模拟深海压力环境下有机涂料/基底金属腐蚀电化学行为研究Ⅰ.海水压力对水在涂层中传输行为和涂层防护性能的影响

于实验室模拟深海压力环境,应用电化学阻抗谱(EIS)研究了有机涂料/基底金属的腐蚀电化学行为.分析海水压力对水在涂层中传输行为和涂层防护性能的影响.结果表明,与常压海水相比,在高压海水(3.5MPa)条件下,该涂层具有不同的电化学阻抗特征,主要表现在高压海水加快了涂层的吸水过程,增大了涂层的吸水率,从而加速了涂层的腐蚀失效过程,致使防护性能变差.     

石墨烯用于金属腐蚀防护的研究

单层无缺陷石墨烯具有优异的屏蔽性能,能阻隔氧气、水分子等腐蚀因子到达金属基体表面,被认为是已知最薄的腐蚀防护涂层。基于石墨烯在金属腐蚀防护领域巨大的应用潜力,本文从石墨烯薄膜防护涂层、石墨烯/有机防护涂层以及石墨烯-导电高分子/有机防护涂层等方面进行系统总结,重点围绕石墨烯薄膜存在的问题以及石墨烯在有机涂层中均匀分散等进行详细分析和介绍,同时对石墨烯基防腐涂料的未来发展进行了展望。     

正十二硫醇自组装单层膜改善环氧涂层腐蚀防护性能的研究

通过在正十二硫醇自组装单层膜表面制备环氧树脂涂层的方法,在涂层/铜基体界面引入自组装界面层.采用X射线光电子能谱、电化学阻抗谱、阻抗-时间谱和相位角-时间谱等方法对硫醇自组装界面层及其对涂层腐蚀防护性能的影响进行了研究.结果表明,引入的自组装单层可极大地改善涂层的腐蚀防护性能.论文还对自组装单层改善涂层腐蚀防护性能的机理进行了探讨.     

颜料体积浓度对水在醇酸涂层中传输行为的影响

水、离子和氧气是导致涂层下金属发生腐蚀的三个重要因素,它们在涂层中的传输过程对其下面金属的腐蚀会产生较大的影响,研究它们在涂层中的传输过程对于弄清涂层下金属发生腐蚀的机制至关重要 .研究表明 [1－ 8], 水在涂层中的传输是一个扩散过程,分起始和饱和两个阶段;在起始阶段,随研究体系和实验条件的不同,水在涂层中的扩散过程遵循不同的规律,可能满足菲克第二扩散定律,也可能会发生较大的偏差 .　　颜料与基料界面间的孔隙是水在涂层中传输的主要通道,调整颜料体积浓度（ PVC）可以改变涂层中这种孔隙的数量和分布,从而…     

改性聚苯胺及其衍生物涂层的防腐性能

导电聚合物作为一种新型高分子材料,由于具有可逆的氧化还原特性,在金属腐蚀防护领域具有潜在的应用前景。在众多的导电聚合物中,聚苯胺因其具有独特的抗点蚀、抗划伤和防止海洋生物附着等特殊性能,被广泛应用于金属材料、化学工业和航海航天等领域, 逐渐成为防腐涂料领域的研究热点。本文通过对单一聚苯胺涂层防腐性能不足的分析,系统总结了近年来改性聚苯胺涂层在金属腐蚀防护领域的研究进展,包括单一环取代聚苯胺涂层和N取代聚苯胺涂层、改性聚苯胺复合涂层和改性聚苯胺复合材料/树脂共混复合涂层;通过各种腐蚀测试手段比较了改性聚苯胺涂层与未改性聚苯胺涂层之间防腐性能的优劣,进一步证明了供电子取代基（如烷基、烷氧基和氨基等）能够提高聚苯胺涂层的防腐性能,复合改性或与树脂共混也能够提高聚苯胺及其衍生物涂层的防腐性能;同时展望了聚苯胺及其衍生物涂料未来发展的新趋势。     

