The effect of bismuth on the structure of zinc hot-dip galvanized coatings

Low carbon steel substrates were galvanized in molten zinc containing 0.0, 0.5, 1.0 and 2.0 wt.% bismuth. The as-cast coatings were examined with optical microscopy, scanning electron microscopy and X-ray diffraction. From the above investigation it was deduced that Bi addition does not affect the morphology of the galvanized coatings with regard to the “traditional” galvanized coatings, although it is mainly accumulated in the eta phase and in the upper part of the zeta phase in the form of inclusions. However these inclusions could accelerate the coating corrosion because Bi is cathodic to Zn. Furthermore the thickness of the galvanized coatings is reduced when Bi is added.     

Effect of four coating structures on corrosion kinetic of galvanized reinforcement in concrete

In the present work is described the effect of the characteristics of the galvanized coating on corrosion rate of reinforcing bars embedded in a concrete without additives and in another with 2% CaCl₂ in terms of cement weight. To this end, the following materials were subjected to the action of a moisture saturated atmosphere for a period of400 days: an annealed-galvanized coating; another one obtained by dipping in a molten Zn bath with0.025% Al and some others produced at450 and430°C in an ordinary bath. The attack evolution vs time was controlled by measuring the polarization resistance. The electrochemical determinations were gravimetrically verified and supplemented by a metallographic examination of tests coatings. In the absence of chlorides, the attack is fully tolerated. Chlorides radically change the corrosion behaviour of galvanized steel and increase the attack by a factor of2.8 in the most favourable case, but in these conditions, coatings with thick, homogeneous η layer outperform the usual ones, and specially the annealed ones.     

Thermal property,wettability and interfacial characterization of novel Sn–Zn–Bi–In alloys as low-temperature lead-free solders

The effect of indium (In) addition on thermal property, microstructure, wettability and interfacial reactions of Sn–8Zn–3Bi lead-free solder alloys has been investigated. Results showed that addition of In could lower both solidus and liquidus temperatures of the solder alloys with wettabilty significantly improved. The spreading area of Sn–8Zn–3Bi–1.0In was increased by 34% compared to that of Sn–8Zn–3Bi. With the increase of In content, Zn-rich precipitates were smaller in size and distributed more uniformly, which might be beneficial for mechanical properties and corrosion resistance of the solders. The intermetallic compounds (IMCs) formed between Sn–8Zn–3Bi–xIn solder/Cu substrate was identified as Cu–Zn with a scallop layer adjacent to the solder and a flat layer to the substrate. The addition of In slightly influenced the thickness of the IMCs. The newly developed Sn–Zn–Bi–In solder system has great potential to replace the Sn–Pb solders as low-temperature lead-free solders.     

Wettability and interfacial whiskers of Sn–9Zn–0.5Ga–0.08Nd solder with Sn,SnBi and Au/Ni coatings

The wettability and interfacial whiskers of Sn–9Zn–0.5Ga–0.08Nd solder were investigated. The results indicated that Sn–9Zn–0.5Nd–0.08Nd solder has shown good wettability using water soluble flux and self made flux based on wetting balance testing, and solder with SnBi coating has shown superiority wettability among all three coatings. Moreover, no whisker was observed in Sn–9Zn–0.5Ga–0.08Nd solder with different coatings. But in Sn–9Zn–0.5Ga–1Nd solder, fewer whiskers were observed in solder with SnBi coating compared with Sn and Au/Ni coatings, which can be attributed to the refinement effect of Bi.     

Microstructure and kinetic analysis of the properties and behavior of nickel (Ni) nano-particle doped tin–zinc–bismuth (Sn–8Zn–3Bi) solders on immersion silver (Ag)-plated copper (Cu) substrates

