多壁异氰酸酯微胶囊的制备及其在自修复防腐涂层中的应用

目的制备多壁异氰酸酯微胶囊及该微胶囊包埋的聚氨酯(PU)自修复防腐涂层。方法在Pickering乳液中,通过界面聚合、原位聚合、自组装,一步生成由内至外依次为聚脲内膜、酚醛壳、聚甲基丙烯酸缩水甘油酯(PGMA)粒子层的多层囊壁包裹异佛尔酮二异氰酸酯(IPDI)芯材的IPDI微胶囊。通过索式提取实验获得了微胶囊的芯材含量,通过SEM、OM对微胶囊形貌及壳层结构进行观测,通过FTIR、DSC测试研究微胶囊的成分及芯材反应活性,通过EIS、加速腐蚀实验研究微胶囊包埋的PU涂层的自修复防腐性能。结果随着芯壳比的增加,微胶囊的芯材含量增大,当芯壳比为2.5∶1时,芯材含量最大,达70.22%。当芯壳比为1.5∶1时,微胶囊的球形度最好,平均粒径最小,为86.12μm,且分布均一。IPDI微胶囊具有一层聚脲内膜、酚醛壳及PGMA粒子层,IPDI芯材被成功包覆,且保持有效性。IPDI微胶囊的初始分解温度为235.8℃,对芯材起到较好的保护作用。包埋IPDI微胶囊的自修复涂层,划痕修复后的阻抗模量恢复至划痕前初始状态阻抗模量的同量级水平。盐水浸泡192h后,自修复涂层划痕处未见腐蚀产生。结论制备的IPDI微胶囊的芯材含量较高,球形度较好,分布均一。该一步法工艺有助于对活泼性芯材达到高效包覆,多囊壁结构有助于提高微胶囊的热稳定性和有效性。自修复涂层由于划痕处生成了固化膜,从而抑制了腐蚀的产生,具有较好的自修复防腐性能。     

可用于生锈基材的自修复防腐涂料

目的 制备具有自修复功能、可用于海洋环境中腐蚀金属部件的涂料。方法 采用原位聚合法制备了以桐油为囊芯、脲醛树脂为囊壁的微胶囊,并将其添加于带锈防锈涂料中,然后将涂料涂覆在生锈的马口铁上。利用扫描电镜、能量色散谱仪、傅里叶变换红外光谱、扫描开尔文探针、热重分析和电化学阻抗谱等测试手段,对微胶囊和涂层的形貌、自修复性能和防腐性能进行表征。结果 桐油被脲醛树脂包裹,制备出的微胶囊形貌良好,微胶囊的平均粒径为(47.37±9.41) μm,微胶囊对桐油的包覆效果良好,囊芯(桐油)的质量分数高达81.57%。含有20%(质量分数)微胶囊的涂层具有良好的自修复性能和耐腐蚀性,被划伤的涂层能够在24 h内完全自修复,通过对涂层的扫描电子观测和扫描开尔文探针可确认划痕区域是涂层自修复实现的,并且涂层能够长时间抵抗腐蚀。结论 微胶囊可显著延长涂层的使用寿命,这种自修复技术有望在防腐涂料系统中得到应用,而且该涂料可直接应用于生锈的金属表面,降低了在复杂应用环境中涂覆金属部件的成本。     

改性酚醛环氧树脂F-51自修复微胶囊的制备

目的研制一种耐温性好、适用于防腐涂料的自修复微胶囊。方法通过活性稀释剂TMPEG改性具有较好耐温性的酚醛环氧树脂F-51,以原位聚合法,采用非离子表面活性剂复合乳化的方法制备脲醛树脂自修复微胶囊。运用光学显微镜(OM)和扫描电子显微镜(SEM)观察微胶囊的分布状况及轮廓形貌,激光粒度分析仪测定微胶囊的粒径值,引入Gauss拟合研究粒径分布。主要讨论乳化剂的选择、用量、原料比、搅拌转速等条件对微胶囊性能的影响,研究最佳合成工艺;利用OM和SEM观察单个微胶囊的形态,结合光衍射原理判断微胶囊芯壁构成;红外光谱仪(FT-IR)探讨其官能团组成,差示扫描量热仪(DSC)测定微胶囊芯材的反应活性,测试室温条件下微胶囊的贮存效果,并由同步热分析仪(TA)测量微胶囊的热失重情况。结果采用OP-10/JFC复合乳化剂,研制出聚脲甲醛包覆酚醛环氧树脂F-51自修复微胶囊,当用量为芯材质量分数的8.0%,原料比为0.8:1,搅拌速率为1600 r/min时,产率最高达82%,粒径分布相对集中,粒径平均值为107μm。OM中光衍射现象明显,在FT-IR特征曲线出现相应特征吸收峰,微胶囊研磨后可固化反应,室温下贮存100 d,失重率不到3.0%,且在250℃范围内可以保持完整囊-芯结构。结论成功制备了包覆修复剂的微胶囊,微胶囊具备反应活性,贮存稳定性及热稳定性良好,研究成果可为自修复防腐涂料的发展提供参考。     