聚合物的分子结构与吸声性能研究

以甲苯二异氰酸酯和聚乙二醇为原料合成了聚氨酯,同时以乙烯基聚二甲基硅氧烷和含氢硅油为原料合成了硅橡胶.然后,以上述合成的硅橡胶和聚氨酯橡胶分别作为消声涂层的基体材料,研究了聚合物分子结构对涂层吸声性能的影响.采用傅利叶变换红外光谱(FTIR)表征了聚合物的分子结构,用驻波管法测量了涂层的吸声系数,用拉伸法和剪切法测定涂层的拉伸模量和剪切模量,并利用有限元程序ANSYS8.0模拟分析了涂层在水压下的形变.测试结果表明,不同结构的聚合物,在常压和高压下呈现出不同的吸声性能.具有柔性链状结构的硅橡胶基涂层,在水压作用下形变较大,吸声系数随水压增大而迅速减小;而含氢键结构的聚氨酯基涂层,在水压作用下形变较小,吸声系数随水压增大而升高.分析认为聚合物自由体积的大小和运动可能是影响涂层吸声性能的重要因素.橡胶体积压缩后,在一定程度上减少了自由体积的大小,限止了自由体积的运动,因此,选择刚性结构的聚合物作为涂层基体,调节自由体积,是制备在高压下具有高吸声性能涂层的重要途径.     

有机硅改性环氧树脂防腐蚀涂层的研究进展

环氧树脂(EPRs)因其良好的耐蚀性、耐化学品性、黏附性及低固化收缩率而广泛应用于防腐蚀涂层。由有机硅烷或线性聚硅氧烷出发,经前者的水解、缩合及两者与EPR的加成等反应,将疏水性良好的有机硅树脂(SR)凝胶或链段作为(EPR-填料)偶联层、(金属基底)底漆、(分散或互穿聚合物网络)相、或(共聚)组分引入到EPR固化涂层体系中,可以通过疏水阻隔及凝胶相或交联点(链段)缓蚀的机理提高改性EPR涂层的防腐蚀性能;SR的体积分数效应亦改善了涂层的耐老化性与耐热性。在无水催化条件下,经有机硅烷的烷氧基与EPR的羟基之间的醇解(缩合)反应,生成硅烷小分子接枝改性EPR固化涂层;亦能通过体系中未反应的烷氧基的水消化(水解)阻隔改良涂层的防腐蚀性能。当向SR改性EPR涂层中加入陶瓷(纳米氧化物、粘土、碳材料)填料时,适中的含量可能导致独特的树脂-陶瓷两相形态而产生结构性疏水;当引入无机酸盐(铬酸盐、磷酸盐、硅酸盐、稀土铈盐、钼酸盐、高锰酸盐)或有机化合物(8-羟基喹啉、四氯代苯对醌)转化膜或颗粒时,可能在涂层-金属界面处发生转化保护型电化学防护;而当填充低电位活性金属(Mg、Zn)粉末时,则可能在金属基底表面形成阴极保护型电化学防护;同时,所有三种填料的加入均可能进一步增强涂层的缓蚀效应。在调控与优化EPR-SR体系结构与形态的同时,辅以各种改性填料的协同耦合使用,成为实现SR改性EPR涂层防腐蚀性能最佳化的必经途径之一。     

乙酸基和羟基对固化的环氧树脂吸水性能的影响

应用称重法、差示扫描量热法和腐蚀测试法研究固化的环氧树脂的吸水行为。实验结果表明,该树脂中的羟基改为乙酸基后可降低树脂的饱和吸水率,并增大水在树脂中的扩散能力。邻甲酚环氧树脂用乙酸线型酚醛酯树脂固化后所得的树脂(EPA)在30℃时饱和吸水率为0.84%(质量分数),而用线型酚醛树脂固化所得的树脂(EP)的则为1.97%;水在EPA和EP中的扩散活化能分别为40和48kJ.mol^-1.这可归因于乙酸基中的甲基的憎水性,降低了吸水率,却因乙酸基的弱相互作用增强了链的柔顺性,而有利于水在链空间中的扩散。EPA涂层/金属铝界面的特殊结构降低了该界面的吸水率,从而提高了该涂层的防护性能。     