In order to identify the effect on the properties and behavior of tin–zinc–bismuth (Sn-8 wt% Zn-3 wt% Bi or Sn-13.6 at.% Zn-1.6 at.% Bi) based solders produced by adding nickel (Ni) nano-particles, the interfacial microstructure between plain and composite solders with newly developed immersion silver (Ag) plated copper (Cu) substrates has been investigated as a function of reaction time, at various temperatures. For plain Sn–8Zn–3Bi solder joints, a scallop-shaped Cu–Zn–Ag intermetallic compound layer was found to adhere to the surface of the immersion Ag-plated Cu substrate. However, after addition of Ni nano-particles into the Sn–8Zn–3Bi solder, Cu–Zn–Ag (at the bottom) and (Cu, Ni)–Zn (at the top) intermetallic compound layers were observed at the interfaces. In addition, these intermetallic compound layer thicknesses increased substantially with increases in the temperature and reaction time. In the solder ball region, needle-shaped α-Zn rich phase and spherically-shaped Bi-particles appeared to be homogeneously distributed throughout a beta-tin (β-Sn) matrix. However, after the addition of Ni nano-particles, needle-shaped α-Zn rich phase appeared that exhibited a fine microstructure, due to the heterogeneous nucleation of the Ni nano-particles. The calculated activation energy for the Cu–Zn–Ag intermetallic compound layer for the plain Sn–8Zn–3Bi solder/immersion Ag-plated Cu system was 29.95 kJ/mol—while the activation energy for the total [Cu–Zn–Ag + (Cu, Ni)–Zn] intermetallic compound layers formed in the Sn–8Zn–3Bi–0.5Ni (Sn-13.6 at.% Zn-1.6 at.% Bi ~1 at.% Ni) composite solder/immersion Ag-plated Cu system was 27.95 kJ/mol. Addition of Ni nano-particles reduces the activation energy which enhanced the reaction rate as we know that lower the activation energy indicates faster the reaction rate.     

Thermodynamics and phase diagrams of lead-free solder materials

Many of the existing and most promising lead-free solders for electronics contain tin or tin and indium as a low melting base alloy with small additions of silver and/or copper. Layers of nickel or palladium are frequently used contact materials. This makes the two quaternary systems Ag–Cu–Ni–Sn and Ag–In–Pd–Sn of considerable importance for the understanding of the processes that occur during soldering and during operation of the soldered devices. The present review gives a brief survey on experimental thermodynamic and phase diagram research in our laboratory. Thermodynamic data were obtained by calorimetric measurements, whereas phase equilibria were determined by X-ray diffraction, thermal analyses and metallographic methods (optical and electron microscopy). Enthalpies of mixing for liquid alloys are reported for the binary systems Ag–Sn, Cu–Sn, Ni–Sn, In–Sn, Pd–Sn, and Ag–Ni, the ternary systems Ag–Cu–Sn, Cu–Ni–Sn, Ag–Ni–Sn, Ag–Pd–Sn, In–Pd–Sn, and Ag–In–Sn, and the two quaternary systems themselves, i.e. Ag–Cu–Ni–Sn, and Ag–In–Pd–Sn. Enthalpies of formation are given for solid intermetallic compounds in the three systems Ag–Sn, Cu–Sn, and Ni–Sn. Phase equilibria are presented for binary Ni–Sn and ternary Ag–Ni–Sn, Ag–In–Pd and In–Pd–Sn. In addition, enthalpies of mixing of liquid alloys are also reported for the two ternary systems Bi–Cu–Sn and Bi–Sn–Zn which are of interest for Bi–Sn and Sn–Zn solders.     

Effect of prior damage on the performance of cement based coatings on rebar: macrocell corrosion studies

The performance of any rebar coating system depends upon its resistance to corrosion in the presence of chloride contaminated concrete. It also mainly depends upon its tolerance towards damage that may occur during handling, transporting and concreting. The severe corrosion of epoxy coated reinforcing steel in long key bridge and other structures in Florida gave raise to the concern over the influence of damages in the coating system [R.J. Kessler, P.G. Powers, Interim report on corrosion evaluation of substructure in Long key bridge, Corrosion Report No. 87-9A, Florida Department of Transportation, Florida, 1987]. The performance of rebar coating such as galvanizing and epoxy based coating with prior surface damage has been evaluated and reported. [J. Hartley, Concrete Jan/Feb (1994) 12–15; A. Sagues, Performance of galvanized rebars in marine substructure service, Project ZE-418, Part I, October, 1994]. To date, the performance of cement based coatings with prior damages has not been widely studied and reported. In the present investigation the effect of prior damage produced during concrete pouring has been studied on inhibited cement slurry coating. To simulate the marine substructure environment, macrocell corrosion has been created via a chloride ion concentration gradient. Test conditions and method of macrocell current measurement as described in ASTM G 109-92 have been followed. The above investigation revealed that the cement based coating appears to have better tolerance towards defects in chloride contaminated concrete as compared to epoxy based coating system. The performance of the coating is independent of the height of concrete pouring.     

