Morphology and growth kinetics of Ag3Sn during soldering reaction between liquid Sn and an Ag substrate

For the soldering of recycled Ag sputtering targets, the interfacial reaction between liquid Sn and an Ag substrate at temperatures ranging from 250 –425°C has been investigated. Experimental results show that a scallop-shaped layer of Ag₃Sn intermetallic compounds formed during the soldering reaction. Kinetics analysis indicated that the growth of such interfacial Ag₃Sn intermetallic compounds is diffusion-controlled with activation energy of 70.3kJ/mol. During the reaction, the Ag substrate dissolves into the molten Sn solder and causes the appearance of needle-shaped Ag₃Sn precipitates in the Sn matrix.     

Interfacial reactions between liquid Sn-8Zn-3Bi solders and Cu substrates

The morphology and growth kinetics of intermetallic compounds formed during the soldering reactions between Sn-8Zn-3Bi and Cu substrates at various temperatures ranging from 225 to 350 °C were investigated. The results indicated that a planar layer of Cu_32.1Zn_66.7Sn_0.7Bi_0.5 (γ phase) along with a great number of scallop-shaped intermetallic compounds Cu_19.3Zn_77.8Sn_2.9 (ɛ phase) appeared at the interfaces at temperatures lower than 325 °C. At temperatures higher than 325 °C, the interfacial intermetallics of a composition similar to the planar intermetallics appeared in cluster shape. Kinetics analysis indicated that the intermetallic growth was diffusion-controlled with activation energy of 24.6 KJ/mol.     

Effects of cooling rates on microstructure and microhardness of lead-flee Sn-3.5%Ag solders

The microstructure and microhardness of Sn-3.5%Ag solders were explored in the cooling rate ranging from 0.08 to 10^4 K/s. Under rapid cooling condition, the strong kinetic undercooling effect leads to the actual solidification process starting at the temperature lower than the equilibrium eutectic point, and the actual metastable eutectic point shifts to the higher Ag concentration. Hence, the higher the applied cooling rate is, the more the volume fraction of primary β-Sn crystal forms. At the same time, the separation of primary β-Sn crystal favors restraining the formation of bulk Ag3Sn intermetallic compounds （IMCs） in solder due to the mismatch crystalline orientation relationship, those Ag3Sn phase separating through the eutectic reaction could hardly cling to the primary β-Sn crystal and grow up. Additionally, the Vickers hardness test shows that free β-Sn and spherical Ag3Sn phase in the rapidly solidified alloy strongly improves the microhardness of the Sn-3.5%Ag solder.     

Reaction diffusions of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> and Cu<Subscript>3</Subscript>Sn intermetallic compound in the couple of Sn-3.5Ag eutectic solder and copper substrate

The growth kinetics of intermetallic compound layers formed between Sn-3.5Ag solder and Cu substrate were investigated as a consequence of solid-state isothermal aging. Isothermal aging was carried out in a temperature range between 70°C and 200°C for 0 to 60 days. A quantitative analysis of the intermetallic compound layer thickness as a function of time and temperature was performed. The diffusion couples showed a composite intermetallic layer comprised of Cu₆Sn₅ and Cu₃Sn. The growth of intermetallic compounds followed diffusion-controlled kinetics and the layer thickness reached only 9 μm after 60 day of aging at 150°C. The apparent activation energies were calculated for the growth of the total intermetallic compound (Cu₆Sn₅+Cu₃Sn); Cu₆Sn₅ and Cu₃Sn intermetallic are 65.4, 55.4 and 75.7 kJ/mol, respectively.     

Sn-3.5Ag-0.5Cu/Cu界面的显微结构

研究了热-剪切循环条件下Sn-3．5Ag-0．5Cu钎料／Cu界面的显微结构，分析了界面金属间化合物的生长行为，并与恒温时效后的Sn-3．5Ag-0．5Cu／Cu界面进行了对比。结果表明：恒温时效至100h，Sn-3．5Ag-0．5Cu／Cu界面上已形成Cu6Sn5和Cu3Sn两层金属间化合物；而热-剪切循环至720周Sn-3．5Ag-0．5Cu／Cu界面上只存在Cu6Sn5金属间化合物层，无Cu3Sn层生成，在界面近域的钎料内，颗粒状的Ag3Sn聚集长大成块状；在热-剪切循环和恒温时效过程中，界面金属间化合物的形态初始都为扇贝状，随着时效时间的延长逐渐趋于平缓，最终以层状形式生长。     

