Electrochemical corrosion behaviour of Pb-free Sn-8.5Zn-0.05Al-XGa and Sn-3Ag-0.5Cu alloys in chloride containing aqueous solution

The electrochemical corrosion behaviour of Pb-free Sn-8.5Zn-0.05Al-XGa and Sn-3Ag-0.5Cu alloys was investigated in 3.5% NaCl solution by using potentiodynamic polarization techniques. The results obtained from polarization studies revealed that there was a negative shift in the corrosion potential with increase in Ga content from 0.02 to 0.2 wt% in the Sn-8.5Zn-0.05Al-XGa alloy. These changes were also reflected in the corrosion current density (I_corr) value, corrosion rate and linear polarization resistance (LPR) of the four element alloy. However, for Sn-3Ag-0.5Cu alloy a significant increase in the corrosion rate and corrosion current density was observed as compared to the four element alloys. SIMS depth profile results established that ZnO present on the outer surface of Sn-8.5Zn-0.05Al-0.05Ga alloy played a major role in the formation of the oxide film. Oxides of Sn, Al and Ga contributed a little towards the formation of film on the outer surface of the alloy. On the other hand, Ag₂O was primarily responsible for the formation of the oxide film on the outer surface of Sn-3Ag-0.5Cu alloy.     

The polarization characteristics of Pb-free Sn-8.5Zn-XAg-0.1Al-0.05Ga alloy in 3.5% NaCl solution

The polarization characteristics of Pb-free Sn-8.5Zn-XAg-0.1Al-0.05Ga alloy with varying Ag content were investigated in 3.5% NaCl solution. The value of Ag content i.e X varied from 0.1 wt% to 2 wt%. An increase in the Ag content up to 2 wt% resulted in a progressive increase in the corrosion current density and shifted the corrosion potential (E_corr) towards more active values. These changes were also reflected in the corrosion rate of the solder alloy. However the linear polarization resistance values decreased with increase in the weight content of silver. Increasing the Ag content from 0.1 to 2 wt% did not show a significant improvement in the passivation behaviour of the solder alloy as reflected in the passivation current density (i_p) and critical current density (i_cc) values. XPS and SIMS depth profile results revealed that the oxides of Zn and Sn were present in high concentrations on the outer surface of the solder alloy along with very low concentration of Al₂O₃.     

Effects of Ga,Al, Ag,and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solder

An orthogonal method was used to evaluate the effects of Ga, Al, Ag, and Ce multi-additions on the wetting characteristics of Sn-9Zn lead-free solders by wetting balance method. The results show that the optimal loading of Ga, Al, Ag, and Ce was 0.2 wt.%, 0.002 wt.%, 0.25 wt.%, and 0.15 wt.%, respectively. Intermetallic compounds (IMCs) formed at the interface between Sn-9Zn-0.2Ga-0.002Al-0.25Ag-0.15Ce solder and Cu substrate were investigated by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) analysis. The SEM images illustrate that the IMCs can be divided into two portions from the substrate side to the solder side: a planar Cu₅Zn₈ layer and an additional continuous scallop-like AgZn₃ layer. The EDS analysis also shows that Ga segregates in the solder abutting upon the interface. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) of the surface components of Sn-9Zn-0.2Ga-0.002Al-0.25Ag-0.15Ce solder indicate that Al aggregates at the surface in the form of Al₂O₃ protective film, which prevents the further oxidation of the solder surface. On the other hand, Ce aggregates at the subsurface, which may reduce the surface tension of the solder and improve the wettability in consequence.     

稀土铈在Sn-Zn无铅钎料表面的高温氧化行为

通过俄歇电子能谱法和X射线光电子能谱法研究了Sn-9Zn-0.15Ce和Sn-9Zn-0.002Al-0.2Ga-0.25Ag-0.15Ce两种钎料表面Ce元素的分布和存在形式.结果表明,铈在Sn-9Zn-0.15Ce钎料表面0~40 nm范围内的富集区浓度达到30%(原子分数)左右,是基体内部的250倍,主要以CeO2和Ce2O3形态存在.在Sn-9Zn-0.15Ce钎料中复合添加镓和铝后,Ga元素在钎料表面0~6 nm范围内富集,Al元素在表面2~20 nm范围内富集并主要以氧化态形式存在.Ce元素富集在距离钎料表面2~60 nm的范围内,处于Ga,Al元素富集层的下方;由Ga,Al元素富集层构成的致密保护膜可显著降低表面铈被氧化的概率.     

