Ultrasonic-assisted soldering of sapphire through metallic transition layers of Al and Zn using Sn-xZn-2Al solder alloys

Ultrasonic-assisted soldering has potential in the electrical industry especially for the joining of ceramics. The Al-activated Sn-based alloys are promising ultrasonic solders due to simple preparation, while the current approaches required long ultrasonic action. In order to increase the efficiency and reduce ultrasonic-induced damage, this study investigated the soldering of sapphire (monocrystalline α-Al₂O₃) performed under an ultrasonic action for 0.5 s by using Sn-xZn-2Al(x = 9, 25, 45) solder alloys. Microstructures of interfacial transition layers between the sapphire and solders were focused on. It has been found that at the interfaces no interfacial reaction phases formed and the interfacial bonding was realized via metallic transition layers. Three kinds of interfacial structures existed, that is, sapphire/Al atomic layer/β-Sn, sapphire/Al atomic layer/(Zn enrichment layer)/β-Sn and sapphire/Al atomic layer/Zn nanocrystalline clusters/β-Sn. The elements of Al and Zn in the solder alloys underwent a selective and asynchronous adsorption process during the ultrasonic action. An Al atomic layer formed on the sapphire surface by the stronger chemical adsorption and acted as a transition layer between sapphire and β-Sn. The Zn enrichment layer was distributed locally along the interface and as the Zn content increased in the solder alloys, more localized Zn nanocrystalline clusters formed. These Zn transition structures strengthened the interfacial bonding by transforming the Al atomic layer/β-Sn interface into the Al atomic layer/Zn transition structures/β-Sn interfaces. The joints possessed a shear strength of up to 28 MPa when soldering with Sn–45Zn–2Al at 350 °C.     

Liquid metal/ceramic interactions in the (Cu,Ag, Au)/ZrB2 systems

Wetting and spreading experiments on ZrB₂ in contact with liquid Cu, Ag and Au have been performed by the sessile drop technique under a vacuum. The wetting and spreading characteristics and the interfacial reactions are discussed as a function of time and of the metal involved. The interfacial morphologies, analysed by optical microscopy, SEM and EDS show the presence of regular interfaces without macroscopic reaction layers. Gold, to a very large extent and copper are shown to give rise to extensive penetration along grain-boundaries, whereas silver neither wets nor penetrates. Interfacial diffusion/dissolution is taken into account and the consequent changes in liquid metal surface tension and wetting behaviours have been evaluated by means of thermodynamic calculations.Moreover, interfacial energetics at the atomistic level has been investigated by means of pseudopotential-based Density Functional Theory (DFT) technique. It is shown how the calculation of the ideal work of separation on the specific transition metal borides-molten metal systems can be used to interpret the wetting behaviour. Moreover, the dependence of the adhesion behaviour on the electronic structure at the interface and on the interface epitaxy and composition is also briefly discussed.     

On the Predominant Electron-Donicity of Polar Solid Surfaces

The reasons for the predominant electron-donicity of almost all solid polar surfaces and its implications are discussed in this paper. By contact angle or interfacial tension measurements, the electron-accepting as well as the electron-donating properties of polar liquids can be ascertained, through the interplay between their energies of adhesion and cohesion. For the solid-liquid interface, direct interfacial tension measurements are not possible, but indirectly, solid/liquid interfacial tensions of polar systems can be obtained by contact angle measurement. However, as the energy of cohesion of a solid does not influence the contact angle formed by a liquid drop placed upon its surface, one can only measure the solid surface'ks residual polar property, manifested by the energy of adhesion between solid and liquid. This residual polar property is of necessity the dominant component; in most cases this turns out to be its electron donicity. When, by means of contact angle measurements with polar liquids, both electron-accepting and electron-donating potentials are found on a polar solid, it is most likely still partly covered with a polar liquid: usually water. The amount of residual water of hydration of a polar solid follows from its polar (Lewis acid-base) surface tension component (γ^AB). The degree of orientation of the residual water of hydration on a polar solid can be expressed by the ratio of the electron-donating to electron-accepting potentials (γ^⊖/γ^⊕), measured on the hydrated surface.     