稀土镧对Sn3．5Ag0．5Cu钎料组织性能的影响

运用莱卡显微镜、显微硬度计、拉伸试验机等仪器设备,研究添加不同含量稀土元素La对Sn3．5Ag0．5Cu钎料及其与Cu基体焊合后微观组织及性能影响。结果表明：添加不同含量的稀土La均能使Sn3．5Ag0．5Cu钎料及其与Cu基体焊合后组织与性能得到改善,其中以La含量达到0．05％时为最优,显微硬度及剪切强度分别提高14％和10．7％;基于热力学理论计算结果表明稀土元素La具有“亲Sn”倾向,可减小钎料中锡基化合物界面锡的活度,降低IMC的长大驱动力。     

锌对Sn3.5Ag0.5Cu钎料组织性能的影响

运用莱卡显微镜、X射线衍射仪等仪器设备,研究添加元素Zn对Sn3.5Ag0.5Cu钎料组织性能的影响.结果表明:Zn与Ag、Cu形成AgZn和CuZn3化合物,能显著细化Sn3.5Ag0.5Cu钎料组织,降低Sn3.5Ag0.5Cu钎料合金的润湿性,同时可提高Sn3.5Ag0.5Cu钎料合金抗拉强度.     

SnAgCu/Cu和SnPb/Cu界面热-剪切循环条件下化合物的生长行为

对热剪切循环条件下Sn-3.5Ag-0.5Cu/Cu和Sn-Pb/Cu界面上原子扩散和化合物的生长行为进行了研究。结果表明:再流焊后,在两界面上均形成一种Cu6Sn5化合物;随着热剪切循环周数的增加,两界面上化合物的形态均从扇贝状向层状生长,其厚度随循环周数的增加而增加,且生长基本遵循抛物线规律,说明Cu原子的扩散控制了Cu6Sn5化合物的生长。界面近域的钎料内,颗粒状的Ag3Sn聚集长大成块状。     

Active soldering of indium tin oxide (ITO) with Cu in air using an Sn3.5Ag4Ti(Ce,Ga) filler

Indium tin oxide (ITO) ceramics are bonded with ITO and Cu at 250 °C in air using an active solder Sn3.5Ag4Ti(Ce, Ga). The mechanism for such low temperature soldering of ITO ceramics in air has been investigated. Electron probe microanalyzer (EPMA) analyses reveal that the element oxygen distributes uniformly within the solder matrix after soldering, while Ti segregates effectively at the ITO/solder and Cu/solder interfaces at such a low temperature, giving satisfactory joining results of Cu/Cu, ITO/ITO, and ITO/Cu in air.     

Active soldering of ZnS–SiO2 sputtering targets to copper backing plates using an Sn3.5Ag4Ti(Ce, Ga) filler metal

An Sn3.5Ag4Ti(Ce, Ga) active solder is used for joining ZnS–SiO₂ ceramic sputtering targets with copper backing plates at 250 °C in air. Direct soldering using the Sn3.5Ag4Ti(Ce, Ga) metal filler has been found to be a reliable and simple technique for ZnS–SiO₂ ceramic bonding with ZnS–SiO₂ and copper. The shear strengths for ZnS–SiO₂/ZnS–SiO₂ and ZnS–SiO₂/Cu joints are 6.5 and 5.2 MPa, respectively. The bonding mechanism is described, with emphasis placed on the action of a rare earth element (Ce) and the active metal reaction. The interfacial reaction between Sn3.5Ag4Ti(Ce, Ga) filler metal and copper at temperatures ranging from 120 to 200 °C is conducted and discussed.     

Mechanical and electrical properties of In-Bi solder at Bi2212 superconductor interface with annealed Ag spray layers and Ag precoating layers

The electrical properties of solder contact layers between Cu-Ni shunt metal and tube type Bi₂₂₁₂ superconductor that is applied in superconducting fault current limiter were studied. The contact properties of the solders are improved not only by Ag precoating layers, but also by the pre-sprayed Ag layer and subsequent Ag precoating layers. The annealed Ag sprayed layers onto Bi₂₂₁₂ superconductor prior to Ag electroplating work as protecting layers for the superconductor from plating solutions. The contact angle of the electroplated Ag layer is 42.91° and decreases to 15.25° and 5.88° with Ag sprayed layer and additional Ag electroplated layers. The Ag sprayed layer with suitable annealing prior to Ag electroplating improves contact strength of the Ag electroplated layer by about 12% due to denser microstructure of the Ag electroplated layers.     

