Influence of fluorine-containing side chain on the properties of waterborne polyurethane-urea

In order to prepare waterborne polyurethane with excellent water resistance and thermodynamic properties, a series of side chain fluorinated waterborne polyurethane-urea (FWPU-UA) was synthesized with polytetramethylene ether glycol, N-(2-methyl-1,3-propanediol-2′-)-perfluoro-1-butanesulfonyl amine (NPBA), isophorone diisocyanate, and isophoronediamine. With the increase of NPBA content, the weight loss temperature, glass transition temperature, and tensile strength of FWPU-UA were all improved. Gaussian fitting analysis of infrared data and density functional theory simulation proved that the introduction of fluorine side chains increased the interaction of hydrogen bonding in the FWPU-UA. X-ray photoelectron spectroscopy analysis indicated that the aggregation of fluorine atoms on the surface of film were caused by the migration and enrichment of fluorine side chains. Furthermore, the water resistance of polyurethane-urea film could be significantly improved by adding a small amount of NPBA, and the seven-day water absorption rate of polyurethane-urea film was reduced from 30.13% to 12.55%.     

A Biologically Muscle-Inspired Polyurethane with Super-Tough,Thermal Reparable and Self-Healing Capabilities for Stretchable Electronics

Polymeric elastomers play an increasingly important role in the development of stretchable electronics. A highly demanded elastic matrix is preferred to own not only excellent mechanical properties, but also additional features like high toughness and fast self-healing. Here, a polyurethane (DA-PU) is synthesized with donor and acceptor groups alternately distributed along the main chain to achieve both intra-chain and inter-chain donor-acceptor self-assembly, which endow the polyurethane with toughness, self-healing, and, more interestingly, thermal repair, like human muscle. In detail, DA-PU exhibits an amazing mechanical performance with elongation at break of 1900% and toughness of 175.9 MJ m⁻³. Moreover, it shows remarkable anti-fatigue and anti-stress relaxation properties as manifested by cyclic tensile and stress relaxation tests, respectively. Even in case of large strain deformation or long-time stretch, it can almost completely restore to original length by thermal repair at 60 °C in 60 s. The self-healing speed of DA-PU is gradually enhanced with the increasing temperature, and can be 1.0–6.15 µm min⁻¹ from 60 to 80 °C. At last, a stretchable and self-healable capacitive sensor is constructed and evaluated to prove that DA-PU matrix can ensure the stability of electronics even after critical deformation and cut off.     

Magnetically Guidable Proteinaceous Adhesive Microbots for Targeted Locoregional Therapeutics Delivery in the Highly Dynamic Environment of the Esophagus

The esophagus is a tubular-shaped muscular organ where swallowed fluids and muscular contractions constitute a highly dynamic environment. The turbulent, coordinated processes that occur through the oropharyngeal conduit can often compromise targeted administration of therapeutic drugs to a lesion, significantly reducing therapeutic efficacy. Here, magnetically guidable drug vehicles capable of strongly adhering to target sites using a bioengineered mussel adhesive protein (MAP) to achieve localized delivery of therapeutic drugs against the hydrodynamic physiological conditions are proposed. A suite of highly uniform microparticles embedded with iron oxide (IO) nanoparticles (MAP@IO MPs) is microfluidically fabricated using the genipin-mediated covalent cross-linking of bioengineered MAP. The MAP@IO MPs are successfully targeted to a specific region and prolongedly retained in the tubular-structured passageway. In particular, orally administered MAP@IO MPs are effectively captured in the esophagus in vivo in a magnetically guidable manner. Moreover, doxorubicin (DOX)-loaded MAP@IO MPs exhibit a sustainable DOX release profile, effective anticancer therapeutic activity, and excellent biocompatibility. Thus, the magnetically guidable locomotion and robust underwater adhesive properties of the proteinaceous soft microbots can provide an intelligent modular approach for targeted locoregional therapeutics delivery to a specific lesion site in dynamic fluid-associated tubular organs such as the esophagus.     

Improved one-dimensional beam model for unbalanced composite single-lap joint

An analytical nonlinear solution was provided for unbalanced composite single-lap joint (CSLJ) using an improved one-dimensional beam model, which incorporated the effect of bending–tension coupling. The bending–tension coupling stiffness was introduced to characterize the coupling bending and tension behavior induced by the un-symmetric stacking sequence of composite laminates. The governing differential equations captured the bending–tension coupling behavior and the geometrically nonlinear features were constructed based on the displacement compatibility conditions of flexible interface. The transverse deformation in overlap region, edge moment factors and adhesive stress distributions for the unbalanced CSLJ with inflexible, intermediate flexibility and flexible adhesive can be determined by the present one-dimensional beam model. The accuracy of the present model was validated by the comparison with nonlinear finite element model. The effect of bending–tension coupling on edge moment factors and peak values of adhesive stresses was shed light on with the present model.     

单组份聚氨酯炮孔填塞剂应用性试验

炮孔填塞是爆破施工过程中的一个关键环节,也是践行精细爆破设计理论的重要措施。传统的炮泥填塞存在着诸多不足,为此,研制了以聚氨酯为基材的TK炮孔填塞剂,通过大量基础性能研究和隧道现场工业性试验,论证了其作为炮孔填塞材料可降低炸药单耗,提高单循环进尺和炮孔利用率,减小空气冲击波、爆破噪声等有害效应的影响,且是安全可靠的。TK炮孔填塞剂优良的填塞效果、方便快捷的施工方法及显著的经济效益,方便于在爆破工程中推广应用。     

Porous polyurethane film fabricated via the breath figure approach for sustained drug release

The breath figure (BF) method is an effective process for fabricating porous polymeric films. In this study, we fabricated porous polymer films from thermoplastic polyurethane (PU) through static BF with CHCl₃ as a solvent under 55–80% relative humidity. The porous PU films were prepared within various pore structures and sizes, which were adjustable, depending on the fabrication conditions. The humidity and exposure time were examined as variable parameters affecting the surface morphology, wettability, and cytotoxicity. Atorvastatin calcium, a hyperlipidemic agent, was loaded into the porous films during the casting process, and the drug-loading and drug-releasing behaviors of the porous PU membranes were evaluated. Approximately 60–80% of the drug was released in 14 days. The films exhibited sustained drug-release performances because of the hydrophobicity and nonbiodegradable nature of PU for perivascular drug administration. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47658.     

