The nano heat effect of replacing macro-particles by nano-particles in drop calorimetry: the case of core/shell metal/oxide nano-particles.

Experimental results are presented here obtained by a drop calorimetric method, in which Ni and Cu particles, both in bulk and nanosized form, were dropped into a liquid Sn-3.8Ag-0.7Cu solder alloy (in wt%). The molar enthalpies of mixing of the liquid (Sn-3.8Ag-0.7Cu)-Ni(Cu) alloys were measured. An extra exothermic heat effect is observed when dropping nano-particles instead of macro-particles. This is partly due to the loss of the large surface area and the corresponding large surface enthalpy of the nano-particles before their dissolution in the liquid alloy. However, a large additional exothermic heat effect was also found in the case of Cu-nano-particles, due to the exchange chemical reaction between the Cu2O shell of the nano-particles and liquid Sn; this is caused by the fact that the Cu-nano-particles are core-shell particles with an inner metallic Cu core and an outer Cu2O shell. This effect is less significant for Ni nano-particles which have a thinner oxide shell.

Enthalpy of mixing of liquid Co-Sn alloys.

A literature overview of enthalpy of mixing data for liquid Co-Sn alloys shows large scattering but no clear temperature dependence. Therefore drop calorimetry was performed in the Co-Sn system at twelve different temperatures in 100 K steps in the temperature range (673 to 1773) K. The integral enthalpy of mixing was determined starting from 1173 K and fitted to a standard Redlich-Kister polynomial. In addition, the limiting partial molar enthalpy of Co in Sn was investigated by small additions of Co to liquid Sn at temperatures (673 to 1773) K. The integral and partial molar enthalpies of the Co-Sn system generally show an exothermic mixing behavior. Significant temperature dependence was detected for the enthalpies of mixing. The minimum integral enthalpy values vary with rising temperature from approx. -7820 J/mol at T = 1173 K to -1350 J/mol at T = 1773 K; the position of the minimum is between (59 and 61) at.% Co. The results are discussed and compared with literature data available for this system. X-ray studies and scanning electron microscopy of selected alloys obtained from the calorimetric measurements were carried out in order to check the completeness of the solution process.

The Enthalpies of Mixing of Liquid Ni-Sn-Zn Alloys.

The partial and integral enthalpies of mixing of liquid ternary Ni-Sn-Zn alloys were determined. The system was investigated along two sections xNi/xSn ≈ 1:9, xNi/xSn ≈ 1:6 at 1073 K and along two sections xSn/xZn ≈ 9:1, xSn/xZn ≈ 4:1 at 873 K. The integral enthalpy of mixing at each temperature is described using the Redlich-Kister-Muggianu model for substitutional ternary solutions. In addition, the experimental results were compared with data calculated according to the Toop extrapolation model. The minimum integral enthalpy of approx. -20000 J mol-1 corresponds to the minimum in the constituent binary Ni-Sn system, the maximum of approx. 3000 J mol-1 is equal to the maximum in the binary Sn-Zn system.

Enthalpies of Formation of (Cu,Ni)3Sn, (Cu,Ni)6Sn5-HT and (Ni,Cu)3Sn2-HT.

Standard enthalpies of formation of ternary phases in the Cu-Ni-Sn system were determined along sections at 25, 41 and 45.5 at.% Sn applying tin solution drop calorimetry. Generally, the interaction of Ni with Sn is much stronger than that of Cu with Sn. Along all sections the enthalpy of formation changes almost linearly with the mutual substitution of Cu and Ni within the respective homogeneity ranges. Thus no additional ternary interaction promoting the formation of further Cu-Ni-Sn phases can be assumed. The results are discussed and compared with literature values relevant to this system.

Calorimetric studies of Cu-Li, Li-Sn, and Cu-Li-Sn.

