Autonomous-Strengthening Adhesive Provides Hydrolysis-Resistance and Enhanced Mechanical Properties in Wet Conditions

The low-viscosity adhesive that is used to bond composite restorative materials to the tooth is readily damaged by acids, enzymes, and oral fluids. Bacteria infiltrate the resulting gaps at the composite/tooth interface, demineralize the tooth, and further erode the adhesive. This paper presents the preparation and characterization of a low-crosslink-density hydrophilic adhesive that capitalizes on sol-gel reactions and free-radical polymerization to resist hydrolysis and provide enhanced mechanical properties in wet environments. Polymerization behavior, water sorption, and leachates were investigated. Dynamic mechanical analyses (DMA) were conducted using water-saturated adhesives to mimic load transfer in wet conditions. Data from all tests were analyzed using appropriate statistical tests (α = 0.05). The degree of conversion was comparable for experimental and control adhesives at 88.3 and 84.3%, respectively. HEMA leachate was significantly lower for the experimental (2.9 wt%) compared to control (7.2 wt%). After 3 days of aqueous aging, the storage and rubbery moduli and the glass transition temperature of the experimental adhesive (57.5MPa, 12.8MPa, and 38.7 °C, respectively) were significantly higher than control (7.4MPa, 4.3 MPa, and 25.9 °C, respectively). The results indicated that the autonomic sol-gel reaction continues in the wet environment, leading to intrinsic reinforcement of the polymer network, improved hydrolytic stability, and enhanced mechanical properties.     

Plasma-Electrospinning Hybrid Process and Plasma Pretreatment to Improve Adhesive Properties of Nanofibers on Fabric Surface

Electrospun nanofiber mats are inherently weak, and hence they are often deposited on mechanically-strong substrates such as porous woven fabrics that can provide good structural support without altering the nanofiber characteristics. One major challenge of this approach is to ensure good adhesion of nanofiber mats onto the substrates and to achieve satisfactory durability of nanofiber mats against flexion and abrasion during practical use. In this work, Nylon 6 nanofibers were deposited on plasma-pretreated woven fabric substrates through a new plasma-electrospinning hybrid process with the objective of improving adhesion between nanofibers and fabric substrates. The as-prepared Nylon 6 nanofiber-deposited woven fabrics were evaluated for adhesion strength and durability of nanofiber mats by carrying out peel strength and flex resistance tests. The test results showed significant improvement in the adhesion of nanofiber mats on woven fabric substrates. The nanofiber-deposited woven fabrics also exhibited good resistance to damage under repetitive flexion. X-Ray photoelectron spectroscopy and water contact angle analyses were conducted to study the plasma effect on the nanofibers and substrate fabric, and the results suggested that both the plasma pretreatment and plasma-electrospinning hybrid process introduced radicals, increased oxygen contents, and led to the formation of active chemical sites on the nanofiber and substrate surfaces. These active sites helped in creating crosslinking bonds between substrate fabric and electrospun nanofibers, which in turn increased the adhesion properties. The work demonstrates that the plasma-electrospinning hybrid process of nanofiber mats is a promising method to prepare durable functional materials.     

Hybrid Microgels with Antibacterial Properties

In the present work, we have used aqueous microgels as containers for the deposition of silver nanoparticles (AgNPs). It has been shown that AgNPs can be effectively incorporated in the microgel interior during the in situ reduction of silver ions. Obtained hybrid microgels with variable AgNPs loading (from 1 to 12 wt.‐%) have been used as antibacterial agents for two bacteria types. The experimental results indicate that porous microgel structure allows the release of the silver ions from the AgNPs surface into an aqueous phase. This ensures effective reduction in the number of bacterial colonies in test plates and complete bacteria killing. The antibacterial efficiency of the microgel particles increases with AgNPs loading.

     

Synthesis and Characterization of Catechol-Containing Polyacrylamides with Adhesive Properties

In this study, a row of four analogous dopamine acryl- and methacrylamide derivatives, namely N-(3,4-dihydroxyphenyethyl) acrylamide, N-(3,4-dihydroxyphenyethyl) meth acrylamide, N-phenethyl methacrylamide, N-(4-hydroxyphenethyl) methacrylamide were synthesized and characterized by ¹H-NMR and ¹³C-NMR, followed by further solvent-based radical polymerization with N-hydroxyethyl acrylamide. All copolymers were characterized by ¹H-NMR, dynamic differential calorimetry, and gel permeation chromatography. The dependency of the used comonomer ratios to the molecular mass of the corresponding copolymers has been described. The synthesis of the various polymers serves as a feasibility study and provides important data for a future biometric application in the medical field. We synthesized N-(3,4-dihydroxyphenyethyl) acrylamide copolymer up to 80 mol% by free radical polymerization without using any protecting groups. All polymers show identical perfect adhesive properties by a simple scratch test. Further, the monomers were used as a photo reactive glue formulation to test its adherence to a medical titanium surface sample by tensile shear test.     

