纤维素/全硫化弹性纳米粒子复合膜的制备与性能

利用碱脲溶剂低温溶解纤维素,在该体系中掺杂一定比例的全硫化羧基丁苯弹性纳米粒子,制备了纤维素/全硫化弹性纳米粒子复合膜.通过透射电镜、扫描电镜、WAXD、固体核磁共振、热分析和力学性能测试等对该复合膜的结构和性能进行了表征.结果表明,全硫化羧基丁苯弹性纳米粒子(CSB ENP)均匀的分散在具有微纳孔洞结构的纤维素基体中.CSB ENP的引入对纤维素再生过程中的结晶性影响不大.纤维素/全硫化弹性纳米粒子复合膜具有良好的透光性,并且热稳定性也有所提高.加入少量的CSB ENP可以增韧纤维素膜,且能保持良好的力学性能.当CSB ENP的含量为5 wt%时复合膜的断裂拉伸强度和断裂伸长率同时得到了提高.     

An Interfacial Dynamic Crosslinking Approach toward Catalyst-free and Mechanically Robust Elastomeric Vitrimer with a Segregated Structure

Elastomeric vitrimers with covalent adaptable networks are promising candidates to overcome the intrinsic drawbacks of conventional covalently-crosslinked elastomers; however, most elastomeric vitrimers show poor mechanical properties and require the addition of exogenous catalysts. Herein, we fabricate a catalyst-free and mechanically robust elastomeric vitrimer by constructing a segregated structure of sodium alginate (SA) in the continuous matrix of epoxidized natural rubber (ENR), and further crosslinking the composite by exchangeable hydroxyl ester bonds at the ENR-SA interfaces. The manufacturing process of the elastomeric vitrimer is facile and environmentally friendly without hazardous solvents or exogenous catalysts, as the abundant hydroxyl groups of the segregated SA phase can act as catalyst to activate the crosslinking reaction and promote the dynamic transesterification reaction. Interestingly, the segregated SA structure bears most of the load owing to its high modulus and small deformability, and thus ruptures preferentially upon deformation, leading to efficient energy dissipation.Moreover, the periodic stiffness fluctuation between rigid segregated SA phase and soft ENR matrix is beneficial to the crack-resisting. As a result,the elastomeric vitrimer manifests exceptional combination of catalyst-free, defect-tolerance, high tensile strength and toughness. In addition,the elastomeric vitrimer also exhibits multi-shape memory behavior which may further broaden its applications.     

Elastomeric/antibacterial properties in novel random Ricinus communis based-copolyesters

Poly(ricinoleic acid) (PRA), coming from the self-polycondensation of ricinoleic acid (RA), which derives from castor oil, is a very interesting polymer because of its intrinsic antimicrobial activity. However, its mechanical properties are insufficient for whatever application, thus copolymerization is required. In this work, two polyesters based on 1,3 propanediol (PD), such as poly(propylene terephthalate) (PPT) and poly(propylene isophthalate) (PPI), were chosen to prepare random copolyesters containing ricinoleate units. Different content of RA have been tested, such as 10 and 25 mol% respect to the comonomer (terephthalic or isophthalic dimethylester), to evaluate the lowest composition able to confer antibacterial activity. The materials were tested against Staphylococcus aureus and Escherichia coli, and 25 mol% of RA unit resulted to impart antimicrobial activity. Furthermore, thermal properties (DSC and TGA) as well as the elastomeric response of films were investigated. The copolymer PPI/PRA containing 10 mol% of RA presents very high elongation at break, around 1300%. Therefore, by tuning the RA amount it is possible to obtain outstanding elastomeric or antibacterial materials, suitable for textiles and/or film engineering applications.     

Testing methods for fatigue properties of rubber materials and vibration isolators

The main purpose of this investigation was to find out if laboratory fatigue tests in tension give results which can be useful in predicting the service life of a vibration isolator.Four natural rubber vulcanizates with different curing systems were used in the tests. The fatigue life in cyclic loading was determined in tension on standard tensile specimens (dumb-bells) and in shear on two types of vibration isolators. The results indicate that the information achieved in tension is relevant for estimating the service life of an isolator. Both relaxing and non-relaxing tests in tension were made and the relaxing tests seem to give the best correlation between dumb-bells and isolators. As the relaxing tests are also the least time-consuming they are to be preferred for material testing.     

