reports the synthesis of polyesteramide–urethane–silica–zinc oxide hybrid coatings from Thevetia peruviana seed oil (TPSO). The periphery of ZnO nano-particles is modified with 3-aminopropyltrimethoxysilane to prepare silica grafted ZnO composite particles. The TPSO based polyesteramide was reacted with 4,4′-diisocyanatodicyclohexylmethane in presence of siloxane modified ZnO to obtain –NCO terminated polyesteramide–urethane–silica ZnO prepolymer. These hybrid pre-polymers were casted on tin foil and cured under atmospheric moisture to obtain eco-friendly, moisture cured polyesteramide–urethanes–silica–zinc oxide hybrid coating films. The synthesized polyester and polyurethane formation was confirmed by using FT-IR and NMR spectroscopic techniques. The resultant hybrid coating films were characterized by using FT-IR, TGA, DSC, SEM, corrosion resistance and microbial resistance. Results confirm that with increase of siloxane modified ZnO content in the polyurethane matrix thermal stability, glass transition temperature and corrosion resistance improved. The antibacterial activity shows that the hybrid films exhibit excellent resistance towards Escherichia coli and Staphylococcus aureus. The salt spray test on coated panel samples show good corrosion resistance properties.     

Microfluidic characterization and continuous separation of cells and particles using conducting poly(dimethyl siloxane) electrode induced alternating current-dielectrophoresis

This paper presents a poly(dimethyl siloxane) (PDMS) polymer microfluidic device using alternating current (ac) dielectrophoresis (DEP) for separating live cells from interfering particles of similar sizes by their polarizabilities under continuous flow and for characterizing DEP behaviors of cells in stagnant flow. The ac-DEP force is generated by three-dimensional (3D) conducting PDMS composite electrodes fabricated on a sidewall of the device main channel. Such 3D PDMS composite electrodes are made by dispersing microsized silver (Ag) fillers into PDMS gel. The sidewall AgPDMS electrodes can generate a 3D electric field that uniformly distributes throughout the channel height and varies along the channel lateral direction, thereby producing stronger lateral DEP effects over the entire channel. This allows not only easy observation of cell/particle lateral motion but also using the lateral DEP force for manipulation of cells/particles. The former feature is used to characterize the frequency-dependent DEP behaviors of Saccharomyces cerevisiae (yeast) and Escherichia coli (bacteria). The latter is utilized for continuous separation of live yeast and bacterial cells from similar-size latex particles as well as live yeast cells from dead yeast cells. The separation efficiency of 97% is achieved in all cases. The demonstration of these functions shows promising applications of the microfluidic device.     

Patterning of TiO2 particles on poly(dimethyl siloxane) films by using proton irradiation and liquid-phase deposition process

Micropatterning of titanium dioxide (TiO2) on the surface of thin poly(dimethyl siloxane) (PDMS) films was described by means of proton irradiation and liquid-phase deposition (LPD) techniques. The surface of thin PDMS films was irradiated with accelerated proton ions through a pattern mask in the absence or presence of oxygen in order to create hydrophilically/hydrophobically patterned surfaces. The results of the surface analysis revealed that the PDMS films irradiated at the fluence of 1 x 10(15) ions cm-2 in the presence of oxygen showed the highest hydrophilicity. The LPD of TiO2 particles on the patterned PDMS film surface showed a selective deposition of TiO2 on the irradiated regions, leading to well defined TiO2 micropatterns. The crystal structure of the formed TiO2 films was found to be in an anatase phase by X-ray diffraction analysis. This process can be applied for patterning various metal and metal oxide particles on a polymer substrate.     

Domain-controlled polymer alloy composed of segmented polyurethane and phospholipid polymer for biomedical applications

Segmented polyurethane(SPU)s are block polymers which have a good elastic property and thermoplasticity. However, the biocompatibility of SPU is not sufficient, and a living organism rejects the SPU as a foreign material. Thus, some modification is needed to provide excellent biocompatibility and retain the good physical characteristics of the SPUs. In this study, we blended the 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer with SPU to prepare an SPU/MPC polymer alloy. We investigated the effects of the molecular weight (M_w) of the MPC polymer on the microdomain structure and mechanical property of the polymer alloy. When the MPC polymer with a higher M_w was blended with SPU, the polymer alloy underwent a reduction in mechanical strength. On the other hand, even when the lower M_w of the MPC polymer was blended with SPU, differential scanning calorimetric analysis revealed that the MPC polymer chains did not disrupt the crystallinity of the hard segments of SPU and the polymer alloy could maintain its physical properties the same as that of the original SPU. We investigated the adsorption of immunoglobulin (IgG) on the surface of the polymer alloy for evaluation of its fundamental biocompatibility. The SPU/MPC polymer alloy lowered the amount of adsorbed IgG compared to that on SPU. This means that the blending of the MPC polymer significantly improved the biocompatibility of the SPU. We succeeded in preparing an SPU/MPC polymer alloy that possesses both the good mechanical property of SPU and the improved biocompatibility using MPC polymers.     