Morphological and electrochemical characterization of electrodeposited Zn–Ag nanoparticle composite coatings

Silver nanoparticles with an average size of 23 nm were chemically synthesized and used to fabricate Zn–Ag composite coatings. The Zn–Ag composite coatings were generated by electrodeposition method using a simple sulfate plating bath dispersed with 0.5, 1 and 1.5 g/l of Ag nanoparticles. Scanning electron microscopy, X-ray diffraction and texture co-efficient calculations revealed that Ag nanoparticles appreciably influenced the morphology, micro-structure and texture of the deposit. It was also noticed that agglomerates of Ag nanoparticles, in the case of high bath load conditions, produced defects and dislocations on the deposit surface. Ag nanoparticles altered the corrosion resistance property of Zn–Ag composite coatings as observed from Tafel polarization, electrochemical impedance analysis and an immersion test. Reduction in corrosion rate with increased charge transfer resistance was observed for Zn–Ag composite coatings when compared to a pure Zn coating. However, the particle concentration in the plating bath and their agglomeration state directly influenced the surface morphology and the subsequent corrosion behavior of the deposits.     

Synthesis of hybrid silica sol–gel coatings containing Zn particles on carbon steel and Al/Zn coated carbon steel

Owing to increasing interest of coatings applied on low alloy steel and galvanised metal plates and their applications, this work presents the study of the process requirements to be fulfilled in order to coat these metals with an hybrid silica coatings containing Zn particles. The main idea was to combine the “barrier” effect of the hybrid silica coatings with the “active protection” effect of the zinc particles inside the coatings. Sol–gel parameters, Zn particles content and suspension stability have been studied. EMPHOS ES 21, an electrostatic dispersant, has been used to obtain stabilised suspensions. Thick, adherent and crack-free coatings containing 10% Zn particles were prepared by dip-coating on carbon steel and Al/Zn coated carbon steel substrates. The applied coating seems to improve corrosion protection of the two metal substrates, and this effect is more noticeable in the case of the Al/Zn system because of the combination of the complementary corrosion protection properties of both coatings.     

铜导线表面热浸镀PbSn合金镀层的组织与性能

为了改善铜导线的可焊性和耐蚀性,采用热浸镀技术在铜导线表面制备Pb40Sn60和Pb37Sn63两种成分的低熔点合金镀层,利用扫描电镜(SEM)、能谱分析(EDS)、X射线衍射(XRD)等分析手段和电阻率检测实验、拉伸实验、中性盐雾实验等方法,系统研究其微观组织、相成分、电阻率、力学性能及耐蚀性。结果表明:Pb40Sn60和Pb37Sn63两种成分的合金镀层均由α相和β相两相组成,镀层的电阻率分别约为2.6832×10^-3,2.5929×10^-3Ω·m,均高于铜基体。铜导线热浸镀Pb40Sn60和Pb37Sn63两种成分合金镀层后的表面硬度分别为13.4,12.6HV0.2;抗拉强度分别为193,180 MPa;伸长率分别为35%和37%,与铜基体相比均降低。铜导线表面热浸镀PbSn合金镀层具有良好的导电性、力学性能及耐腐蚀性等综合性能。随着Pb含量的降低或Sn含量的增加,PbSn合金镀层中α相的相对量减少、β相的相对量增大,其电阻率、硬度和强度降低,塑性略有增大,耐蚀性增强。Pb40Sn60比Pb37Sn63合金镀层的腐蚀速率较高,分别为2.44×10^-2,3.65×10^-3 g·cm^-2·a^-1,耐腐蚀性较差。PbSn合金镀层中α相比β相的腐蚀程度更为严重,α相比β相的耐蚀性要差。     

Effect of strain waveform on creep-fatigue life for Sn–8Zn–3Bi solder

This paper describes the creep‐fatigue life of Sn–8Zn–3Bi under push–pull loading. Creep‐fatigue tests were carried out using Sn–8Zn–3Bi specimens in fast–fast, fast–slow, slow–fast, slow–slow and hold–time strain waveforms. Creep‐fatigue lives in the slow–slow and hold‐time waveforms showed a small reduction from the fast–fast lives but those in the slow–fast and fast–slow waveforms showed a significant reduction from the fast–fast lives. Conventional creep‐fatigue life prediction methods were applied to the experimental data and the applicability of the methods was discussed. Creep‐fatigue characteristics of Sn–8Zn–3Bi were compared with those of Sn–3.5Ag and Sn–37Pb.     