Preparation of Ti3AlC2 by mechanically activated sintering with Sn aids

The mechanically activated sintering process was adapted to synthesize Ti₃AlC₂ using 3Ti/Al/2C/0.05Sn powder mixtures. The result showed that the powders containing TiC, Ti₃AlC₂ and Ti₂AlC were obtained by mechanical alloying (MA) 3Ti/Al/2C powders. Addition of appropriate Sn reduced the content of Ti₂AlC and enhanced the synthesis of Ti₃AlC₂ significantly. The powders with highest content of Ti₃AlC₂ were obtained by MA 3Ti/Al/2C/0.05Sn powders. Through pressureless sintering the mechanical alloyed powders at 900–1100 °C for 2 h, the high purity Ti₃AlC₂ material with fine organization was produced.     

Phase transformation and morphology of the intermetallic compounds formed at the Sn–9Zn–3.5Ag/Cu interface in aging

The morphology and phase transformation of the intermetallic compounds (IMCs) formed at the Sn–9Zn–3.5Ag/Cu interface in a solid-state reaction have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). The monoclinic η′-Cu₆Sn₅ transforms to the hexagonal η-Cu₆Sn₅ and the orthorhombic Cu₅Zn₈ transforms to the body-centered cubic (bcc) γ-Cu₅Zn₈ as aged at 180 °C. The scallop-shaped Cu₆Sn₅ layer is retained after aging at 180 °C for 1000 h. In the solid-state reaction, Ag is repelled from η′-Cu₆Sn₅ and reacts with Sn to form Ag₃Sn, and the Cu₅Zn₈ layer decomposes. Kirkendall voids are not observed at the Sn–9Zn–3.5Ag/Cu interface even after aging at 180 °C for 1000 h.     

Corrosion resistance of Fe2O3-Cr2O3 artificial passive films formed with LP-MOCVD

Fe₂O₃-Cr₂O₃ artificial passive films were formed with a low pressure MOCVD technique using iron (III) acetylacetonate and chromium (III) acetylacetonate. The relationships between the crystal structure, the chemical state of the constituent elements, and the corrosion resistance of the films were examined in acid solutions. The films deposited above 300°C hardly dissolved in 1.0 M HCl and those deposited below 250°C, however, easily dissolved in the same solution. The dissolution rate of the films in solution increased with decreasing substrate temperature. When polarized cathodically in 1.0 M H₂SO₄, the films deposited below 250°C dissolved due to the reduction of the Fe₂O₃ component in the films. The reduction of the Fe₂O₃ component was, however, suppressed on the films deposited above 300°C. Therefore, with increasing crystallinity and the amount of M-O type chemical bonds, the corrosion resistance of the films increases in HCl and H₂SO₄ solutions.     

The corrosion of Ni3Al in a combustion gas with and without Na2SO4-NaCl deposits at 600–800°C

The corrosion behavior of Ni₃Al containing small additions of Ti, Zr, and B in combustion gases both with and without Na₂SO₄–NaCl deposits at 600–800°C has been studied for times up to four days. The corrosion of the saltfree Ni₃Al leads to the formation of very thin alumina scales at 600°C but of mixed NiO–Al₂O₃ scales containing also some sulfur compounds at higher temperatures, while the rate increases with temperature up to 800°C. The presence of the salt deposits considerably accelerates the corrosion rate, especially at 600 and 800°C. The duplex scales formed at 600°C are composed mostly of a mixture of NiO and unreacted salt in the outer layer and of alumina and aluminum sulfide with some nickel compounds in the inner layer. The scales grown at 700°C contain only one layer of complex composition, while those grown at 800°C are similar but have an additional outer layer containing similar amounts of nickel and aluminum. At 600 and 700°C NiSO₄ can be detected also in the salt layer. The samples corroded at 700°C and 800°C also show an Al-depleted zone containing titanium sulfide precipitates at the surface of the alloy. The hot corrosion of Ni₃Al involves a combination of various mechanisms, including fluxing of the oxide scale as well as mixed oxidation-sulfidation attack. At all temperatures Ni₃Al shows poor resistance to hotcorrosion attack as a result of the formation of large amounts of Ni compounds in the scales.     