Telechelic Polybutadienes or Polyisoprenes Precursors for Recyclable Elastomeric Networks

(Bis)furan‐telechelic, low‐molar‐mass polybutadienes and polyisoprenes are synthesized by controlled degradation of high molar mass polymers and chain‐end modifications yielding difunctional, trifunctional, or tetrafunctional polymers. Addition of a bismaleimide to the liquid‐modified polymer leads to the formation of a thermoreversible elastomeric network based on the Diels–Alder chemistry for the trifunctional or tetrafunctional polymers, whereas only chain extension occurs for the bifunctional one. Dynamic mechanical analyses or tensile tests are performed on the networks and reveal a similar behavior for polyisoprene and polybutadiene with nevertheless quite different Young modulus or strain at break. The retro Diels–Alder reaction occurs upon heating, allowing the remolding of the used elastomer. The remolded network exhibits the same mechanical properties as the initial network, showing an efficient material recyclability.     

NFR (Natural Frequency Region) approach for dynamic evaluation of anti-vibration systems with rebound resilience method

There is no universal method to perform dynamic analysis on solid rubber anti-vibration systems. In this article, an equivalent damping ratio is introduced to account for rubber hysteresis using a resilience experiment. A new concept, NFR (Natural Frequency Region), is defined for dynamic evaluation based on natural characteristics of a rubber anti-vibration system itself. Two typical industrial products were selected to verify the proposed NFR approach. The verification procedure involves three parts: natural frequencies, harmonic spectra and impact responses. The dynamic responses from both simulation and experiment have been compared and have not only demonstrated that the proposed approach is reliable but that it could also be used to guide the design of rubber anti-vibration systems in industry. The key points for applying this approach are also presented through the verification procedure.     

Performance of radar absorbing materials by waveguide measurements for X- and Ku-band frequencies

In this work, samples consisting of an elastomeric matrix containing different kinds of active materials in particulate form were prepared for reflectivity measurements. The materials individually used in weight contents of 80% in polychloroprene matrix were: carbonyl-iron (CI) and doped ferrite powders. The microwave reflectivity levels were determined from the magnetic and dielectric properties of the elastomeric composites obtained from scattering data, by fitting the samples in a waveguide, for measurements in the frequency range from 8 to 16 GHz. Better microwave absorption for X-band was obtained for CI while doped ferrite absorbed at higher frequencies (Ku-band).     

Thermal characterization of Al2O3 and ZnO reinforced silicone rubber as thermal pads for heat dissipation purposes

Silicone rubber filled with thermally conductive, but electrically insulating Al₂O₃ or ZnO fillers were investigated to be used as elastomeric thermal pads, a class of thermal interface materials. The effect of Al₂O₃ or ZnO fillers on the thermal conductivity and coefficient of thermal expansion (CTE) of the silicone rubber were investigated, and it was found that with increasing Al₂O₃ or ZnO fillers, the thermal conductivity of the thermal pads increases, while the coefficient of thermal expansion (CTE) decreases. The thermal conductivity results obtained were also analyzed using the Agari model to explain the effect of Al₂O₃ or ZnO fillers on the formation of thermal conductive networks. Thermal gravimetry analysis (TGA) showed that the addition of either Al₂O₃ or ZnO fillers increases the thermal stability of the silicone rubber, while the scanning electron microscope (SEM) showed that at 10 vol.% filler loading percolation threshold has yet to be reached.     

Synthesis and characterization of elastic aliphatic polyesters from sebacic acid, glycol and glycerol

A series of biodegradable polyesters have been prepared from sebacic acid (SA), glycol (Go) and glycerol (Ge) through a two-step process. First the linear prepolymers were prepared from SA and Go, then crosslinked polyesters were obtained from the prepolymer and Ge with different molar ratios. The resulting samples were characterized by Fourier Transform Infrared Spectrum (FTIR), X-ray Photoelectron Spectroscopy (XPS), and Differential Scanning Calorimetry (DSC). Dynamic Contact Angle tests (DCA) and mechanical tests were also investigated. The enzymatic degradation studies were performed at 37 °C in phosphate buffer solution with porcine pancreas lipase. The resultant polyesters were transparent, flexible, insoluble in organic solvents, and the surfaces of the polyesters were hydrophilic. Young’s modulus, tensile strength, glass transition temperature (T_g) and the degree of enzymatic degradation increased with increasing the content of Ge. It was also worth noticing that the surface content of -COOC- groups was a key factor in the enzymatic degradability.     