宽谱响应的混合碳纳米管光电探测器的制备和性能

基于表面等离子体增强的机理,利用银纳米线及半导体性单壁碳纳米管通过微纳加工手段制备了一种混合光电探测器,使用扫描电子显微镜、拉曼光谱分析仪、半导体装备分析仪及光电流谱技术等手段分别表征了制得混合光电探测器的微观形貌、响应光谱特征、光吸收性能和光响应性能及光电流光谱性能。结果表明,制得混合光电探测器沟道薄膜形貌均匀紧密,沉积成膜的碳纳米管直径约为1.4 nm,主要由半导体性单壁碳纳米管所构成。该杂化的光电探测器在可见光到近红外光谱范围内都表现出优良的宽谱响应特性。在近红外波段(约1 050 nm)下,混合光电探测器的光响应度可以达到34.9 mA/W,远优于无银纳米线光电探测器(7.45 mA/W)。并且混合器件在受到532 nm激光激发时的响应时间约为200μs,同时保持了超快的光响应性能。与无银纳米线光电探测器相比,混合光电探测器在宽谱范围内的光响应性能增强,其中,在光电流模式下的光响应性能最高增强7.5倍。     

Sealants with increased heat and cold resistances

Problems relevant to the development of new, and improvement of available, organosilicon sealants are set forth. Newly elaborated materials, which, in addition to enhanced heat and cold resistance, exhibit a number of other valuable properties and technological advantages, are described.     

烯丙基化碳纳米管改善丙烯酸酯压敏胶的性能

本文利用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)对多壁碳纳米管(MWNTs)进行修饰使其表面接枝上烯丙基官能团,与丙烯酸酯类单体进行原位聚合,制备了一种耐高温丙烯酸酯压敏胶(PSA)。 通过傅里叶变换红外光谱仪(FT-IR)、热重分析仪(TGA)和扫描电子显微镜(SEM)表征了MWNTs和丙烯酸酯PSA的结构与性能,探讨了改性MWNTs的质量分数对PSA耐热性能和粘接性能的影响。 结果表明,与未改性的丙烯酸酯PSA相比,当改性MWNTs的质量分数为1.5%时,改性丙烯酸酯PSA的耐热性能和粘接性能最佳,热分解温度从360 ℃提高到了382 ℃,耐热温度从80 ℃提高到了155 ℃,初粘力、持粘力和180°剥离强度分别从2 h和13.66 N/(25 mm)(12号小球)提高到了27 h和17.34 N/(25 mm)(17号小球)。     

CO2-based Biodegradable Supramolecular Polymers with Well-tunable Adhesive Properties

Supramolecular adhesives that enable debonding on-demand are of significant research interest for the development of adaptive and smart materials,yet,biodegrable supramolecular adhesives have been rarely exploited.Herein,telechelic,three-armed and four-armed CO₂-based polyols with close molecular weights and various content(or carbonate unite content)have been synthesized via a zinc-cobalt double metal cyanide complex catalyzed ring-opening copolymerization of CO₂ and propylene oxide,and further exploited as sustainable and biodegradable building blocks for supramolecular polymers(SMPs)with 2-ureido-4[1H]-pyrimidinone(UPy)motifs.Notably,the orthogonal modulation of the CO₂ content and the topology of CO₂-based polyols provide a unique opportunity to fine-tune the surface energy as well as the cohesive strength of the resulting CO₂-based SMPs.Notably,a three-armed SMP with 44%CO₂(3UPy-CO₂-44%)can well balance the trade-off between surface energy and cohesive strength,therefore bestowing a high adhesive strength of 7.5 and 9.7 MPa towards stainless steel and wood substrates respectively by testing the corresponding single lap joints.Moreover,the light-responsive adhesion property of 3UPy-CO₂-44%has been demonstrated exemplarily by blending with a UV sensitizer.     