碳钢基自修复涂层的制备和耐蚀性研究

目的 通过在有机防腐涂层中添加小粒径的自修复微胶囊,增强防腐涂层的自修复能力,提高碳钢的耐腐蚀性能.方法 通过乳液聚合法,采用桐油和金属缓蚀剂作为囊芯,分别合成得到了粒径均一的单组分和双组分自修复胶囊,均匀分散于防腐涂层中,获得自修复涂层.结果 SEM和热重分析显示,合成的单组分和双组分自修复微胶囊的平均粒径在3μm左右,囊芯包覆率分别达到48％和49％.人为破损涂层的中性盐雾试验和浸泡试验表明,在囊芯中桐油和金属缓蚀剂的比例为5:1且防腐涂层中微胶囊含量为10％的条件下,经历110 h中性盐雾试验后,防腐涂层划痕处仍旧保持完整,未出现鼓泡和腐蚀现象.同时,浸泡675 h后,自修复涂层仍然保持较高的低频阻抗模值,表明此时涂层的耐蚀性最佳.结论 含有双组分微胶囊的自修复涂层具有较好的自修复能力,可以较好地阻碍腐蚀环境侵蚀,起到长期保护金属基体材料的作用.     

仿生自修复环氧树脂涂层制备及性能

采用一步原位聚合法制备了脲醛树脂包覆E-51/711微胶囊,观察微胶囊形貌呈球形,为单核结构,表面致密,粒径大小分布为25～375μm。模仿生物组织损伤自愈合原理,将微胶囊引入环氧树脂涂层结构中,设计了潜伏型微胶囊自修复环氧涂层。对不同微胶囊质量分数(5%,10%,15%,20%)的环氧自修复涂层的力学性能进行测试分析,结果表明:随着微胶囊的添加量增大,涂层的冲击强度、附着力级别和巴尔霍兹硬度不断降低,而适量添加微胶囊可提高涂层的附着力。对微胶囊环氧树脂涂料块体试样进行拉伸断裂测试试验,并对涂层进行预置划痕修复试验,结果表明:少量添加微胶囊对涂层起到了一定增韧作用,含微胶囊自修复体系的涂层在受到损伤时能够释放修复剂,填充修复损伤部位。     

含环氧树脂微胶囊自修复涂层的制备及其性能

目的制备含环氧树脂微胶囊的二元自修复涂层,并对其力学性能和自修复性能进行研究。方法将自制环氧树脂E-51/三聚氰胺-脲醛树脂微胶囊和潜伏型固化剂(2-甲基咪唑)按一定比例添加到环氧树脂基体中,制备二元自修复环氧树脂涂层。利用漆膜弹性试验机、漆膜冲击试验机和万能拉伸试验机对涂层的弯曲性能、耐冲击性能和拉伸性能进行测试。利用扫描电子显微镜(SEM)、光学显微镜(OM)对涂层的自修复性能进行考察。采用EIS对涂层的电化学性能进行测试。结果成功制备了含环氧树脂微胶囊二元自修复涂层,当涂层中微胶囊的质量分数为3%时,涂层的冲击强度和拉伸强度分别提高了10.6%和14.6%。当涂层中2-甲基咪唑和微胶囊质量分数分别为6%和5%时,涂层的自修复性能较佳。当微胶囊质量分数为9%时,涂层的电化学阻抗值可达1.2×105?。结论微胶囊的加入可有效提高涂层的冲击强度和拉伸强度。随着涂层中潜伏型固化剂含量的增大,涂层的自修复性能增强。当潜伏型固化剂含量达到一定值时,涂层的自修复性能随着微胶囊含量的增大而增强。随着微胶囊含量的增加,涂层的电化学阻抗值增大。     