添加氧化铈对AZ91D镁合金表面富镁涂层的保护作用

通过Machu测试、电化学交流阻抗(EIS)和扫描电子显微镜(SEM)等方法研究了添加氧化铈对AZ91D镁合金表面富镁涂层防护性能的影响.氧化铈添加量较少(0.1%,w)时,对涂层耐蚀性无影响;添加量过多(3%)时,涂层耐蚀性降低;添加氧化铈颗粒为0.5%时,涂层的阻抗增大,涂层电容降低,对AZ91D镁合金基体的保护性能明显提高.尽管添加氧化铈不改变富镁涂层对AZ91D镁合金的保护机制,但可显著延长涂层的服役寿命.氧化铈能够降低纯镁颗粒的电化学反应活性,使镁粉腐蚀速率降低,阴极保护时间延长.添加一定量氧化铈后,也有利于涂层屏蔽性能提高,氧化铈能降低AZ91D镁合金表面阳极腐蚀电流密度,提高镁合金腐蚀电位,从而有利于富镁涂层发挥对镁合金基体的阴极保护作用.     

丙烯酸酯-苯胺共聚乳液的制备及防腐蚀性能

采用两步乳液聚合法制备丙烯酸酯-苯胺共聚乳液.通过红外光谱(FT-IR)、X射线衍射(XRD)、热重分析(TGA)和透射电镜(TEM)等表征手段对产物的结构进行了研究.将共聚乳液涂覆在Q235低碳钢表面,利用电化学交流阻抗谱(EIS)、塔菲尔(Tafel)曲线和平衡开路电位(OCP)考察共聚乳液涂层对Q235低碳钢的腐蚀防护性能.结果表明:丙烯酸酯与苯胺之间形成了化学键,丙烯酸酯乳液有效地起到了掺杂酸的作用;共聚乳液具有良好的成膜性;共聚乳液涂层具有较高的交流阻抗值(3.0×105Ω·cm2),降低了金属的腐蚀电流密度(10-8 A/cm2),显著提高了腐蚀电位(-0.44 V),防腐蚀性能较好.     

Mechanism Studies on Water Sorption and Permeation in Epoxy Resin by Impedance Spectroscopy. II. Cure Kinetics of O-Cresol Novolac Resin with Esterfied Phenol Novolac Resin

Abstract

To study the effect of water affinity of the cured epoxy resin on water sorption and permeation in the cured epoxy resin, a novel hardener (esterfied phenol novolac was synthesized and used for obtaining the cured product without free hydroxyl group. Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) were used to study the cure kinetics of o-cresol novolac epoxy resin using esterfied phenol novolac resin as curing agent in the presence of 2-methylimidazole as accelerator. Some kinetic parameters of the curing reaction such as the reaction order, activation energy, and frequency factor were obtained in the temperature range studied. The results show that this curing process is a first-order kinetic mechanism, which was different with that cured with phenol novolac resin.     

吸水过程对环氧树脂的动态松弛行为的影响

以酚醛树脂和乙酸、正丁酸和苯乙酸酯化的酚醛树脂固化邻甲酚环氧树脂.应用称重法、示差扫描量热法(DSC)和动态机械分析法(DMA)等手段研究吸水过程对环氧树脂的动态松弛行为的影响.结果表明,吸水过程对酚醛树脂和酯化酚醛树脂固化体系的动态松驰行为有显著的影响,这是由于两种体系中侧基对吸水过程及与水分子的相互作用不同所致.     

