Mussel-inspired cellulose-based adhesive with underwater adhesion ability

Inspired by mussels, a new cellulose-based (CTP) adhesive was fabricated by simply blending via cellulose nanofibrils (CNFs), tannic acid (TA), and polyethyleneimine (PEI), where the preparation method was green, facile, and simple. The structure and properties were examined by FT-IR, TGA, XRD, SEM, lap shear tensile, and water absorption tests. The results showed that chemical bonds, hydrogen bonds, and chain entanglement were formed among CNFs, TA, and PEI. Compared with the CNF adhesive, the dry shear strength of the CTP adhesive increased 103% to 392.2?±?32.2 kPa. And the wet shear strength of CTP adhesive increased from 0 kPa to 144.7?±?20.1 kPa, indicating that the CTP adhesive can be used in humid or even water environments. Meanwhile, the water absorption of CTP adhesive decreased from 37.9?±?14.1% to 12.8?±?5.9%. It was the introduction of catechol groups and physical–chemical interactions of three components that endow the CTP adhesive with improved dry and wet adhesion strength and water resistance. Moreover, the proposed CTP adhesive could be used on the surface of various materials, including rubber, plastic, paper, wood, metal, and glass. Overall, this work shows that the CTP adhesive has a wide range of application prospects.

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Shape-memory poly(p-dioxanone)-poly(ε-caprolactone)/sepiolite nanocomposites with enhanced recovery stress

Shape-memory poly(p-dioxanone)-poly(ε-caprolactone)/sepiolite (PPDO-PCL/OSEP) nanocomposites with different OSEP nanofiber loading were fabricated by chain-extending the PPDO-diol and PCL/OSEP precursors. The precursors and the composites were characterized by ¹H NMR, FT-IR, GPC, SEM and TEM. The results demonstrate that a part of PCL segments grafted on the surface of OSEP and composites display a fine dispersion of OSEP fiber in nanoscale with low OSEP content. The shape memory effect (SME) was evaluated by DMA, the results reveal that the PPDO-PCL/OSEP nanocomposites exhibit desirable shape-memory performance. The reinforcement of composites by incorporation of trace OSEP nanofiber evokes an effective improvement in shape-memory recovery stress.     

The influence of organo-modified sepiolite on the flame-retardant and thermal properties of intumescent flame-retardant polylactide composites

Polylactide (PLA) composites based on intumescent flame-retardant (IFR) and organo-modified sepiolite (OSEP) were prepared via direct melt compounding. The uniform dispersion of OSEP in the PLA matrix was observed by TEM, but some agglomerates still existed at the high loading. Tensile results showed that high loading of the conventional IFR led to a reduction in tensile strength of PLA composites; however, replacing a portion of the IFR with modified sepiolite in the PLA matrix improved this result. The thermal degradation temperature of the PLA/IFR/OSEP composites determined by thermogravimetric analysis was lower than that of neat PLA, as a consequence of the catalyzed carbonization induced by the addition of IFR and OSEP. The formulation with 13 mass% IFR and 2 mass% OSEP exhibited the highest LOI value of 32 vol% and also reached UL-94 V-0 rating in the vertical burning tests. Furthermore, the co-addition of IFR and OSEP gave rise to a significant reduction in peak heat release rate (PHRR) and total heat release (THR) of PLA composites during combustion, particularly in the case of PLA/IFR13/OSEP2 (82% reduction in PHRR and 69% in THR). The excellent fire resistance of PLA/IFR13/OSEP2 could be attributed to that IFR catalyzed carbonization of PLA to form the char, while OSEP resulted in further stabilization in the charred layers.     