Ag,Al,Ga对Sn-9Zn无铅钎料润湿性能的影响

采用润湿平衡法测试了Sn-9Zn-X(X为Ag,Al,Ga)无铅钎料分别配合ZnCl2-NH4Cl钎剂和免清洗助焊剂,在空气和氮气保护的两种条件下的润湿性能,分析研究了合金元素Ag,Al,Ga的添加量对Sn-9Zn-X无铅钎料润湿性的影响规律.结果表明,合金元素Ag,Al,Ga在Sn-9Zn中的最佳添加量(质量分数)分别为0.3%,0.005%～0.02%,0.5%.采用氮气保护可以显著改善Sn-9Zn-X无铅钎料的润湿性,而Sn-9Zn-X无铅钎料配合ZnCl2-NH4Cl钎剂时具有较好的润湿性,甚至优于Sn-3.5Ag-0.5Cu在相同条件下的润湿性.这一研究结果表明,通过研发适合于Sn-Zn系无铅钎料的高性能助焊剂,从而改善Sn-Zn系钎料的润湿性能是完全可行的.     

复合添加Ga,Al,Ag对Sn-9Zn钎料性能的影响

采用润湿平衡法研究了合金元素Ga,Al,Ag复合添加对Sn-9Zn钎料润湿性的影响.结果表明,Ga,Al,Ag的最佳添加量分别为0.2,0.002,0.25(质量分数,%);添加合金元素后钎料的高温抗氧化性能显著提高.俄歇电子能谱分析表明,Sn-9Zn-0.2Ga-0.002Al-0.25Ag钎料表面Al高度富集并形成一层致密的氧化膜,可阻挡氧向液态钎料内部扩散,减少钎料的氧化.Sn-9Zn-0.2Ga-0.002Al-0.25Ag钎料与Cu/Ni/Au基板之间的金属间化合物由一层平坦的AuZn3和颗粒状的AuAgZn2化合物组成.另外,微焊点力学试验表明,采用Sn-9Zn-0.2Ga-0.002Al-0.25Ag钎料时,电子元器件与基板间微焊点的力学性能比Sn-9Zn钎料略有提高.     

Sn-0.3Ag-0.7Cu-xSb无铅钎料润湿性

研究了微量Sb元素对Sn-0.3Ag-0.7Cu无铅钎料润湿性的影响,采用润湿平衡法探讨了Sn-0.3Ag-0.7Cu-xSb钎料在不同氛围和不同钎剂条件下的润湿性能.结果表明,微量的Sb元素可以显著提高Sn-0.3Ag-0.7Cu无铅钎料润湿性.在氮气氛围条件下,Sn-0.3Ag-0.7Cu-xSb钎料的润湿性得到显著改善,主要基于氮气氛围减小熔融钎料的氧化.辅助不同的钎剂,钎料的润湿性差异较大,选择合适的钎剂可以明显提高Sn-0.3Ag-0.7Cu-xSb钎料的润湿性.     

用循环极化曲线研究Al和铝合金的点蚀行为

通过循环极化确定纯Al和Al-7Zn-0.1Sn-0.015Ga (质量分数,%) 合金在3.5%NaCl溶液中的自腐蚀电位E_corr、点蚀电位E_pit、点蚀转变电位E_ptp和保护电位E_rp,并通过Al和铝合金在这些特征电位的点蚀形貌研究了它们的点蚀行为及点蚀扩展机理。结果表明：在点蚀电位时开始出现点蚀坑,随着电位升高点蚀坑迅速向横向和纵向扩展直至保护电位;纯Al的点蚀坑为窄而深的方形点蚀形貌,蚀坑内部为粗糙的结晶状结构,且表面出现明显的丝状腐蚀。Al-7Zn-0.1Sn-0.015Ga合金的点蚀形貌为宽而浅的圆形腐蚀坑,蚀坑内部比较光滑,且丝状腐蚀消失。合金元素能明显活化合金,降低点蚀坑深度,改善其腐蚀形貌。     