A novel method for contact analysis of rubber and various surfaces using micro-computerized-tomography

The experimental analysis of the contact state in a tribosystem is of great importance in the study of contact mechanics. In order to make a realistic analysis on the micro scale, it is desirable to keep the tribosystem unperturbed, i.e., without any surface treatment or incorporation of a third body to facilitate the analysis. This study presents the use of a novel technique, micro-computerized tomography (micro-CT), in the investigation of contact between rubber compounds and various counter-surfaces. The goal of this study was to further advance the use of micro-CT in contact mechanics. Specific image analysis techniques were developed in order to process micro-CT images of contact pairs formed by rubber compounds of different hardness levels against counter-surfaces with varying surface roughness and mechanical properties. The micro-CT method has been shown to allow the direct visualization and precise quantification of the real area of contact without altering the original characteristics of the contact pair.     

橡胶贮存寿命预测方法研究进展与思考建议

概述了用数学模型法预测橡胶贮存寿命的方法,包括阿伦尼斯模型,用ASTM D412评估橡胶拉伸性能,应力应变老化模型,压缩永久变形的预测方法,橡胶疲劳寿命损伤模型,用有限元法考核橡胶的裂纹长度与抗裂能之间的关系,基于叠加原理的寿命预测模型等,针对上述模型预测研究结果提出了相关思考建议。认为以老化动力学为基础预测材料寿命的数学模型法发展非常迅速,建议深入研究并拓宽应用;在透彻了解和掌握必需的分子结构参数的基础上,如果结合计算机技术模拟长期贮存或使用条件,对橡胶老化反应机理的研究可能是一个有前景的发展方向。     

An energy dissipation approach on complete loading-unloading and dynamic impact predictions with experimental verification for rubber anti-vibration component

Accurate evaluations of a completed loading-unloading cycle and dynamic impact response for rubber anti-vibration components have been very challenging for industry over many years. In this article, we have altered the classic hyperelastic models to predict complete loading-unloading response using an energy dissipation approach. In addition, we proposed NFR (Natural Frequency Region) approach to simulate a dynamic impact event instead of using the usual viscoelastic methodology, as results from different viscoelastic models may vary widely and to avoid complex parameter fitting procedures. The proposed approaches have been validated in laboratory experiments using industrial anti-vibration components. We have also detailed a procedure for engineers to implement this approach in commercial finite element software without writing intricate user subroutines, as simulation based on finite element method has been routinely used in industry to support design of new products. It is suggested that these methodologies could be used for a design stage in engineering applications.     

Curing and properties of chloroprene and butadiene rubber (CR/BR) blends cross-linked with copper(I) oxide or copper(II) oxide

This paper discusses the curing and properties of chloroprene and butadiene rubber (CR/BR) blends cross-linked with copper(I) oxide (Cu₂O) or copper(II) oxide (CuO). The results revealed that the cross-linking degree of CR/BR blends decreased with the increasing amount of butadiene rubber (BR) in the blends. The mechanical properties of cured CR/BR blends depended on the proportion of elastomers in blends, as well as on the type and amount of the cross-linking agent (Cu₂O, CuO). The cross-linking of CR/BR/Cu₂O or CR/BR/CuO blends followed according to cationic mechanism, using Lewis acid, copper(I) chloride (CuCl) or copper(II) chloride (CuCl₂) generated in situ. Additionally, the prepared compositions, both unfilled and filled, were characterized by very high resistance to flame.     

脂肪族聚酯弹性体的合成及其性能研究

介绍了一种以癸二酸、乙二醇和甘油为原料合成可降解脂肪族聚酯的方法,并利用红外光谱、光电子能谱、示差扫描量热法、X射线衍射和力学测试等方法对聚酯的性质进行了研究.结果显示,产物表现出典型的高弹性,随着原料中癸二酸/乙二醇的比值增加,产物的弹性模量呈增加趋势,微观结构由局部有序向无序转变.产物具有良好的生物降解能力,37℃下在含猪胰脂肪酶的磷酸缓冲溶液里72h失重率在6.1%～14.4%之间.     