CaSO_4晶须补强增韧聚氨酯弹性体机理的研究

提高聚氨酯弹性体的力学性能是聚氨酯研究领域里普遍关心的课题之一,一般采用刚性粒子和纤维类无机填料增强聚氨酯弹性体,但上述填料在提高强度的同时,会导致韧性降低,空易造成脆性断裂,因此填料能否同时补强增韧聚氨酯弹性体具有重要的实际应用价值,晶须是一种单晶纤维状材料,其直径极小,几乎不存在任何缺陷,由于内在的完整性,高度有序的原子排列,使其强度接近晶体理论－－原子间价键的强度,晶须凭借微细的直径、较短的长度、极高的强度,成为一种新型补强增韧剂,目前晶须的复合基体多为陶瓷基、金属基和树脂基,有关复合基体多为陶瓷基、金属基和树脂基,有关复合聚氨酯弹性体的理论及应用研究报道很少,本文制备了具有较高强度和韧性的CaSO4晶须／聚氨酯弹性体复合材料,通过微观分析揭示了CaSO4晶须对聚氨酯弹性体补强增韧的机理,并对其影响因素进行了讨论。     

Reusable antifouling viscoelastic adhesive with an elastic skin

Although the viscoelasticity or tackiness of a pressure-sensitive adhesive gives it strength owing to energy dissipation during peeling, it also renders it nonreusable because of structural changes such as the formation of fibrils, cohesive failure, and fouling. However, an elastic layer has good structural integrity and cohesive strength but low adhesive energy. We demonstrate an effective composite adhesive in which a soft viscoelastic bulk layer is imbedded in a largely elastic thin skin layer. The composite layer is able to meet the conflicting demands of the high peel strength comparable to the viscoelastic core and the structural integrity, reusability, and antifouling properties of the elastic skin. Our model adhesive is made of poly(dimethylsiloxane), where its core and skin are created by varying the cross-linking percentage from 2 to 10%.     

Influence of Backbone Structure on Properties of Directly Polymerized Phenoxy Resins from Epichlorohydrin and Various Aromatic Dihydric Phenols Monomers

A series of phenoxy resins was directly prepared through the polymerization of each of the various aromatic dihydric phenols and epichlorohydrin.FTIR and 1H NMR spectra were recorded to characterize the structures of the re-sins.The GPC curves were used to determine the molecular weight distribution.In addition,the thermal properties of the resins were studied with differential scanning calorimetry(DSC)and thermal gravimetric analysis(TGA).The thermal stabilities of the polymers increased with the content of the benzene ring,pendant group increasing or biphenyl groups emerging.The adhesive properties of the polymers were evaluated in terms of the lap shear strength with Fe-Fe adherends.The fracture mechanisms were determined by SEM observation and it was found that there was an important participation of cohesive fracture mechanisms.Also,it has been demonstrated that the extension of these micro-cohesive mechanisms is directly correlated with the adhesive strength.According to these results,the phenoxy resin containing biphenyl groups presented a higher adhesive strength and could improve the adhesive property of the epoxy/phenoxy system to a certain extent.     

Robust Hydrogel Adhesive with Dual Hydrogen Bond Networks

Hydrogel adhesives are attractive for applications in intelligent soft materials and tissue engineering, but conventional hydrogels usually have poor adhesion. In this study, we designed a strategy to synthesize a novel adhesive with a thin hydrogel adhesive layer integrated on a tough substrate hydrogel. The adhesive layer with positive charges of ammonium groups on the polymer backbones strongly bonds to a wide range of nonporous materials’ surfaces. The substrate layer with a dual hydrogen bond system consists of (i) weak hydrogen bonds between N,N-dimethyl acrylamide (DMAA) and acrylic acid (AAc) units and (ii) strong multiple hydrogen bonds between 2-ureido-4[1H]-pyrimidinone (UPy) units. The dual hydrogen-bond network endowed the hydrogel adhesives with unique mechanical properties, e.g., toughness, highly stretchability, and insensitivity to notches. The hydrogel adhesion to four types of materials like glass, 316L stainless steel, aluminum, Al₂O₃ ceramic, and two biological tissues including pig skin and pig kidney was investigated. The hydrogel bonds strongly to dry solid surfaces and wet tissue, which is promising for biomedical applications.     