石墨烯-二氧化钛复合催化剂对光催化性能的提高(英文)

以石墨烯氧化物和钛酸四丁酯为原料,通过水热法、无氧煅烧转晶合成了graphene-TiO2复合催化剂,并采用透射电镜、X射线衍射、拉曼光谱和X射线光电子能谱等手段对其进行了表征.结果表明,TiO2全部为锐钛矿晶型,呈纳米颗粒状附着在薄膜状的graphene表面.以亚甲基蓝为目标物,评价了graphene-TiO2催化剂的光催化性能.结果表明,graphene-TiO2的光催化降解能力明显优于相同方法制备的纳米TiO2颗粒,且具有较好的稳定性,空穴在降解过程中起主要作用,碱性溶液更有利于催化剂对MB的降解.     

Cryogenic Properties of a Polyurethane Adhesive*

Abstract

Differential thermal analysis (DTA), rebound resilience, and tensile proerties of a polyurethane adhesive were measured at cryogenic temperatures. The experimental methods are described, and test results which aid in evaluating the polyurethane for use at low temperatures are discussed. The DTA thermogram reveals that the glass transition temperature (T_g) is 235°K. The resilience profile indicates a resilience minimum (T_r) at 270°K and a frequency of 3800 Hz, which is consistent with the T_g measured by DTA. The low resilience below T_r, caused by secondary low-temperature transitions, shows the high energy absorption capabilities of the polyurethane. Considerable plastic flow at 195°K (40°K below T_g) is evidenced in the results of the tensile tests. The results of the three tests indicate that the polyurethane adhesive will perform well at low temperatures. The test methods should also be useful for evaluating the low-temperature performance of new polymers.     

聚氨酯/苯丙杂化乳液的合成、表征和特性及其在复膜胶中的应用

由聚氨酯(PU)预聚物、丙烯酸丁酯和苯乙烯单体的乳液聚合制备了聚氨酯-苯乙烯-丙烯酸酯(PUSA)杂化乳液,1H NMR显示所得的PU预聚物由烯烃基团封端。 TEM表明,其粒径约为150 nm,且为颜色深浅不同的两部分所组成。 随着PU含量的降低,杂化乳液的热稳定性增加。 DSC分析表明,所得杂化乳液有单一的Tg值,且处于聚氨酯和聚苯丙(PSA)乳液Tg值的中间。 当将得到的杂化乳液用于纸塑和塑塑复合时,其剥离强度分别为14.1 N/2.5 cm和12.2 N/2.5 cm。     

Hydrogel-Stiffening and Non-Cell Adhesive Properties of Amphiphilic Peptides with Central Alkylene Chains

Amphiphilic peptides bearing terminal alkyl tails form supramolecular nanofibers that are increasingly used as biomaterials with multiple functionalities. Insertion of alkylene chains in peptides can be designed as another type of amphiphilic peptide, yet the influence of the internal alkylene chains on self-assembly and biological properties remains poorly defined. Unlike the terminal alkyl tails, the internal alkylene chains can affect not only the hydrophobicity but also the flexibility and packing of the peptides. Herein, we demonstrate the supramolecular and biological effects of the central alkylene chain length inserted in a peptide. Insertion of the alkylene chain at the center of the peptide allowed for strengthened β-sheet hydrogen bonds and modulation of the packing order, and consequently the amphiphilic peptide bearing C2 alkylene chain formed a hydrogel with the highest stiffness. Interestingly, the amphiphilic peptides bearing internal alkylene chains longer than C2 showed a diminished cell-adhesive property. This study offers a novel molecular design to tune mechanical and biological properties of peptide materials.     

Porous Iron-and Cobalt-based Single Crystals with Enhanced Electrocatalysis Performance

Porous single crystals have the characteristics of long-range ordering structure and large specific surface area,which will significantly enhance their electrochemical performance.Here,we report a method different from the conventional porous single crystal growth method.This method is to directly convert single crystal precursors Co₃O₄ and Fe₃O₄ into Co₂N and Fe₂N,and then further reduces them to porous single crystals Co and Fe particles under H2/Ar atmosphere.The removal of O^2–in the lattice channel at the pressure of 25~300 torr and the temperature of 300~600℃ will promote nitridation of the single-crystalline Co–O and Fe–O frames,and further remove N^3–in H2/Ar atmosphere and recrystallize as Co and Fe.These porous single crystals exhibit enhanced electrochemical properties due to their structural coherence and highly active surface.We demonstrated that the aminobenzene yield was up to 91%and the selectivity reached 92%in the electrochemical reduction of nitrobenzene.     