Influence of oxide dopants on the wetting of doped graphite by cryolite/alumina melts

In the aluminium smelting industry, the wetting of the electrolyte on the carbon anode is an important property associated with the onset of the anode effect. The effect of dopants on the wettability of the anode was investigated in this study. The carbon material selected was graphite. The composition of the cryolite/alumina melts varied between a very low alumina content and 6 wt.% alumina. The sessile drop approach was adopted to measure the contact angle between the melt and the graphite at 1030 °C. The influence of oxide dopants, chromium III oxide and alumina, in the graphite on the wettability was studied. The wettability on a pure graphite surface depends to a small extent on the liquid surface tension but mostly on the liquid–solid interfacial tension that varies with the concentration of alumina in the liquid. The wettability on an oxide doped graphite surface depends on the dissolution of the oxide in the melt that changes the liquid–solid interfacial tension. The alumina dissolution has a double effect on the liquid–solid interfacial tension: the chemical reaction as well as the change in the oxy-anions concentration at the interface decrease the interfacial tension.     

Interface reactions between rutile coatings and molten aluminium or AlSi7Mg0.6 alloy

Rutile coatings deposited on corundum substrates are considered as promising functional elements improving the efficiency of the filtration of oxide inclusions out of aluminium melts. This contribution describes the reactions between rutile and two kinds of the aluminium melts and discusses the consequences of these reactions for the filtration process. It was found that the contact of rutile coatings with molten aluminium leads to the formation of a corundum layer at the solid/liquid interface. The exposure of the rutile coatings to molten AlSi7Mg0.6 alloy produces an interface layer of MgTiO₃. The interface layers possess defined orientation relationship to rutile which is characteristic for locally heteroepitaxial growth. The density functional theory calculations revealed that the TiO₂/α-Al₂O₃ and TiO₂/MgTiO₃ interfaces with the orientation relationships observed experimentally have low interface energies. The mechanisms of the interface layer formation and the impact of these layers on the degradation of the rutile coatings are discussed.     

The effect of polymer surface on the wetting and adhesion of liquid systems

Young's equation describes the wetting phenomenon in terms of the contact angle between a liquid and a solid surface. However, the contact angle is not the only parameter that defines liquid–solid interactions, an additional parameter related to the adhesion between the liquid drop and the solid surface is also of importance in cases where liquid sliding is involved. It is postulated that wetting which is related to the contact angle, and interfacial adhesion, which is related to the sliding angle, are interdependent phenomena and have to be considered simultaneously. A variety of models that relate the sliding angle to the forces developed along the contact periphery between a liquid drop and a solid surface have been proposed in the literature. Here, a modified model is proposed that quantifies the drop-sliding phenomenon, based also on the interfacial adhesion that develops across the contact area of the liquid/solid interface. Consequently, an interfacial adhesion strength parameter can be defined depending on the mass of the drop, the contact angle and the sliding angle. To verify the proposed approach the adhesion strength parameter has been calculated, based on experimental results, for a number of polymer surfaces and has been correlated with their composition and structure. The interaction strength parameter can be calculated for any smooth surface from measurements of the contact and the sliding angles.     

Some Observations on the Wetting of Al2O3, by Aluminum

The contact angle of liquid aluminum with recrystallized alumina and with sapphire, respectively, was measured using the sessile-drop technique, The variation in contact angle with time was determined at temperatures of the order of 1200°C. in vacuo at 10-⁴ mm. Hg. A significant difference in spreading behavior was observed for aluminum on the respective aluminas. In the case of aluminum on recrystallized Al₂O₃ the contact angle attained a steady value, whereas on sapphire the drop was observed to spread and contract repeatedly. The contact angle assumed after each contraction was essentially constant. The observations are discussed and an explanation is proposed for the effect in terms of changes in the interfacial geometry between liquid aluminum and the alumina due to dissolution.     