Specific oxidants improve the wood bonding strength of soy and other plant flours

To meet newer environmental standards, modified plant proteins have been studied as no‐added formaldehyde wood adhesives for interior applications. Many methods have been developed to increase the wet strength of wood products bonded with soy adhesives. These methods involve modifying the soy in separate steps prior to formulating the adhesive or adding a polymerizable co‐reactant to the soy. We show that adding periodate, permanganate, or iodate to soy flour improved the strength of soy adhesive bonds in small‐scale testing and in plywood shear, especially when tested under wet conditions. Periodate improved the bond strength of other plant materials (lupine, canola, and cottonseed) but none of these produced as high of a wet strength as the soy flour. We investigated other oxidants with plant proteins. Permanganate was quite effective and iodate was somewhat effective, whereas nitric acid, chlorate, perchlorate, and bromate were not effective in increasing wet strength. The available data are consistent with oxidation of the carbohydrate–protein mixture in plant flours to provide adhesives with increased wet strength in wood bonds. This mechanism was also supported by the improved wet strength with the addition of dialdehydes (glyoxal and glutaraldehyde). The purified soy protein also gave strength improvement with periodate. Published 2019. This article is a U.S. Government work and is in the public domain in the USA. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1017–1023     

Surface orientation effect of asymmetric polyimide hollow fibers on their gas transport properties

In this study, we focused on the shear stress effects within a spinneret during hollow fiber spinning on the formation of the hollow fibers and their gas transport properties. We fabricated asymmetric polyimide hollow fibers with a completely defect-free thin skin layer using a dry/wet phase inversion process. The apparent calculated skin layer thickness of the hollow fiber was 280 nm and the O₂ permeance was 2.9×10⁻⁵ cm³ (STP)/(cm² s cmHg). Interestingly, the skin layer thickness was reduced at the high shear rate. In addition, the gas permeances and selectivities of the hollow fibers increased with the increasing shear rate. We concluded that the oriented skin layer of the hollow fiber induced by shear stress had a significant influence on the formation of the skin layer and its gas transport properties. From the ATR-IR spectra results, it was clear that the surface skin layer of the hollow fiber was parallel oriented.     

聚醚酰亚胺耐热大分子偶联剂增强增韧石英纤维/含硅芳炔复合材料

设计并制备了一种新型乙炔基封端聚醚酰亚胺大分子偶联剂(BDA-K),探究了其对石英纤维(QF)/含硅芳炔(PSA)复合材料界面增强增韧的效果.在常温下,加入大分子偶联剂的复合材料层间剪切强度、弯曲强度和缺口冲击强度分别提高了54.1%,59.0%和23.8%;在250℃时,层间剪切强度和弯曲强度保留率分别达到89.0%和89.6%,500℃时保留率分别达到63.3%和67.9%.傅里叶变换红外光谱和X光电子能谱分析结果表明,BDA-K参与PSA的交联固化,与QF发生有效化学键合;热重分析(TGA)结果表明,由于BDA-K的分子结构中引入耐热官能团酰亚胺环等,使其大分子偶联剂的T_(d5)达到489℃;扫描电子显微镜(SEM)结果表明,柔软的大分子层提供了适中的界面结合,使强度和韧性都得到提高.     

Diffusive Adhesives for Water-Rich Materials: Strong and Tunable Adhesion Beyond the Interface

It is notoriously difficult to adhere water-rich materials, such as hydrogels and biological tissues. Existing adhesives usually suffer from weak and nonadjustable adhesion strength, in part because the contact between the adhesive and substrate is largely restrained to the adhesive/substrate interface. In this study, we have attempted to overcome this shortcoming by developing a class of diffusive adhesives (DAs) that can extend adhesion deep into the substrate to maximize the adhesive/substrate contact. The DAs consist of hydrogel matrices and preloaded water-soluble monomers and crosslinkers that can diffuse extensively into the water-rich substrates after adhesive/substrate contact. Polymerization and crosslinking of the monomers are then triggered leading to a bridging network that interpenetrates the DA and substrate skeletons and topologically binds them together. This kind of adhesion, in the absence of adhesive/substrate covalent bonding, is of high strength and toughness, comparable to those of the best-performing natural and artificial adhesives. More importantly, we can precisely tune the adhesion strength on demand by manipulating the diffusion profile. It is envisioned that the DA family could be extended to include a large pool of hydrogel matrices and monomers, and that they could be particularly useful in biological and medical applications.     