Integral molar enthalpies of mixing were determined by drop calorimetry for Cu-Li-Sn at 1073 K along five sections xCu/xSn ≈ 1:1, xCu/xSn ≈ 2:3, xCu/xSn ≈ 1:4, xLi/xSn ≈ 1:1, and xLi/xSn ≈ 1:4. The integral and partial molar mixing enthalpies of Cu-Li and Li-Sn were measured at the same temperature, for Li-Sn in addition at 773 K. All binary data could be described by Redlich-Kister-polynomials. Cu-Li shows an endothermic mixing effect with a maximum in the integral molar mixing enthalpy of ∼5300 J · mol-1 at xCu = 0.5, Li-Sn an exothermic minimum of ∼ -37,000 J · mol-1 at xSn âˆ¼ 0.2. For Li-Sn no significant temperature dependence between 773 K and 1073 K could be deduced. Our measured ternary data were fitted on the basis of an extended Redlich-Kister-Muggianu model for substitutional solutions. Additionally, a comparison of these results to the extrapolation model of Chou is given.

The Cu-Sn phase diagram, Part I: New experimental results.

Phase diagram investigation of the Cu-Sn system was carried out on twenty Cu-rich samples by thermal analysis (DTA), metallographic methods (EPMA/SEM-EDX) and crystallographic analysis (powder XRD, high temperature powder XRD). One main issue in this work was to investigate the high temperature phases beta (W-type) and gamma (BiF3-type) and to check the phase relations between them. In the high temperature powder XRD experiments the presence of the two-phase-field between the beta- and the gamma-phase could not be confirmed. Detailed study of primary literature together with our experimental results leads to a new phase diagram version with a higher order transformation between these two high temperature phases. The present work is designated as part I of our joint publication. The new findings described here have been included into a completely new thermodynamic assessment of the Cu-Sn phase diagram which is presented in part II.

Phase equilibria in the ternary In-Ni-Sn system at 700 °C.

The phase equilibria of the ternary system In-Ni-Sn were investigated experimentally at 700 °C using X-ray diffraction (XRD) and scanning electron microscopy (SEM) including electron micro probe analysis (EMPA) and energy dispersive X-ray spectroscopy (EDX). A corresponding isothermal section was established based on these results. This particular temperature was chosen because it allowed obtaining reliable results within reasonable time. The existence of the ternary phase InNi6Sn5 was confirmed whereas the ternary compound In2NiSn, reported earlier in literature, was found to be part of a large solid solution field based on binary InNi. The ternary solubility of the binary phases was established, and continuous solid solutions were found between the isostructural phases Ni3Sn LT and InNi3 as well as between Ni3Sn2 HT and InNi2. In addition, this isothermal section could be well reproduced by CALPHAD modelling. The resulting calculated isotherm at 700 °C is presented, too, and compared with the experimental results.

Enthalpies of mixing of liquid systems for lead free soldering: Co-Sb-Sn.

The partial and integral enthalpy of mixing of molten ternary Co-Sb-Sn alloys was determined performing high temperature drop calorimetry in a large compositional range at 1273 K. Measurements have been done along five sections, xSb/xSn ≈ 1:1, xSb/xSn ≈ 1:3, xSb/xSn ≈ 3:1, xCo/xSn ≈ 1:4, and xCo/xSb ≈ 1:5. Additionally, binary alloys of the constituent systems Co-Sb and Co-Sn were investigated at the same temperature. All the binary data were evaluated by means of a standard Redlich-Kister polynomial fit whereas ternary data were fitted on the basis of an extended Redlich-Kister-Muggianu model for substitutional solutions. An iso-enthalpy plot of the ternary system was constructed. In addition, the extrapolation Model of Toop was applied and compared to our data.

Enthalpy of mixing of liquid systems for lead free soldering: Ni-Sb-Sn system.

The partial and integral enthalpies of mixing of liquid ternary Ni-Sb-Sn alloys were determined along five sections xSb/xSn = 3:1, xSb/xSn = 1:1, xSb/xSn = 1:3, xNi/xSn = 1:4, and xNi/xSb = 1:4 at 1000 °C in a large compositional range using drop calorimetry techniques. The mixing enthalpy of Ni-Sb alloys was determined at the same temperature and described by a Redlich-Kister polynomial. The other binary data were carefully evaluated from literature values. Our measured ternary data were fitted on the basis of an extended Redlich-Kister-Muggianu model for substitutional solutions. Additionally, a comparison of these results to the extrapolation model of Toop is given. The entire ternary system shows exothermic values of ΔmixH ranging from approx. -1300 J/mol, the minimum in the Sb-Sn binary system down to approx. -24,500 J/mol towards Ni-Sb. No significant ternary interaction could be deduced from our data.