Contributions of side groups to the water diffusion in cured epoxy resins (2) study on physical aging

Novolac epoxy resins cured with novolac resin, novolac acetate resin, novolac butyrate resin, and novolac phenylacetate resin named as EP, EPA, EPB, and EPP, respectively, were prepared. Their physical aging behavior at a T_g‐30 °C (30 °C below glass‐transition temperature) was examined by positron annihilation lifetime spectroscopy and differential scanning calorimetry. The ortho‐positronium annihilation lifetime τ₃ variation extent of EP is less apparent than that of the other three esterified samples during physical aging. The time dependence of ops intensity I₃ agreed with the Kohlrausch‐Williams‐Watts (KWW) equation. The relaxation time (τ₀) and nonexponential parameter were calculated. The free volume and enthalpy relaxation rate characterized by the reciprocal of τ₀ and ?ΔH/?logt, respectively, exhibit the same order—EPP > EPB > EPA > EP. These results suggest that the extend and rate of relaxation are not only related to the frozen free volume produced by quenching but also significantly influenced by segmental mobility of the network that attributed to the side‐group flexibility and their interaction with networks. This work also supports the fact that side‐group flexibility and the free‐volume fraction and distribution act in concert to control the water‐diffusion behavior in epoxy networks. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1135–1142, 2003     

Synthesis and properties of novel fluorinated epoxy resins based on 1,1-bis(4-glycidylesterphenyl)-1-(3′-trifluoromethylphenyl)-2,2,2-trifluoroethane

A novel fluorinated epoxy resin, 1,1-bis(4-glycidylesterphenyl)-1-(3′-trifluoromethylphenyl)-2,2,2-trifluoroethane (BGTF), was synthesized through a four-step procedure, which was then cured with hexahydro-4-methylphthalic anhydride (HMPA) and 4,4′-diaminodiphenyl-methane (DDM). As comparison, a commercial available epoxy resin, bisphenol A diglycidyl ether (BADGE), cured with the same curing agents was also investigated. We found that the BGTF gave the exothermic starting temperature lower than BADGE no mater what kind of curing agents applied, implying the reactivity of the former is higher than the latter. The fully cured fluorinated BGTF epoxy resins have good thermal stability with glass transition temperature of 170-175 °C and thermal decomposition temperature at 5% weight loss of 370-382 °C in nitrogen. The fluorinated BGTF epoxy resins also showed the mechanical properties as good as the commercial BADGE epoxy resins. The cured BGTF epoxy resins exhibited improved dielectric properties as compared with the BADGE epoxy resins with the dielectric constants and the dissipation factors lower than 3.3 and dissipation 2.8 × 10⁻³, respectively, which is related to the low polarizability of the C-F bond and the large free volume of CF₃ groups in the polymer. The BGTF epoxy resins also gave low water absorption because of the existence of hydrophobic fluorine atom.     

Thermal and flame retardant properties of epoxy resin cured by a novel phosphorus-containing 4,4′-bisphenol novolac curing agent

A novel flame retardant curing agent for epoxy resin (EP), i.e., a DOPO (9,10-dihydro-9-oxa-10-phosphaphenan-threne-10-oxide)-containing 4,4'-bisphenol novolac (BIP-DOPO) was synthesized and characterized by Fourier transform infrared (FTIR), ¹H NMR, ³¹P NMR spectroscopy, and gel permeation chromatography. The epoxy resin cured by BIP-DOPO itself or its mixture with a commonly used bisphenol A-formaldehyde novolac resin (NPEH720) was prepared. The flame retardancy of the cured EP thermosets were studied by limiting oxygen index (LOI), UL 94 and cone calorimeter test (CCT), and the thermal properties by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results show that the cured epoxy resin EPNP/BI/3/1, which contains 2.2% phosphorus, possesses a value of 26.2% and achieves the UL 94 V-0 rating. The data from cone calorimeter test demonstrated that the peak release rate, average heat release rate, total heat release decline sharply for the flame retarded epoxy resins, compared with those of pure ones. DSC results show that the glass-transition temperatures of cured epoxy resins decrease with increasing phosphorus content. TGA indicates that the incorporation of BIP-DOPO promotes the decomposition of epoxy resin matrix ahead of time and leads to higher char yield. The surface morphological structures of the char residues reveal that the introduction of BIP-DOPO benefits to the formation of a continuous and solid char layer on the epoxy resin material surface during combustion.     