Evolution of the elastic modulus at the interfaces of amorphous glassy polymers

The method of shear deformation of adhesive compounds based on high-molecular-mass glassy polymers is used for the pioneering analysis of changes in the elastic modulus as a function of contact time and temperature at the symmetric and asymmetric polymer-polymer interfaces. The kinetics of changes in the elastic modulus and strength of adhesive joints during shearing at a contact temperature below the actual glass-transition temperature of the polymer bulk is analyzed. The elastic modulus can be generally described in terms of the classical principle of the temperature-time analogy with respect to the conditions of the formation of adhesive joints. Molecular and thermoactivation mechanisms of the evolution of adhesive viscoelastic and strength characteristics are discussed.     

Simultaneously Improving the Tensile and Impact Properties of Isotactic Polypropylene with the Cooperation of co-PP and β-nucleating Agent through Pressure Vibration Injection Molding

In this article, crystalline morphology and molecular orientation of isotactic polypropylene(i PP), random copolymerized polypropylene(co-PP) and ?-nucleating agent(?-NA) composites prepared by pressure vibration injection molding(PVIM) have been investigated via polarized light microscopy, scanning electron microscopy, wide-angle X-ray diffraction and differential scanning calorimetry. Results demonstrated that the interaction between co-PP and i PP molecular chains was beneficial for the mechanical improvement and the introduction of ?-NA further improved the toughness of i PP. In addition, after applying the pressure vibration injection molding(PVIM) technology, the shear layer thickness increased remarkably and the tensile strength improved consequently. Thus, the strength and toughness of i PP/co-PP/?-NA composites prepared by PVIM were simultaneously improved compared to those of the pure i PP prepared by conventional injection molding(CIM): the impact toughness was increased by five times and tensile strength was increased by 9 MPa. This work provided a new method to further enhance the properties of i PP/co-PP composites through dynamic processing strategy.     

The influence of KH-550 on properties of ammonium polyphosphate and polypropylene flame retardant composites

Ammonium polyphosphate (APP)/polypropylene (PP) composites were prepared by melt blending and extrusion in a twin-screw extruder. APP was first modified by a silane coupling agent KH-550 then added to polypropylene. The surface modification of APP by the coupling agent decreased its water solubility and its interface compatibility with the PP matrix. Limiting oxygen index (LOI) and thermogravimetric analysis (TGA) were used to characterize the flame retardant property and the thermal stability of the composites. The addition of APP improved the flame retardancy of PP remarkably. The crystal structures of APP/PP composites were characterized by X-ray diffraction (XRD). The results indicated that β-crystal phase PP may be formed. The structures and morphologies of APP, KH-550/APP and APP/PP composites were characterized by field-emission scanning electron microscope (FESEM). The mechanical property tests showed good mechanical properties of composite materials. Compared with unmodified one, the impact strength, tensile strength and elongation of modified APP/PP were all improved.     

Enhanced wet adhesion and shear of elastomeric micro-fiber arrays with mushroom tip geometry and a photopolymerized p(DMA-co-MEA) tip coating

Using principles inspired by the study of naturally occurring sticky systems such as the micro- and nanoscale fibers on the toes of geckos and the adhesive proteins secreted by marine animals such as mussels, this study describes the development and evaluation of a novel patterned and coated elastomeric microfibrillar material for enhanced repeatable adhesion and shear in wet environments. A multistep fabrication process consisting of optical lithography, micromolding, polymer synthesis, dipping, stamping, and photopolymerization is described to produce uniform arrays of polyurethane elastomeric microfibers with mushroom-shaped tips coated with a thin layer of lightly cross-linked p(DMA-co-MEA), an intrinsically adhesive synthetic polymer. Adhesion and shear force characterization of these arrays in contact with a glass hemisphere is demonstrated, and significant pull-off force, overall work of adhesion, and shear force enhancements in submerged aqueous environments are shown when compared to both unpatterned and uncoated samples, as well as previously evaluated patterned and coated arrays with differing geometry. Such materials may have potential value as repeatable adhesives for wet environments, such as for medical devices.     