Thermal properties of Sn-based solder alloys

During last few decades, emerging environmental regulations worldwide, more notably in Europe and Japan, have targeted the elimination of Pb usage in electronic assemblies due to the inherent toxicity of this element. This situation drives to the replacement of the Sn–Pb solder alloy of eutectic composition commonly used as joining material to suitable lead-free solders for microelectronic assembly. Sn-based alloys containing Ag, Cu, Bi, and Zn are potential lead-free solders, usually close to the binary or ternary eutectic composition. For this reason a great effort was directed to establish reliable thermophysical data fundamental to interpret the solidification process and fluidity of alloys belonging to these systems. In this work, an analysis of the solidification process of pure Sn, binary Sn–Ag, Sn–Cu, Sn–Bi, Sn–Zn, Sn–Pb and ternary Sn–Ag–Cu eutectic alloys was carried out using computer aided-cooling curve analysis and differential scanning calorimetry.     

The combined effect of nickel and bismuth on the structure of hot-dip zinc coatings

The combined effect of nickel and bismuth on the structure and the morphology of zinc hot-dip galvanized coatings were studied with optical microscopy, scanning electron microscopy and X-ray diffraction. From this investigation it turned out that the coating produced from a zinc melt containing 1% Ni and 1% Bi is composed of three layers corresponding to δ- and η-phase of the Fe-Zn system and T-phase of the Fe-Zn-Ni system. Bi was not detected in these phases. However inclusions of this element were identified between the grains of the T-phase. Their presence could negatively affect the corrosion performance of the coating because bismuth is cathodic to zinc.     

Effects of 0.1 wt% Ni addition and rapid solidification process on Sn–9Zn solder

Effects of 0.1 wt% Ni addition and rapid solidification process on Sn–9Zn solder alloy were investigated. Characteristics of Sn–9Zn–0.1Ni alloy were analyzed compared with those of as-solidified Sn–9Zn alloy. Mechanical properties and interfacial microstructure of solder/Cu joints obtained using these solders were comparatively studied. By comparison with as-solidified Sn–9Zn alloy, the wettability of solder was obviously improved with 0.1 wt% Ni addition, and the melting behavior of the solder was promoted due to the rapid solidification process. The corrosion resistance of as-solidified and rapidly solidified Sn–9Zn–0.1Ni alloys was improved due to the formation of Ni–Zn intermetallic compound (IMC) and the refining of Zn-rich phases. Formation and growth of IMCs at the interface of Sn–9Zn–0.1Ni/Cu joints was significantly depressed. Rapid solidification process promoted the interfacial reaction during soldering and improved the bonding strength of joints.     

锌浴中镍含量对热浸锌镀层厚度的影响

应用SEM,EPMA等方法研究了锌浴中镍含量对热浸锌镀层厚度的影响,试验结果表明,当锌浴中镍含量小于0．12％（wt)时,镀层随镍含量增加而减薄,当镍含量大于0．12％时,镀层则随镍含量增加而增厚,在热镀锌生产线上对0．10％以下的不同镍含量锌浴的应用结果表明,为了兼顾不同产品对最低镀层厚度的要求,镍含量可在0．04％－0．10％间选择,这时由于减少镀层超厚,节锌效果明显。     

Effect of isothermal aging on room temperature impression creep of lead free Sn–9Zn and Sn–8Zn–3Bi solders

Abstract

The influence of isothermal aging on the creep behaviour of Sn–9Zn and Sn–8Zn–3Bi solder alloys was studied by impression testing. The tests were carried out under constant impression stress in the range from 90 to 230 MPa at room temperature. Aging affected the microstructure and, thus, the creep behaviour of the materials. The binary Sn–9Zn alloy, with an as cast microstructure characterised by an almost uniform distribution of fine Zn precipitates, was much more creep resistant than the aged condition containing a more sparse precipitate in a softer matrix. In the ternary Sn–8Zn–3Bi alloy, however, isothermal aging enhanced Bi precipitation with almost no change in the distribution and density of Zn particles, the result being an improved creep resistance of the aged material. Irrespective of the processing condition, Sn–8Zn–3Bi showed much lower steady state creep rates than the Sn–9Zn due to both precipitation and a solid solutioning effect of Bi in the Sn matrix. The stress exponents of the as cast and aged conditions were found to be respectively 8·5 and 7·7 for Sn–9Zn and 9·8 and 7·8 for Sn–8Zn–3Bi. These values are in agreement with those determined by room temperature conventional creep testing of the same materials reported in the literature.     