On the Predominant Electron-Donicity of Polar Solid Surfaces

The reasons for the predominant electron-donicity of almost all solid polar surfaces and its implications are discussed in this paper. By contact angle or interfacial tension measurements, the electron-accepting as well as the electron-donating properties of polar liquids can be ascertained, through the interplay between their energies of adhesion and cohesion. For the solid-liquid interface, direct interfacial tension measurements are not possible, but indirectly, solid/liquid interfacial tensions of polar systems can be obtained by contact angle measurement. However, as the energy of cohesion of a solid does not influence the contact angle formed by a liquid drop placed upon its surface, one can only measure the solid surface'ks residual polar property, manifested by the energy of adhesion between solid and liquid. This residual polar property is of necessity the dominant component; in most cases this turns out to be its electron donicity. When, by means of contact angle measurements with polar liquids, both electron-accepting and electron-donating potentials are found on a polar solid, it is most likely still partly covered with a polar liquid: usually water. The amount of residual water of hydration of a polar solid follows from its polar (Lewis acid-base) surface tension component (γ^AB). The degree of orientation of the residual water of hydration on a polar solid can be expressed by the ratio of the electron-donating to electron-accepting potentials (γ^?/γ^⊕), measured on the hydrated surface.     

High-Temperature Wetting of Sapphire by Aluminum

Sessile drop studies of molten aluminum on single-crystal sapphire substrates were conducted to investigate the effects of atmosphere on contact angle, substrate reactions, and interfacial crystal growth. Unlike previous investigations performed briefly in a vacuum environment in a temperature range within 600°C of the aluminum melting point, these experiments were conducted at higher temperatures (1200° to 1600°C) and at 1-atm total pressure over longer experimental times to more closely approach equilibrium conditions. A continuously flowing buffered gas system utilizing high-purity metered mixtures of hydrogen and helium in combination with a thoria ceramic electrolyte sensor were employed to achieve variations of the oxygen partial pressure from 10⁻¹⁹ to 10⁻¹⁵ atm while continuously maintaining the total pressure at 1 atm. At constant temperature, it was found that neither the oxygen partial pressure nor the crystallographic orientation of the sapphire substrate had a significant effect on the observed contact angles. A continuous decrease of acute contact angles and a single reaction ring characterized the 8-h experiments without the alternating spreading and contracting behavior repeatedly reported in the literature. This phenomenon can be attributed to the lower rate of metal evaporation and interfacial reaction at the higher total gas pressure and yet extremely low oxygen partial pressure of these experiments. Profilometric analysis of sapphire substrates subsequent to the removal of the quenched sessile drops indicates a reduction in metal–solid interaction due to the closer approach to equilibrium than in previous studies. An epitaxial orientation with respect to the substrate was observed in α-alumina crystallite formation at the metal–ceramic interface. Experimental evidence suggests that it was formed by a nucleation and growth process during the cooling period.     

Interface Reactions Between Metals and Ceramics: IV, Wetting of Sapphire by Liquid Copper-Oxygen Alloys

The wettability of sapphire single crystals by liquid copper which contained oxygen added as cupric oxide was investigated using the sessile drop technique in vacuum at 1230°C. Additions of cupric oxide to copper, varying from 1 to 72% of copper weight, resulted in rapid chemical reaction at the solid-liquid interface with a significant reduction of the contact angle, the final value being dependent on the oxygen in the system. In all cases the interfacial product was CuAlO₂. A linear relation between the fourth power of the basal radius of the molten drop and the amount of oxygen present was observed. The initial stage of the reaction could be explained by the formation of a Cu₂O layer at the interface, followed by reaction between Cu₂O and Al₂O₃ to form CuAlO₂.     

Critical Surface Tension for Spreading in the Systems (Al-Mg)/Graphite and (Cu-O)/Sapphire

According to Zisman and co-workers, in organic systems the cosine of the contact angle of a sessile drop increases with the decreasing surface tension of the drop at room temperature. The applicability of the Zisman relation to liquid metal-ceramic systems is discussed using the systems (Al-Mg)/graphite and (Cu-O)/sapphire. Also discussed is the significance of the critical surface tension for spreading, γ_c, in the systems where the surface tension of the liquid is greater than that of the solid substrate; γ_c is 230 dynes/cm for graphite at 720°C and 440 dynes/cm for sapphire at 1230°C.     