In situ photocrosslinkable hyaluronic acid‐based surgical glue with tunable mechanical properties and high adhesive strength

Hyaluronic acid (HA), a naturally occurring linear polysaccharide, has been widely used as a key biomaterial in a range of cosmetic and therapeutic applications. Its excellent biocompatibility and bio‐functions related to tissue regeneration encourage the development of HA‐based hydrogels to expand its applications. This study details an in situ forming surgical glue based on photocrosslinkable HA, providing tunable mechanical properties and firm tissue adhesion under wet and dynamic conditions. Depending on the degree of photocrosslinkable methacrylate groups in HA polymer chains, the mechanical properties of hyaluronate methacrylate (HAMA) hydrogels prepared by UV photocrosslinking was improved. Ex vivo adhesion tests revealed that HAMA hydrogels exhibited 3‐fold higher shear adhesive strength compared to gelatin methacryloyl hydrogels and achieved firm adherence to the porcine skin tissue for several weeks. The high adhesive strength of HAMA hydrogels, under dry and wet conditions, suggests that it may have great promise as a tissue adhesive. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 522–530     

Bovine Serum Albumin (BSA) as an adhesive for wet cellulose

Regenerated cellulose films were laminated using very thin layers of the protein Bovine Serum Albumin (BSA) as an adhesive. The wet delamination strength was measured as functions of pH, lamination time, temperature and pressure, as well as cellulose oxidation. Drying at elevated temperature (120 °C) was required for strong adhesion. Oxidation of the cellulose membranes to introduce surface carboxyl/aldehyde groups increased the wet delamination strength by 60%, implying that the peel failures happened at the protein/cellulose interface. The wet delamination force was independent of the pH and ionic strength of solutions used to apply the BSA; whereas adhesion decreased with increasing pH of the rewetting solution. Furthermore, the swelling of the BSA interplay region was also increased at high pH. It is proposed that covalent grafting of BSA onto the oxidized cellulose, and disulfide crosslinking within the protein layer contributed to wet adhesion.     

Bio-based tri-functional epoxy resin (TEIA) blend cured with anhydride (MHHPA) based cross-linker: Thermal,mechanical and morphological characterization

A novel renewable resource based tri-functional epoxy resin from itaconic acid (TEIA) was blended with petroleum based epoxy resin (DGEBA) and fabricated at different ratios. Then, it was by thermally cured with methylhexahydrophthalic anhydride (MHHPA) in presence of 2-methylimidazole (2-MI) catalyst. The tensile, modulus, strength of virgin epoxy resin (41.97 MPa, 2222 MPa) increased to 47.59 MPa, 2515 MPa, respectively, with the addition of 30% of TEIA. The fracture toughness parameter, critical stress intensity factor (K_IC) revealed enhancement of toughness in the TEIA bio-based blends system. The thermomechanical properties of TEIA (tri-functional epoxy resin from itaconic acid) modified petroleum-epoxy networks were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The fracture morphology was also studied by the scanning electron microscopy and atomic force microscopy respectively.     

Force variation of chlorinated butyl-rubber peeling from steel in the process of vulcanization

Vulcanization of an adhered layer with the use of low-temperature vulcanizing agents with different adhesion activities was carried out to increase the heat resistance and resistance to displacement of the adhesive tapes with different adhesive activity. It is shown that the force variation of the vulcanized adherent layer based on the chlorobutyl rubber and polymeric petroleum resin for peeling from steel depends on the measurement temperature: at 25°C, the peeling force decreases, while at 80°C it increases as compared with nonvulcanized adhesive. The observed changes are conditioned both by the increase of the cohesion strength of the adhered layer and by decrease of the elastic component in the layer peeling energy.     

Synergistic Covalent and Supramolecular Polymers for Mechanically Robust but Dynamic Materials

Nature has engineered delicate synergistic covalent and supramolecular polymers (CSPs) to achieve advanced life functions, such as the thin filaments that assist in muscle contraction. Constructing artificial synergistic CSP materials with bioinspired mechanically adaptive features, however, represents a challenging goal. Here, we report an artificial CSP system to illustrate the integration of a covalent polymer (CP) and a supramolecular polymer (SP) in a synergistic fashion, along with the emergence of notable mechanical and dynamic properties which are unattainable when the two polymers are formed individually. The synergistic effect relies on the peculiar network structures of the SP and CPs, which endow the resultant CSPs with overall improved mechanical performance in terms of the stiffness, strength, stretchability, toughness, and elastic recovery. Moreover, the dynamic properties of the SP, including self‐healing, stimuli‐responsiveness, and reprocessing, are also retained in the CSPs, thus leading to their application as programmable and tunable materials.