Effect of doping Al on the liquid oxidation of Sn–Bi–Zn solder

The liquid oxidation behaviors of Sn–40Bi–2Zn and Sn–40Bi–2Zn–0.005Al solders were investigated from thermal dynamics and kinetics analysis. The characteristics of surface oxidation film at 170 °C were studied by thermo gravimetric analysis and X-ray photoelectron spectroscopy (XPS). Sn–40Bi–2Zn solder performed inferiorly in oxidation prevention performance, due to the formation of ZnO, which exhibits lower Gibbs free energy of formation and higher growth rate. Trace amount of Al addition, however, alleviated the oxidation behavior of Zn. XPS depth profile results indicated that the surface layer of Sn–40Bi–2Zn–0.005Al consisted of oxides of Al and Zn formed on the outer surface of the solder film and in the subsequent layer, mainly formed by the oxides of Sn, Bi. Al, basically formed as Al₂O₃, segregated towards the outer surface, seemed to deter the Zn oxidation on the solder surface.     

焙烧Mg-Al水滑石水泥浆涂层对钢筋氯离子腐蚀的缓蚀性能

本工作研究了焙烧Mg-Al水滑石(LDO)水泥浆涂层对钢筋氯离子腐蚀的缓蚀性能。将焙烧Mg-Al水滑石材料添加到水泥浆中制备了复合水泥浆涂层,并涂覆在钢筋表面。由等温吸附实验、线性极化测试(LP)、电化学阻抗谱测试(EIS)研究了在混凝土模拟孔溶液中复合水泥浆涂层对钢筋氯离子腐蚀的缓蚀性能;此外,采用X射线衍射仪(XRD)和傅里叶变换红外光谱(FT-IR)检测了吸附实验前后水泥浆的物相变化,探讨了焙烧Mg-Al水滑石水泥浆涂层对钢筋氯离子腐蚀的缓蚀机理。结果表明,LDO的掺入能显著提高水泥浆体对氯离子的饱和吸附量,且随着LDO掺量的增加,复合水泥浆涂层的综合阻锈效果增强。复合LDO涂层缓释机理归因于层状结构的复原使其能有效地吸附氯离子并释放氢氧根离子,从而能有效阻止氯离子的侵蚀。     

Study on growth factors of intermetallic layer within hot-dipped 25% Al-Zn alloy coating on steel

25% A1-Zn alloy coating performs better than hot dip galvanized coating and 55% A1-Zn-Si coating with regard to general seawater corrosion protection. This study deals with the interfacial intermetallic layer’s growth, which affects considerably the corrosion resistance and mechanical properties of 25%A1-Zn alloy coatings, by means of three-factor quadratic regressive orthogonal experiments. The regression equation shows that the intermetallic layer thickness decreases rapidly with increasing content of Si added to the Zn-Al alloy bath, increases with rise in bath temperature and prolonging dip time. The most effective factor that determined the thickness of intermetallic layer was the amount of Si added to Zn-Al alloy bath, while the effect of bath temperature and dip time on the thickness of intermetallic layer were not very obvious.     

锌镍合金镀层耐腐蚀性的研究

锌镍合金层具有优异的耐蚀性,从全硫酸盐体系中用电沉积的方法制备了纯锌镀层和锌镍合金镀层.应用能量色散X射线分析仪检测了合金层的相对含量.通过中性盐雾试验、极化曲线、交流阻抗和腐蚀浸泡等试验方法研究了镀层的耐腐蚀性能.试验表明,含镍16%的锌镍合金镀层的腐蚀电位较纯锌镀层的腐蚀电位正移230 mV,该合金的耐盐雾性能达到1 000 h,是相同厚度纯锌镀层的4.5倍,具有优良的耐腐蚀性.