Mechanism of the interfacial reaction between sapphire and Sn-3.5Ag-4Ti solder at a low temperature in air by ultrasound

The joining of sapphire at a low temperature is necessary for the packaging of temperature-sensitive components. In current processes, the sapphire was bonded to Sn-based Ti-activated solders by mechanical scraping and stirring. To improve the efficiency and the bonding strength, the joining of sapphire by ultrasonic-assisted hot dipping and soldering at 250 °C in air was investigated. The relationship between the interfacial structure and shear strength of the soldered joints was revealed. The joints dipped for different durations and soldered for 0.5 s had similar interface morphologies, while the shear strength of the joints was controlled by the dipping duration. The shear strength of the joints dipped for 100 s reached 33 MPa. An uneven reaction layer of Ti oxides was found at the interface by TEM and EDS. A physical model was established to explain the formation of the reaction layer and the evolution of the interface microstructure. The mechanism of the interfacial reaction was discussed based on thermodynamics. The results of the thermodynamic calculations show that the replacement reaction between Ti and sapphire could not occur at the joining temperature of 250 °C. The increasing temperature induced by ultrasound at the liquid/solid interface was calculated by bubble dynamics and thermal conduction methods. It could be inferred that the reaction may be dominated by a local high temperature at the interface. Our finding demonstrates that the ultrasonic effects promote and facilitate the interfacial reaction of sapphire and Sn-3.5Ag-4Ti.     

Surface energy of liquid copper and single-crystal sapphire and the wetting behavior of copper on sapphire

The wetting behavior of liquid copper on sapphire is affected by the crystallographic orientation of the sapphire surface, the oxygen partial pressure, and the temperature. The influences of each of these conditions have been studied by the sessile drop technique over the oxygen partial pressure range 10^-2-10^-20 atm at temperatures of 1100 and 1250°C. The effect of oxygen partial pressure on the liquid copper surface energy follows the Gibbs-Langmuir law. The contact angle varies with the crystallographic orientation of the sapphire surface. This variation is more significant at higher oxygen partial pressures, but is eliminated at higher temperatures. The liquid copper surface energy was determined to be γ_lv = 1.757-3.3 x 10^-4T(°C) J/m². The solid surface energy of sapphire was estimated as γ_sv = 1.961-4.7x 10^-4T(°C) J/m², which applies only to the temperature range 927-2077°C.     

Interfacial Tension of CO2 and Organic Liquid under High Pressure and Temperature

In order to investigate the effect of organic liquid molecular structure and the intermolecular force operating with CO₂ molecules and organic liquid molecules on interfacial tension (IFT) between CO₂ and organic liquid at the first contact, the interfacial tension between CO₂ and hexane, octane, ethanol and cyclohexane at different temperatures and pressures is measured by using the pendant drop method and the axisymmetric drop shape analysis (ADSA). The results show that the interfacial tension between CO₂ and organic liquids is affected by the polarity and the structure of the organic liquid molecule obviously. The intermolecular force operating within CO₂ molecules or organic liquid, and that between CO₂ and organic liquids molecules play a dominate role on the interfacial tension between CO₂ and the organic liquids.     

Evolution of interfacial structures and mechanical performance of sapphire and Sn–9Zn–2Al joints by ultrasound

A method of ultrasonic-assisted soldering was applied to join sapphire with Sn–9Zn–2Al at 250°C in air. The sapphire samples were hot-dipped in the liquid filler metal under the ultrasonic action before ultrasonic-assisted soldering. The experimental results have shown that the joints dipped for different durations had similar morphologies, while the shear strength was dependent on the dipping duration. The shear strength of the joints increased rapidly from 13 to 22 MPa within the hot-dipping duration of 50 seconds, and increased slowly to 46 MPa at 2000 seconds. The evolution of the interface structure and the fracture mode was analyzed. The interfacial strength was dominated by the deposited Al₂O₃ at the interface in the early stage. After the entire surface of sapphire was covered by deposited Al₂O₃, Zn-rich phases at the interface and the thickening of deposited Al₂O₃ layer enhanced the interfacial strength at the later stage. Our study revealed the evolution of the interface structure and the strengthening mechanism in the joint of sapphire with Sn–Zn–Al alloys.     