聚脲包覆KH560硅烷偶联剂微胶囊的制备研究

为实现涂层自修复,制备了聚脲包覆KH560硅烷偶联剂微胶囊.研究了温度、搅拌速度和多元胺种类对微胶囊的形貌、粒径大小、分布状况及囊壁强度等的影响.结果表明:在25℃制备的微胶囊为囊泡结构的大粒径微胶囊,在5℃下制备的为小粒径的微胶囊;随搅拌速度的提高,微胶囊的粒径下降,分布变窄;采用三乙烯四胺制备的微胶囊强度高.在5℃下以2 000r/min的速度乳化,采用三乙烯四胺和TDI的三聚体制备的微胶囊是适用于自修复材料的微胶囊.     

纳米Al2O3改性三聚氰胺-脲醛自修复微胶囊的制备及应用

以纳米Al_2O_3改性三聚氰胺-脲醛树脂(MUF)为壁材,环氧树脂为芯材,采用原位聚合法合成了微胶囊,并采用光学显微镜(OM)、扫描电子显微镜(SEM)、红外光谱仪(FTIR)、X射线光电子能谱分析仪(XPS)、热重分析仪(TGA)等对其表面形貌、结构及热性能等进行了表征和测试;将改性后的微胶囊加入自修复环氧树脂涂层中,并对其热性能、力学性能、自修复性能及电化学性能进行测试。结果表明,当芯壁比为1.5:1、纳米Al_2O_3质量分数为4.5%时,纳米Al_2O_3在壁材中均匀分布,微胶囊的表面粗糙度和热稳定性均增加。当涂层中改性微胶囊质量分数为5%时,涂层的热稳定性提高,且涂层的拉伸强度、弯曲强度、冲击强度及粘结强度分别提高了111.9%、55.1%、10.6%和51.9%;制备的涂层具备较好的自修复性能;涂层的耐腐蚀性能随着微胶囊质量分数的增大而增强。     

聚甲基丙烯酸甲酯包覆双酚F环氧树脂微胶囊的研制

为实现环氧防腐涂料单包装,以甲基丙烯酸甲酯为壁材原料,双酚F环氧树脂为芯材原料,采用原位聚合法制备了聚甲基丙烯酸甲酯包覆双酚F环氧树脂微胶囊.研究了表面活性剂配比、壁材和芯材质量比及反应温度对微胶囊的形貌、粒径大小及囊芯含量等的影响.实验结果表明:随着十二烷基苯环酸钠用量的增加,微胶囊粒径变小,芯材含量增加;壁材与芯材的比例增加,乳液分散容易,形成的微胶囊粒径变小;70℃时反应缓慢,85℃时微胶囊聚集成团.     

聚吡咯包覆二氧化钛纳米自修复微胶囊制备及其形成机制

目的以聚吡咯为有机囊壁、纳米二氧化钛为无机囊芯制备粒径均一的纳米级自修复微胶,并探讨其形成机制。方法采用化学氧化法于超声环境中制备出有机/无机复合自修复微胶囊,利用SEM、FT-IR和XRD等方法,研究了不同制备工艺对微胶囊粒径、形貌、结构的影响。结果阴离子型表面活性剂更有利于聚吡咯在二氧化钛颗粒表面包覆,在十二烷基苯磺酸钠(SDBS)和超声波作用下,吡咯单体以纳米二氧化钛为核心聚合,形成具有纳米晶结构的聚吡咯囊壁,进而获得粒径均一、直径约为100 nm的球形PPy-TiO_2复合纳米微胶囊。结论由于阴离子表面活性剂在二氧化钛粉体表面的化学吸附,形成了有机修饰层,从而可在有效抑制纳米二氧化钛自身团聚的同时,促进吡咯单体在其表面的包覆聚合。     

Effects of Post-weld Heat Treatment on Microstructure,Mechanical Properties and the Role of Weld Reinforcement in 2219 Aluminum Alloy TIG-Welded Joints