In对Sn-8Zn-3Bi无铅钎料润湿性的影响

首先采用铺展法测试了Sn-8Zn-3Bi-(0～5)In钎料合金的铺展性.结果表明,少量In的加入提高了钎料的润湿性.当In含量达到0.5%时(质量分数,下同),钎料在铜基底上的铺展面积最大.采用气泡最大压力法对Sn-8Zn-3Bi-(0～1.5)In钎料熔体进行了表面张力测试.加入0.5%的In大大降低了Sn-8Zn-3Bi钎料熔体的表面张力,但进一步增加In的含量导致熔体表面张力增大.最后采用润湿平衡法对上述钎料进行了润湿力测试.结果表明0.5%In的加入使合金的润湿力达到最大,其原因是钎料/铜界面的界面张力减小.     

Effect of carbon on stress corrosion cracking and anodic oxidation of iron in NaOH solutions

Anodic behaviour of decarburised iron and of quenched Fe-C materials with up to 0.875 wt% C was examined in 8.5 M NaOH at 100 °C to explain the role of carbon in caustic stress corrosion cracking (SCC) of plain steels. Removal of carbon from Armco iron strongly reduced its intergranular SCC. Slip steps on grains did not initiate cracks. It has been shown that carbon at low contents deteriorates the passivation of iron, whereas at high contents it promotes the formation of magnetite. High resistance to SCC of high carbon steels can be explained by an intense formation of magnetite on these steels.     

The electrochemical behaviour of leaded brass in neutral CL and SO4 media

The electrochemical behaviour of lead brass with different leaded content in neutral chloride and sulphate solutions was investigated using the EIS technique. For comparison, the behaviour of the pure components of the alloy was investigated under the same conditions. The corrosion process was found to proceed via oxygen reduction following a diffusion controlled mechanism. The Cu electrode showed a higher polarization resistance due to film formation during oxygen reduction. Zn and Pb showed markedly lower impedance values due to continuous dissolution. The two investigated brass alloys (1.8% and 3.5% Pb, respectively) showed higher impedance values indicating the passivation of the surface in the Cl⁻ or SO₄⁻ media. Brass II was found to be more stable against corrosion indicating the beneficial effect of the lead content in the alloy.At cathodic potentials, the only process is the oxygen reduction. Anodic polarization leads to selective dissolution of Zn. At more positive potentials simultaneous dissolution of the alloy components with the deposition of Cu(I) salt takes place leading to the passivation of the alloy surface. At higher potentials, film breakdown occurs producing Cu(II) compounds whose diffusion control the corrosion process. At potentials higher than − 0.1 V, pitting corrosion was observed and a transmission line type in the impedance spectra was recorded.     

Effects of pH and chloride concentration on pitting corrosion of AA6061 aluminum alloy

Effects of pH solution and chloride (Cl⁻) ion concentration on the corrosion behaviour of alloy AA6061 immersed in aqueous solutions of NaCl have been investigated using measurements of weight loss, potentiodynamic polarisation, linear polarisation, cyclic polarisation experiment combined with open circuit potential transient technique and optical or scanning electron microscopy.The corrosion behaviour of the AA6061 aluminum alloy was found to be dependant on the pH and chloride concentration [NaCl] of solution. In acidic or slightly neutral solutions, general and pitting corrosion occurred simultaneously. In contrast, exposure to alkaline solutions results in general corrosion. Experience revealed that the alloy AA6061 was susceptible to pitting corrosion in all chloride solution of concentration ranging between 0.003 wt% and 5.5 wt% NaCl and an increase in the chloride concentration slightly shifted both the pitting E_pit and corrosion E_cor potentials to more active values. In function of the conditions of treatment, the sheets of the alloy AA6061 undergo two types of localised corrosion process, leading to the formation of hemispherical and crystallographic pits.Polarisation resistance measurements in acidic (pH = 2) and alkaline chloride solutions (pH = 12) which are in good agreement with those of weight loss, show that the corrosion kinetic is minimised in slightly neutral solutions (pH = 6).     