High temperature electrode‐electrolyte interface formation between LiMn1.5Ni0.5O4 and Li1.4Al0.4Ge1.6(PO4)3

All‐solid‐state lithium‐ion electrolytes offer substantial safety benefits compared to flammable liquid organic electrolytes. However, a great challenge in solid electrolyte batteries is forming a stable and ion conducting interface between the electrolyte and active material. This study investigates and characterizes a possible solid‐state electrode‐electrolyte pair for the high voltage active cathode material LiMn_1.5Ni_0.5O₄ (LMNO) and electrolyte Li_1+xAl_xGe_2‐x(PO₄)₃ (LAGP). In situ X‐ray diffraction measurements were taken on pressed pellets comprised of a blend of LMNO and LAGP during exposure to elevated temperatures to determine the product materials that form at the interface of LMNO and LAGP and the temperatures at which they form. In particular, above 600°C a material consistent with LiMnPO₄ was formed. Scanning electron microscopy and energy‐dispersive X‐ray spectroscopy were used to image the morphology and elemental compositions of product materials at the interface, and electrochemical characterization was performed on LMNO‐coated LAGP electrolyte pellet half cells. Although the voltage of Li/LAGP/LMNO assembled batteries was promising, thick interfacial phases resulted in high electrochemical resistance, demonstrating the need for further understanding and control over material processing in the LAGP/LMNO system to reduce interfacial resistance and improve electrochemical performance.     

Interfacial tension measurements and evidence of order in high‐density polyethylene melts

Polyethylene (PE) is a widely used product commercially. However, our knowledge is incomplete about the properties of high‐density polyethylene (HDPE) at temperatures above its melting point, where solid crystals disappear. Recently, there has been increasing evidence from rheological, differential scanning calorimetry, and NMR studies that suggests the presence of microstructural order in the bulk of PE melts. In this study, the interfacial tension of HDPE melts in contact with silicone oil was measured with a spinning drop tensiometer in the same temperature range in which phase transitions have been observed in the bulk HDPE. Anomalous temperature dependence of interfacial tension was found between 200 and 230°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4061–4067, 2003     

Studies on cocurrent gas-liquid flow in helically coiled tubes. II. Theory and experiments on turbulent mass transfer with and without chemical reaction

Pure carbon dioxide was absorbed into distilled water and sodium hydroxide solution, in cocurrent two phase annular flow in helically coiled tubes in order to measure physical and chemical mass transfer coefficients and interfacial areas. (k*_La) was correlated by the pressure drop in the test sections and interfacial areas were found to vary with the liquid phase energy dissipation. According to a new theory, (k*_L) has been shown to be a function of the root mean square vorticity near the interface. The root mean square vorticity has been related to the pressure drop, gas density, liquid flow rate and liquid velocity. The physical mass transfer coefficients theoretically predicted are in good agreement with experimental results.     

Indirect Dissolution of Sapphire into Calcia-Magnesia-Alumina-Silica Melts: Electron Microprobe Analysis of the Dissolution Process

Spinel, MgAl₂O₄, has been observed to form on sapphire during sapphire dissolution into CaO-MgO-Al₂O₃-SiO₂ (CMAS) melts at 1450°. and 1550°C. Electron microprobe analysis was used to characterize the sapphire/melt interface for cases in which spinel did (indirect dissolution) or did not (direct dissolution) form on the sapphire during dissolution into CMAS melts. The concentrations of Al₂O₃, MgO, CaO, and SiO₂ were determined as a function of position within the spinel reaction product and in the adjacent melt. The rate-limiting steps for direct and indirect sapphire dissolution into CMAS melts are discussed.     

Wetting and interfacial phenomena in relation to joining of alumina via Co/Nb/Co interlayers

When designing multilayer metallic interlayers for transient-liquid-phase (TLP) bonding of ceramics, the phenomena that occur at the interface between the liquid metal alloy formed at the joining temperature and the solid ceramic to be joined have a major effect on the success or failure of the joining process. To assess the behavior of liquids that could develop when using Co/Nb/Co trilayers to bond Al₂O₃ ceramics, the wettability and interfacial behavior of pure Co and Co–Nb alloys on sapphire and polycrystalline Al₂O₃ were studied. Contact angles were measured at 1500 °C using the sessile-drop technique, and the microstructures of the resulting metal/ceramic interfaces were characterized by scanning electron microscopy and energy-dispersive spectroscopy. Observations were assessed and evaluated in the context of predictions of thermodynamic properties. Additions of Nb to Co reduced the contact angle and thus improved the adhesion between the ceramic and metal. Nb additions also enhanced dissolution of Al₂O₃.