In as-welded state, each region of 2219 aluminum alloy TIG-welded joint shows diff erent microstructure and microhardness due to the diff erent welding heat cycles and the resulting evolution of second phases. After the post-weld heat treatment, both the amount and the size of the eutectic structure or θ phases decreased. Correspondingly, both the Cu content in α-Al matrix and the microhardness increased to a similar level in each region of the joint, and the tensile strength of the entire joint was greatly improved. Post-weld heat treatment played the role of solid solution strengthening and aging strengthening. After the post-weld heat treatment, the weld performance became similar to other regions, but weld reinforcements lost their reinforcing eff ect on the weld and their existence was more of an adverse eff ect. The joint without weld reinforcements after the post-weld heat treatment had the optimal tensile properties, and the specimens randomly crack in the weld zone.     

The First Phase of the SRIF Industrialized Base in ＂West Area＂ Has Been Put into Operation

After nearly two years＇ tense construction, the first phase of industrialized base of Shenyang Research Institute of Foundry （SRIF）, located at the Tiexi Casting and Forging Industrial Park in the west of Tiexi District, has now been completed and formally put into operation.     

Thermodynamics Study on the Decomposition of Chromite with KOH

Institute of Process Engineering, Chinese Academy of Sciences, China, has proposed a method for oxidative leaching of chromite with potassium hydroxide. Understanding the mechanism of chromite decomposition, especially in the potassium hydroxide fusion, is important for the optimization of the operating parameters of the oxidative leaching process. A traditional thermodynamic method is proposed and the thermal decomposition and the reaction decomposition during the oxidative leaching of chromite with KOH and oxygen is discussed, which suggests that chromite is mainly destroyed by reactions with KOH and oxygen. Meanwhile, equilibrium of the main reactions of the above process was calculated at different temperatures and oxygen partial pressures. The stable zones of productions, namely, K2CrO4 and Fe2O3, increase with the decrease of temperature, which indicates that higher temperature is not beneficial to thermodynamic reactions. In addition, a comparison of the general alkali methods is carried out, and it is concluded that the KOH leaching process is thermodynamically superior to the conventional chromate production process.     

Influence of Heat Treatment on Damping Behaviour of the Magnesium Wrought Alloy AZ61

The effect of isochronal heat treatments for 1h on variation of damping, hardness and microstructural change of the magnesium wrought alloy AZ61 was investigated. Damping and hardness behaviour could be attributed to the evolution of precipitation process. The influence of precipitation on damping behaviour was explained in the framework of the dislocation string model of Granato and Lücke.     

Effect of Rare Earth Doping on Impedance,Modulus and Conductivity Properties of Multiferroic Composites:0.5(BiLa_xFe_(1-x)O_3)–0.5(PbTiO_3)

The Lanthanum-doped bismuth ferrite–lead titanate compositions of 0.5(Bi LaxFe1-xO3)–0.5(Pb Ti O3)(x = 0.05,0.10,0.15,0.20)(BLxF1-x-PT) were prepared by mixed oxide method.Structural characterization was performed by X-ray diffraction and shows a tetragonal structure at room temperature.The lattice parameter c/a ratio decreases with increasing of La(x = 0.05–0.20) concentration of the composites.The effect of charge carrier/ion hopping mechanism,conductivity,relaxation process and impedance parameters was studied using an impedance analyzer in a wide frequency range(102–106Hz) at different temperatures.The nature of Nyquist plot confirms the presence of bulk effects only,and non-Debye type of relaxation processes occurs in the composites.The electrical modulus exhibits an important role of the hopping mechanism in the electrical transport process of the materials.The ac conductivity and dc conductivity of the materials were studied,and the activation energy found to be 0.81,0.77,0.76 and 0.74 e V for all compositions of x = 0.05–0.20 at different temperatures(200–300 °C).     