Water-Mediated Epoxy/Surface Adhesion: Understanding the Interphase Region

Epoxy resins coatings are commonly found in corrosion protection coatings but the presence of water can affect their adhesion to the substrate, often weakening the adhesion of the coating to the solid, reducing its efficiency. Nevertheless, small amounts of water can enhance the epoxy/substrate interactions. In this work, the interphase region of an epoxy precursor and metal oxide substrates is investigated using molecular simulations and it is found that water accumulates between the epoxy layer and the solid substrate. At high water concentrations (9 wt %) the interaction between the epoxy precursor and the solid surface is weakened regardless of the nature of the solid, but at low water concentrations the nature of the solid surface becomes important. For hematite, the presence of water decreases the strength of adhesion but for goethite the presence of a small amount of water (3 wt %) enhances the adhesion to the surface resulting in a densification at the interface.     

Novel flame‐retardant thermosets: Phosphine oxide‐containing diglycidylether as curing agent of phenolic novolac resins

Phosphorus‐containing novolac–epoxy systems were prepared from novolac resins and isobutyl bis(glycidylpropylether) phosphine oxide (IHPOGly) as crosslinking agent. Their curing behavior was studied and the thermal, thermomechanical, and flame‐retardant properties of the cured materials were measured. The T_g and decomposition temperatures of the resulting thermosets are moderate and decrease when the phosphorous content increases. Whereas the phosphorous species decrease the thermal stability, at higher temperatures the degradation rates are lower than the degradation rate of the phosphorous‐free resin. V‐O materials were obtained when the resins were tested for ignition resistance with the UL‐94 test. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3516–3526, 2004     

Preparation and properties of epoxy resins cured with silyl esters of phenol novolak and cresol novolak

The curing agents of epoxy resin, trimethylsilyl ethers of phenol novolak (TMSPN) and cresol novolak (TMSCN) were prepared by refluxing phenol novolak and cresol novolak respectively, with the mixture of hexamethyldisilazane and chlorotrimethylsilane in THF. The curing reaction of epoxy resin with these curing agents and the thermal properties of cured resins were examined. The Tg values of epoxy resins cured with TMSPN were a little higher than those cured with TMSCN. The maximum of Tg is 118°C for TMSPN-cured epoxy resin against 112°C for TMSPN-cured epoxy resin. The water absorption of hydrophobic epoxy resins cured with TMSPN was a little lower than those cured with TMSCN. The clear decrease of water absorption is attributed to the difficulty of the micro-void formation caused by the more tight primary structures of TMSPN. The water absorption at 25°C containing trimethylsilyl groups is about one-tenth of that of epoxy resins cured with conventional curing agents and even one-half of that of the epoxy resins cured with active esters. The low water absorption is attributed to the presence of trimethylsilyl groups, which are more hydrophobic than ester groups, and to the absence of hydroxyl groups of the cured resins. This revised version was published online in July 2006 with corrections to the Cover Date.     

Factors affecting H2O absorption of the epoxy tetraglycidyl-4,4′-diaminodiphenyl methane cured with diaminodiphenyl sulfone

It was found that the amount of water absorbed at room temperature in cured tetraglycidyl-4,4′-diaminodiphenyl methane/diaminodiphenyl sulfone epoxy resins increases as the curing time or temperature increases while the amount of tetrahydrofuran-soluble extractables and the room temperature density decreases. These data suggest that the free volume increases with the extent of cure and the resins become more accessible to water. While the driving force for water absorption is the electrostatic attraction between water and the functional groups in the epoxy, the results suggest that equilibrium H₂O absorption is determined primarily by unoccupied volume of the epoxy resin.