Development of high strength Sn-0.7Cu solders with the addition of small amount of Ag and In

Nowadays, a major concern of Sn-Cu based solder alloys is focused on continuously improving the comprehensive properties of solder joints formed between the solders and substrates. In this study, the influence of Ag and/or In doping on the microstructures and tensile properties of eutectic Sn-0.7Cu lead free solder alloy have been investigated. Also, the effects of temperature and strain rate on the mechanical performance of Sn-0.7Cu, Sn-0.7Cu-2Ag, Sn-0.7Cu-2In and Sn-0.7Cu-2Ag-2In solders were investigated. The tensile tests showed that while the ultimate tensile strength (UTS) and yield stress (YS) increased with increasing strain rate, they decreased with increasing temperature, showing strong strain rate and temperature dependence. The results also revealed that with the addition of Ag and In into Sn-0.7Cu, significant improvement in YS (∼255%) and UTS (∼215%) is realized when compared with the other commercially available Sn-0.7 wt. % Cu solder alloys. Furthermore, the Sn-0.7Cu-2Ag-2In solder material developed here also exhibits higher ductility and well-behaved mechanical performance than that of eutectic Sn-0.7Cu commercial solder. Microstructural analysis revealed that the origin of change in mechanical properties is attributed to smaller β-Sn dendrite grain dimensions and formation of new inter-metallic compounds (IMCs) in the ternary and quaternary alloys.     

The corrosion behaviour of Fe-15Mn-7Si-9Cr-5Ni shape memory alloy

The corrosion behaviour of Fe-15Mn-7Si-9Cr-5Ni (mass%) shape memory alloy at 25 °C in 0.5 M H₂SO₄ and 3.5% NaCl solutions has been studied using potentiodynamic polarization and electrochemical impedance techniques. Three different microstructures viz., single-phase γ, γ-δ and γ-Fe₅Ni₃Si₂, were produced by heat-treating the alloy in different equilibrium phase fields. The corrosion behaviour in 0.5 M H₂SO₄ solution is almost same for all three microstructures, barring a slight difference in the passivation range. Although, the passivation current in 0.5 M H₂SO₄, is in the same range as that of SS 304, the critical current required for onset of passivation is almost three orders higher and the passivation range is much shorter. In 3.5% NaCl solution the corrosion behaviour of all three microstructures of the Fe-15Mn-7Si-9Cr-5Ni shape memory alloy was that of general dissolution without passivity or localized attack (pitting). The best corrosion resistance in both H₂SO₄ and NaCl solutions is shown by the single-phase γ microstructure.     

Corrosion studies of single crystals of iron-gallium alloys in aqueous environments

Iron-gallium (Fe-Ga) alloys have attracted lot of attention for use in sensor and actuator applications due to an excellent combination of large low-field magnetostriction, high mechanical strength, good ductility and low cost. This paper reports the very first measurement of the corrosion behavior of single crystals of Fe-Ga alloys. The corrosion behaviors of single crystals of Fe-15 at.% Ga, Fe-20 at.% Ga and Fe-27.5 at.% Ga alloys were studied in acidic (0.1 M HCl), basic (0.1 M NaOH) and simulated seawater (3.5 wt.% NaCl) environments. Dependence of corrosion rates on the crystal orientation is also examined. The polarization resistance technique was used for measuring the corrosion potentials and corrosion rates. The corrosion rate of single crystals of Fe-Ga alloys in 0.1 M HCl aqueous solution is higher than that in 3.5 wt.% NaCl aqueous solutions. The corrosion rate of single crystals of Fe-Ga alloys is least in 0.1 M NaOH aqueous solutions.     

The initial stage of pitting corrosion on coated steels investigated by photon rupture in chloride containing solutions

A photon rupture method, film removal by a focused pulse of pulsed Nd-YAG laser beam irradiation, has been developed to enable oxide film stripping at extremely high rates without contamination from the film removal tools. In the present study, Zn-55mass%Al alloy and Al-9mass%Si alloy-coated steel specimens covered with protective nitrocellulose film were irradiated with a focused pulse of a pulsed Nd-YAG laser beam at a constant potential in 0.5 kmol m⁻³ H₃BO₃-0.05 kmol m⁻³ Na₂B₄O₇ (pH = 7.4) with 0.01 kmol m⁻³ of chloride ions to investigate the initial stage of localized corrosion. At low potentials, oxide films on both coated alloys were reformed after the nitrocellulose films were removed by this method. The oxide film formation kinetics follows an inverse logarithmic law, in agreement with Cabrera-Mott theory. However, at high potentials, localized corrosion producing corrosion products occurs at the area where nitrocellulose film was removed. Nevertheless, when the applied potential is less noble, the dissolution current of the Zn-55mass%Al-coated steel samples is higher than that of Al-9mass%Si-coated samples.     