Quantitative Analysis of the Crystallographic Orientation Relationship Between the Martensite and Austenite in Quenching–Partitioning–Tempering Steels

The orientation relationships(ORs)between the martensite and the retained austenite in low-and medium-carbon steels after quenching–partitioning–tempering process were studied in this work.The ORs in the studied steels are identified by selected-area electron diffraction(SAED)as either K–S or N–W ORs.Meanwhile,the ORs were also studied based on numerical fitting of electron backscatter diffraction data method suggested by Miyamoto.The simulated K–S and N–W ORs in the low-index directions generally do not well coincide with the experimental pole figure,which may be attributed to both the orientation spread from the ideal variant orientations and high symmetry of the low-index directions.However,the simulated results coincide well with experimental pole figures in the high-index directions{123}_(bcc).A modified method with simplicity based on Miyamoto’s work was proposed.The results indicate that the ORs determined by modified method are similar to those determined by Miyamoto’method,that is,the OR is near K–S OR for the low-carbon Q–P–T steel,and with the increase of carbon content,the OR is closer to N–W OR in medium-carbon Q–P–T steel.     

Growth Kinetics of Single Inclusion Particle in Molten Melts

On the basis of the single-particle framework, a new theory on inclusion growth in metallurgical melts is developed to study the kinetics of inclusion growth on account of reaction and collision. The studies show that the early growth of inclusion depends on reaction growth and Brawnian motion collision, and where the former is decisive, the late growth depends on turbulence collision and Stokes＇ collision, and where the former is dominant; collision growth is very quick during the smelting process, lessened in the refining process, but nearly negligible in the continuous casting process.     

Theoretical Analysis for the Motion and Temperature of Melt Droplets in Spray Degassing Process

The motion of melt droplets in spray degassing process was analyzed theoretically. The height of the treatment tank in spray degassing process could be determined by the results of theoretical calculation of motion of melt droplets. To know whether the melt droplets would solidify during spraying process, the balance temperature of melt droplets was also theoretically analyzed. Then proof experiments for theoretical results about temperature of melt droplets were carried. In comparison, the experimental results were nearly similar to the calculation results.     

Using Finite Element and Contour Method to Evaluate Residual Stress in Thick Ti-6Al-4V Alloy Welded by Electron Beam Welding

This work was to reveal the residual stress profile in electron beam welded Ti-6Al-4V alloy plates(50 mm thick) by using finite element and contour measurement methods.A three-dimensional finite element model of 50-mmthick titanium component was proposed,in which a column–cone combined heat source model was used to simulate the temperature field and a thermo-elastic–plastic model to analyze residual stress in a weld joint based on ABAQUS software.Considering the uncertainty of welding simulation,the computation was calibrated by experimental data of contour measurement method.Both test and simulated results show that residual stresses on the surface and inside the weld zone are significantly different and present a narrow and large gradient feature in the weld joint.The peak tensile stress exceeds the yield strength of base materials inside weld,which are distinctly different from residual stress of the thin Ti-6Al-4V alloy plates presented in references before.     

Microstructures and Tensile Properties of Ultrafine-Grained Ni–(1–3.5) wt% SiC_(NP) Composites Prepared by a Powder Metallurgy Route

Silicon carbide nanoparticle-reinforced nickel-based composites(Ni–Si CNP),with a Si CNPcontent ranged from1 to 3.5 wt%,were prepared using mechanical alloying and spark plasma sintering.In addition,unreinforced pure nickel samples were also prepared for comparative purposes.To characterize the microstructural properties of both the unreinforced pure nickel and the Ni–Si CNPcomposites transmission electron microscopy(TEM) was used,while their mechanical behavior was investigated using the Vickers pyramid method for hardness measurements and a universal tensile testing machine for tensile tests.TEM results showed an array of dislocation lines decorated in the sintered pure nickel sample,whereas,for the Ni–Si CNPcomposites,the presence of nano-dispersed Si CNPand twinning crystals was observed.These homogeneously distributed Si CNPwere found located either within the matrix,between twins or on grain boundaries.For the Ni–Si CNPcomposites,coerced coarsening of the Si CNPassembly occurred with increasing Si CNPcontent.Furthermore,the grain sizes of the Ni–Si CNPcomposites were much finer than that of the unreinforced pure nickel,which was considered to be due to the composite ball milling process.In all cases,the Ni–Si CNPcomposites showed higher strengths and hardness values than the unreinforced pure nickel,likely due to a combination of dispersion strengthening(Orowan effects) and particle strengthening(Hall–Petch effects).For the Ni–Si CNPcomposites,the strength increased initially and then decreased as a function of Si CNPcontent,whereas their elongation percentages decreased linearly.Compared to all materials tested,the Ni–Si CNPcomposite containing 1.5% Si C was found more superior considering both their strength and plastic properties.