Hydrolysis-resistant polyurethane elastomers synthesized from hydrophobic bio-based polyfarnesene diol

Hydrolytic stability is an essential requirement for polyurethanes (PUs) that are used in highly humid and aqueous environments. In this study, hydrolysis-resistant PU elastomers (PUEs) are synthesized based on hydrophobic bio-based polyfarnesene diol (PFD), which contains unique “bottle brushes” structure (with long branched hydrocarbon side chains). The effect of hard segment (HS) content, ranging from 30 to 50%, on the morphology and properties of PUEs is investigated by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, tensile, water absorption, and contact angle measurements. The results show that there are prominent phase separations in the synthesized PUEs. The PUEs show a three-stage degradation process and two T_g, one is at about −66 °C and the other 61 °C, which are related to the soft segment and HS, respectively. Water contact angles of PUEs increase from 98.6 to 105.2° with the increasing of PFD structural unit fraction. After being immersed in deionized water for 30 days, PUEs show no significant degradation of both tensile strength and elongation at break, and mass changes of all samples are less than 0.5%. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47673.     

Effects of typical soybean meal type on the properties of soybean-based adhesive

In order to effectively apply soybean meal for the preparation of water-resistant soybean-based adhesives for plywood, the effects of three typical soybean meal products, namely, low-temperature soybean meal (LM), high-temperature soybean meal (HM), and physical soybean meal (PM), on the properties of soybean-based adhesive were investigated. The results indicated that the number of reactive groups in the three soybean meals followed the order LM > HM > PM, which in turn led to various crosslinking densities when these soybean meals were crosslinked by epichlorohydrin-modified polyamide (EMPA) during the curing process. The LM soybean adhesive had 6.6% higher soaking bond strength and 16.5% higher boiling-dry-boiling bond strength than the HM soybean adhesive, and 19% higher soaking bond strength and 33% higher boiling-dry-boiling bond strength than the PM soybean adhesive, respectively. These three soybean meals could be used to prepare soybean adhesives for interior-use plywood because all plywood panels bonded with their adhesives passed a water-soaking test at 63 °C for 3 h, but only the LM soybean adhesive achieved the desired water resistance for floor-base plywood. Among the three evaluated soybean meals, LM was the most promising raw material for the preparation of soybean-based adhesive because of a greater number of reactive groups, higher crosslinking density, and superior bond strength. Plywood panel bonded with HM soybean adhesive had a water resistance lower than, but very close to, the standard required value (>0.8 MPa) for floor-base plywood.     

Surface modification of TiO2 particles with 12-hydroxy stearic acid and the effect of particle size on the mechanical and thermal properties of thermoplastic polyurethane urea elastomers

The efficient surface modification of titanium dioxide (TiO₂) particles with different sizes was first carried out with “water only method” (Appl. Surf. Sci. 2018, 447, 664–672) developed in our group using 12-hydroxy stearic acid (12-HSA) as the modifier. The 12-HSA-modified TiO₂ particles with different sizes were then used to explore their effect on the mechanical and thermal properties of a thermoplastic polyurethane urea (TPUU) elastomer with superior mechanical and thermal properties produced newly in our lab using nonsymmetric alicyclic diisocyanate and diamine. Orthogonal experimental results showed that the order of impact of each factor on the modification efficiency of TiO₂ particles was: Temperature > time > modifier content. It was found that, in the nanometer (≤100 nm) range, smaller particles were more helpful to enhance the tensile strength of the TPUU elastomer, while larger ones to increase more significantly the elongation at break. Besides, the TiO₂/polyurethane urea nanocomposites exhibited much better thermomechanical performance than the pristine TPUU elastomer, and the thermomechanical performance of the nanocomposites increased with decreasing particle size.     

Acoustic damping flexible polyurethane foams: Effect of isocyanate index and water content on the soundproofing

High-efficiency sound absorbing flexible polyurethane foams (FPUFs) are manufactured using nonpolar polyester resin, methylene diphenyl diisocyanate, and other reagents by one-shot bulk polymerization. In this study, the impact of the isocyanate index (90, 100, and 110) and water content (2.5 and 5%) on the microphase separation and soundproofing behavior of FPUFs are examined using atomic force microscopy, Fourier transform infrared spectroscopy, optical microscope, and an impedance tube device. The results reveal that the increase of the isocyanate index and water content leads to the increase of the cell size, cell size distribution, open-cell content, cell wall roughness, and microphase separation. Also, maximum sound absorption coefficient (α) reaches to 0.98 and the average of α in the frequency range of 1500–4000 Hz increases from 0.7 to 0.87 by increasing the water content from 2.5 to 5% and isocyanate index from 90 to 110; therefore, acoustic damping performance enhances up to 26.24% due to the synergic effects of microphase separation on the viscose media formation, open-cell content, cell wall roughness, cell size, and cell size distribution. In conclusion, FPUFs with an optimal amount of microphase separation and drainage flow can be a promising candidate for sound insulating materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47363.