Domain-controlled polymer alloy composed of segmented polyurethane and phospholipid polymer for biomedical applications

Segmented polyurethane(SPU)s are block polymers which have a good elastic property and thermoplasticity. However, the biocompatibility of SPU is not sufficient, and a living organism rejects the SPU as a foreign material. Thus, some modification is needed to provide excellent biocompatibility and retain the good physical characteristics of the SPUs. In this study, we blended the 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer with SPU to prepare an SPU/MPC polymer alloy. We investigated the effects of the molecular weight (M_w) of the MPC polymer on the microdomain structure and mechanical property of the polymer alloy. When the MPC polymer with a higher M_w was blended with SPU, the polymer alloy underwent a reduction in mechanical strength. On the other hand, even when the lower M_w of the MPC polymer was blended with SPU, differential scanning calorimetric analysis revealed that the MPC polymer chains did not disrupt the crystallinity of the hard segments of SPU and the polymer alloy could maintain its physical properties the same as that of the original SPU. We investigated the adsorption of immunoglobulin (IgG) on the surface of the polymer alloy for evaluation of its fundamental biocompatibility. The SPU/MPC polymer alloy lowered the amount of adsorbed IgG compared to that on SPU. This means that the blending of the MPC polymer significantly improved the biocompatibility of the SPU. We succeeded in preparing an SPU/MPC polymer alloy that possesses both the good mechanical property of SPU and the improved biocompatibility using MPC polymers.     

Studies on biodegradable and crosslinkable poly(castor oil fumarate)/poly(propylene fumarate) composite adhesive as a potential injectable biomaterial

Microparticles (MP) spray dried from hydroxyapatite (HA) nanoparticle (NP) sugar suspensions are currently under development as a prolonged release vaccine vehicle. Those with a significant sugar component cannot be sectioned by ultramicrotomy as resins are excluded by the sugar. Focused ion beam (FIB) milling is the only method to prepare thin sections that enables the inspection of the MPs ultrastructure by transmission electron microscopy (TEM). Several methods have been explored and we have found it is simplest to encapsulate MPs in silver dag, sandwiched between gold foils for FIB-milling to enable multiple MPs to be sectioned simultaneously. Spray dried MPs containing 80% sugar have an inter-nanoparticle separation that is comparable with NP size (~50 nm). MPs spray dried with 50% sugar or no sugar are more tightly packed. Nano-porosity in the order of 10 nm exists between NPs. MPs spray dried in the absence of sugar and sectioned by ultramicrotomy or by FIB-milling have comparable nanoscale morphologies. Selected area electron diffraction (SAED) demonstrates that the HA remains (substantially) crystalline following FIB-milling.     

Modification of polyurethane with wholly-rigid poly (m-phenylene isophthalamide)

Flexible polyurethane (PU) was reinforced by wholly-rigid aromatic polyamide poly (m-phenylene isophthalamide) (PmlA) (Nomex) by physical polyblending and chemical copolymerization. Three polyurethane elastomers were blended physically with various amounts of high molecular weight Nomex to form twelve PU/Nomex polyblends in order to modify their physical properties. Also three multiblock copolyamides (PU-Nomex)were synthesised with a low molecular weight diamine-terminated Nomex prepolymer as a hydrogen donor for chain extending. From differential scanning calorimetry and Rheovibron measurements it was shown that both the polyblends and multiblock copolyamides exhibited a glass transition temperature under 0 °C and had a higher storage modulus, E, than those of the polyurethane. Scanning electron microscopy revealed that the polyblends and multiblock copolyamides had a dispersed phase structure. From the wide-angle X-ray diffraction pattern of the polyurethane and multiblock copolyamides it was found that the degree of stress-induced crystallization was dependent on the composition of the soft and hard segments and also the degree of its stretching. With regard to mechanical properties, it was found that both the tensile strength and elongation of the multiblock copolyamides had a more significant reinforcing effect than those of the polyblends and polyurethanes.