Wetting of Sn-Zn-<Emphasis Type="Italic">x</Emphasis>In (<Emphasis Type="Italic">x</Emphasis> = 0.5, 1.0, 1.5 wt%) Alloys on Cu and Ni Substrates

Wetting angles of Sn-8.8Zn and Sn-8.8Zn-xIn alloys (x = 0.5, 1.0, 1.5 wt%) were studied with the sessile drop method. Wetting tests were carried out for 900 s in the presence of ORM0 flux at 493, 523, and 573 K on copper and at 523 K on nickel substrates, respectively. It was found that the addition of In to Sn-8.8Zn alloy improves its wetting on both substrates by reducing the value of apparent wetting angle. Also, with increasing temperature a decrease of wetting angle on copper is observed in the case of 0 and 1.5 wt% of In alloys. Solidified solder-substrate couples were cross-sectioned and examined with scanning electron microscopy coupled with electron dispersive X-ray analysis. Interlayers were found at the interface of solders with copper and nickel, and their compositions are close to Cu₅Zn₈ and Ni₅Zn₂₁ intermetallics, respectively. However, in the case of Sn-8.8Zn-1.5/Ni couple small scallops are observed instead of continuous interlayer.     

Corrosion characterization of new tin-silver binary alloys in nitric acid solutions

Electrochemical techniques were used to characterize the corrosion behavior of four new binary alloys xSn-Ag (x = 26, 50, 70 and 96.5 wt%) alloys and their individual metal components in nitric acid solutions. The experimental data were collected by using open-circuit potential, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Over the concentration range studied (0.075-4.5 M), each of the two corrosion parameters (E_corr and i_corr) shows a regular dependency on both the alloy composition and the solution concentration. In general, for all studied samples, especially pure Ag and those with lower Sn contents (26 and 50 wt%), increasing the acid concentration increases i_corr, meanwhile causes a shift of the corresponding E_corr towards more positive values. This is probably due to the increase in the effect of cathodic depolarizer as the nitric acid concentration is increased. EIS results at the free corrosion potential confirmed well this behavior, where at concentrations ?1.5 M the thickness of the surface film increases while its resistance decreases with increasing tin wt%, indicating formation of less protective thicker film. However, at higher concentrations all samples exhibit identical behavior.     

Repassivation of the damage generated by cavitation on UNS N08031 in a LiBr solution by means of electrochemical techniques and Confocal Laser Scanning Microscopy

The objective of this work is to study the influence of cavitation on the corrosion behaviour of Alloy 31, a highly-alloyed austenitic stainless steel (UNS N08031), in a LiBr heavy brine solution (992 g/L) at 25 °C. The presence of cavitation shifted the OCP value towards the active direction by 708 mV_Ag/AgCl, increased anodic current densities and passivation current density, i_p, and reduced the pitting potential, E_p.Repassivation behaviour of Alloy 31 has been investigated by using potentiostatic tests at different potentials. The current density transient obtained after interrupting cavitation was used to obtain the repassivation index, n, provided by the slope of the log i(t) vs. log t representation. The value of n decreased as the applied potential was increased, reaching values near zero for potentials close to the pitting potential. The damage generated during the potentiostatic tests has been quantified by means of Confocal Laser Scanning Microscopy.     

Bi对Sn-0.3Ag-0.7Cu无铅钎料熔点及润湿性能的影响

研究了添加适量的Bi元素对低银型Sn-0．3Ag-0．7Cu无铅钎料合金性能的影响,应用差示扫描量热仪和SAT-5100型润湿平衡仪对Sn-0．3Ag-0．7Cu&#183;xBi（x=0.1,3,4．5）钎料的熔点、润湿性能作了对比试验分析。结果表明,一定量Bi元素的加入可以降低Sn-0．3Ag-0．7Cu钎料合金的熔点,并改善其润湿性能。但过多的Bi元素会导致钎料的液固相线温度差增大,塑性下降,造成焊点剥离缺陷。综合考虑得到Sn-0．3Ag-0．7Cu-3．0Bi无铅钎料具有最佳的综合性能。