膦亚胺半茂钛催化体系合成无规聚丙烯弹性体的研究

采用2种膦亚胺半茂化合物[(t-Bu)_3P=N]CpTiCl_2(PT1)和[(t-Bu)_3P=N]CpTiMe_2(PT2)为主催化剂,分别以甲基铝氧烷(MAO)或[Ph_3C][B(C_6F_5)_4]为助催化剂用于丙烯聚合研究.详细考察了不同n(Al)/n(Ti)、反应温度、反应压力、反应时间等因素对丙烯聚合活性、分子量与分子量分布及其分子结构的影响.还与典型的(rac-[En(IndH_4)_2]ZrCl_2)(1),CpTiCl_3(2)及Cp_2TiCl_2(3)催化剂的催化效果进行了比较.凝胶渗透色谱(GPC)、核磁共振氢谱与碳谱(1H/13C-NMR)、示差扫描量热分析(DSC)和红外(FTIR)分析结果表明:这2种催化剂催化丙烯聚合的活性可高达3.25×10~6g聚合物/molTi×h,重均分子量高达4.4×10~5,分子量分布2.0.降低温度及升高反应压力和延长反应时间都能使聚丙烯分子量增加.观察到聚合初期产物分子量随聚合时间线性增大.在-100~200oC范围内没有观察到熔融峰出现,但在-3.7~-2.6oC区间可以观察到有玻璃化转变温度出现.序列结构分析表明,所生成的聚丙烯为无规结构,但二元组r(62.28%)高于m(37.72%),意味着聚合过程中有间规聚合倾向.[mr/(2mm+mr)]+[mr/(2rr+mr)]=1.04的计算结果进一步说明,由此类催化剂体系催化丙烯聚合生成的产物立体结构序列分布服从伯努利统计模型,聚合主要以1,2-插入方式为主,同时含有少量2,1-插入.     

Chromatographic Analysis of Tire Rubber Samples as the Basis of Their Differentiation and Classification for Forensic Purposes

A pyrolysis gas chromatography-mass spectrometry (GC-MS) method was applied for the comparative analysis of 42 samples of rubber collected from passenger car tires. It was found that rubber samples originating from different tires can, in most cases, be effectively differentiated. The rubber samples were first assigned to one of three classes on the basis of the main components present in chromatograms (styrene and limonene). Then peaks obtained from trace constituents of the rubber were taken into account. In most cases, the differences between the analyzed samples were sufficient to distinguish them. In this study, an on-line derivatization technique (using tetramethylammonium hydroxide) was applied. In some cases, this technique made it possible to demonstrate differences that were invisible in normal analysis. The study showed that the pyrolysis GC-MS method was an effective tool to differentiate between samples of tire rubber. The estimated discrimination power without derivatization ranged from 90% (styrene-butadiene rubber based) to 100% (natural/styrene-butadiene rubber samples). Derivatization increased the former discrimination power to 99%.     

软刻蚀及其应用

软刻蚀是一类基于自组装和复制模塑等原理的非光刻微米和纳米加工方法。它为形成和制作微米、纳米图案提供了简便、有效、价廉的途径。在软刻蚀中，用一个表面带图案的弹性模板来实现图案的转移，其加工的分辨率可达30nm－100μm。软刻蚀是微接触印刷、复制模塑、转移微模塑、毛细微模塑、溶剂辅助微模塑等的总称。本文将简介软刻蚀的原理、方法以及它们在微米和纳米加工、微电子学、材料科学、光学、微电子机械系统、表面化学等方面的应用。     

Effect of Elastomeric Nanoparticles on Toughness and Heat Resistance of Epoxy Resins

A new composite consisting of epoxy resin and elastomeric nanoparticles with high toughness and high heat‐distortion temperature is prepared. The size of the nanoparticles used was less than 90 nm. The excellent properties of the composite seem to be due to stronger interactions between the carboxyl groups of the nanoparticles and the epoxy groups of the resin, and to enhanced hydrogen bonding between the nitrile groups of the rubber and the hydroxyl groups of the resin.     

橡胶的老化机理及老化行为的研究进展

橡胶制品在使用过程中会受到热、氧、热氧、光、辐照及机械应力等因素影响,会产生降解、交联等老化行为.不同种类橡胶因其使用环境和要求不同,其老化机理也各不相同.本文介绍了橡胶老化的化学机理、研究方法及预测方法和模型,综述了近年来不同品种的橡胶及橡胶/橡胶并用体系的老化行为研究进展.通过对橡胶老化行为和机理的综述,有助于系统...     

Robust and Semi‐Interpenetrating Hydrogels from Poly(ethylene glycol) and Collagen for Elastomeric Tissue Scaffolds

Here we present an injectable PEG/collagen hydrogel system with robust networks for use as elastomeric tissue scaffolds. Covalently crosslinked PEG and physically crosslinked collagen form semi‐interpenetrating networks. The mechanical strength of the hydrogels depends predominantely on the PEG concentration but the incorporation of collagen into the PEG network enhances hydrogel viscoelasticity, elongation, and also cell adhesion properties. Experimental data show that this hydrogel system exhibits tunable mechanical properties that can be further developed. The hydrogels allow cell adhesion and proliferation in vitro. The results support the prospect of a robust and semi‐interpenetrating biomaterial for elastomeric tissue scaffolds applications.