Amorphous Silk Fibroin Nanofiber Hydrogels with Enhanced Mechanical Properties

Silk fibroin (SF) hydrogels have been engineered as universal substrates for various tissue regenerations and drug delivery. Although different physical and chemical crosslinking strategies are developed to form SF hydrogels with suitable performances, a significant gap remains to match specific requirements of various tissues. Here, amorphous SF nanofibers with more tyrosine residues outside the surfaces are used to replace traditional SF. Under the same crosslinking conditions, the use of amorphous SF nanofibers results in tougher properties, four times higher stiffness than that from traditional SF solutions. Unlike previous SF hydrogels, the SF nanofiber hydrogels show high tunability in wide modulus range of 0.6–160 kPa under low SF concentrations (below 5 wt%), showing improved mechanical match with various soft tissues. Better stability and cytocompatibility are also achieved, further confirming the superiority of the hydrogels as the tissue substrates. Therefore, a feasible strategy is developed to optimize the performances of SF hydrogel via tuning the nano‐structural state in aqueous solutions, which will enrich SF‐based hydrogel family in future.     

Hybrid Hydrogels Assembled from Phenylalanine Derivatives and Agarose with Enhanced Mechanical Strength

A roadblock for supramolecular hydrogels is their poor mechanical properties. Herein, to enhance the mechanical strength of supramolecular hydrogels, agarose(AG) was incorporated into the low molecular weight hydrogelator(G1). The results of scanning electron microscopy(SEM), circular dichroism(CD) and Fourier transform infrared spectroscopy(FTIR) prove that G1 gelators can self-assemble into cross-linked network together with AG. The mechanical properties of the gels are characterized by a rotary rheometer and the mechanical properties of the hybrid hydrogels(Hgel) can be significantly improved and may be further tuned by changing the ratio of the two components. For example, the elastic modulus of Hgel Ⅱ[m(G1):m(AG)=7:3] is about 2 times higher than that of G1 hydrogel. The results demonstrate that the mechanical property of hybrid supramolecular hydrogels can be adjusted through the formation of a cross-linked network.     

贵金属负载的棒状ZnO复合光催化剂的制备及其提升的光催化性能

以水热制备的ZnO纳米棒为基底,通过乙二醇液相还原法负载不同贵金属颗粒(Pt、Pd、Ru)构筑贵金属负载的ZnO纳米棒复合光催化剂。实验结果表明在制备条件相同时,Pt/ZnO样品中Pt颗粒尺寸较小,分布均匀;Pd/ZnO样品中Pd颗粒尺寸较大且团聚严重;Ru/ZnO样品则几乎没有Ru颗粒负载。在紫外光照射下降解亚甲基蓝的反应中,Pt/ZnO表现出最高的光催化性能,Pd/ZnO样品次之,而Ru/ZnO则表现出与ZnO纳米棒相似的光催化活性;表明小尺寸和大小均匀的贵金属颗粒对ZnO纳米棒的催化性能有着显著的提升作用。对Pt/ZnO来说,当Pt载量为3.2%时Pt/ZnO催化剂的光催化活性最高。     

钯纳米粒子的形貌可控合成与催化性能

借助于一种全新的表面活性剂N,N-dimethyloctadecylammonium bromide acetate sodium（OTAB-Na）,成功实现了对小尺寸钯纳米粒子微结构的控制。通过对合成条件的微扰,高度均匀且分散性良好的枝化结构和凹面体结构的钯纳米粒子被成功地制备。催化测试（利用氨硼烷作为氢化试剂来还原4-硝基苯酚为4-胺基苯酚）发现,钯纳米粒子的催化活性与其微观纳米结构相关,其中枝化结构的钯纳米粒子表现出了更为突出的催化性能。     

碱化辅助水热法制备高活性CdZnS可见光催化剂

利用碱化辅助水热法制备Cd Zn S固溶体可见光催化剂CZS-r[r=n(Na OH)/2n(Cd2++Zn2+)].采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)、氮气吸附-脱附仪和紫外-可见漫反射光谱仪(UV-Vis DRS)等对材料的晶体结构、微观结构及带隙能量(Eg)进行了表征.结果表明,碱化辅助能有效减小晶体的粒径,提高颗粒的分散性,增大材料的比表面积,并使得材料的带隙宽度变大,最值得注意的是,晶体中堆叠层错结构具有的独特界面电位能有效分离光生电子和空穴,阻碍其复合,从而显著提高材料的可见光催化制氢活性.材料的可见光(λ≥420 nm)催化还原制氢实验结果表明,CZS-0.5的5 h平均产氢速率为2154μmol/(h·g),是CZS-0[72μmol/(h·g)]的29.92倍.