Effect of CF4 plasma treatment on the interfacial fracture energy between inkjet-printed Ag and flexible polyimide films

The effects of a CF₄ plasma treatment on the interfacial fracture energy of an inkjet-printed Ag/polyimide system were investigated for inkjet printing metallization techniques in flexible printed circuit board applications. The interfacial fracture energy was evaluated by using a 180° peel test and by calculating the plastic deformation energy of the peeled metal and polyimide films from an energy balance relationship during the steady-state peeling process. The interfacial fracture energy between the Ag and the polyimide increased after the CF₄ plasma treatment to the polyimide surface. This was caused by an increase in the surface roughness as well as changes to the surface functional groups of the polyimide film. Therefore, both the mechanical interlocking effect and the chemical bonding effect were responsible for the improvement in the interfacial adhesion in inkjet-printed Ag/polyimide systems.     

Influence of nanometer lanthanum fluoride on friction and wear behaviors of bonded molybdenum disulfide solid lubricating films

Influence of nanometer lanthanum fluoride (nano-LaF₃) on the friction and wear behavior of bonded molybdenum disulfide (MoS₂) solid lubricating film was investigated using an oscillating friction-wear tester under dry friction condition. The worn surface of the lubricating film and the transfer film formed on the surface of the counterpart ball were observed by SEM. The microstructure of the lubricating film filled with nano-LaF₃ and the distribution of F and La in the lubricating film were investigated with transmission electron microscopy (TEM) and field emission scanning electron microscope (FESEM) equipped with an energy dispersive X-ray spectrometer, respectively. It was found that nano-LaF₃ as a filler contributes to improve the wear-resistance property of the lubricating film. The lubricating film modified with nano-LaF₃ filler exhibits better wear-resistance property than that of the lubricating film without nano-LaF₃ filler at a relatively lower load (less than 250 N) and within a wide oscillatory frequency range between 5 and 35 Hz. However, the incorporation of nano-LaF₃ filler results in small increase of friction coefficient of the lubricating film. Transmission electron microscopy (TEM) and elementally X-ray map results of the lubricating film modified with nano-LaF₃ filler indicate that partial LaF₃ nanoparticles distribute around the MoS₂ particles, while other LaF₃ nanoparticles disperse in the binder. The SEM morphology of the frictional surface shows that the filler of nano-LaF₃ is able to enhance the compactness of the frictional surface, and results in an improvement of the wear-resistance property of the MoS₂ lubricating film.     

Effect of Ag-doping on crystal structure and high temperature thermoelectric properties of c-axis oriented Ca3Co4O9 thin films by pulsed laser deposition

Ag-doped Ca₃Co₄O₉ thin films with nominal composition of Ca_3−xAg_xCo₄O₉ (x = 0∼0.4) have been prepared on sapphire (0 0 0 1) substrates by pulsed laser deposition (PLD). Structural characterizations and surface chemical states analysis have shown that Ag substitution for Ca in the thin films can be achieved with doping amount of x ≤ 0.15; while x > 0.15, excessive Ag was found as isolated and metallic species, resulting in composite structure. Based on the perfect c-axis orientation of the thin films, Ag-doping has been found to facilitate a remarkable decrease in the in-plane electrical resistivity. However, if doped beyond the substitution limit, excessive Ag was observed to severely reduce the Seebeck coefficient. Through carrier concentration adjustment by Ag-substitution, power factor of the Ag-Ca₃Co₄O₉ thin films could reach 0.73 mW m⁻¹ K⁻² at around 700 K, which was about 16% higher than that of the pure Ca₃Co₄O₉ thin film.     

Application of auger electron spectroscopy and inert metal marker techniques to determine metal and oxygen transport in oxide films on metals

Auger electron spectroscopy in combination with depth profiling by Ar ion sputtering was employed as a surface analytical technique to determine the positions of thin (3–5 nm) inert Pd markers during growth of oxide films on Al, Ni, and -NiAl. Alumina films 35 and 120 nm thick formed on Al and -NiAl, respectively, grew by inward diffusion of oxygen. Metal migration accounted predominantly for the growth of a NiO film 150 nm thick on the (111) crystal face of Ni. However, an assessment could not be made with respect to oxygen diffusion, if any, in this film due to the limitations imposed on precise depth profiling of the marker position caused by uneven sputtering of the oxide and metal phases.