Thermal analysis of the compositional shift in a transient liquid phase during sintering of a ternary Cu-Sn-Bi powder mixture

In this work, differential scanning calorimetry (DSC) and microstructural analysis were used to study the transient-liquid-phase sintering (TLPS) of a Cu-Sn-Bi powder mixture. During sintering, the liquid phase shifts from a Sn-rich (i.e., ∼90 wt pct Sn) to a Bi-rich (i.e., >78 wt pct Bi) composition. In addition, the presence of Bi creates two melting events: a Sn:Bi eutectic reaction at 139 °C and a reaction involving the melting of (Bi) at 191 °C. The Sn:Bi eutectic melting event was fully transient. The melting event at 191 °C was consistent with the formation of a terminal Bi-rich liquid phase. The rate of compositional shift toward this terminal liquid phase at 260 °C was dependent on the rate of the reaction of the Sn with the Cu powder to form intermetallic phases. For mixtures made with medium and fine Cu powder, the terminal Bi-rich composition was reached after isothermal hold times of 20 and 15 minutes, respectively. This resulted in a new melting point for the mixture of 191 °C. For coarse Cu powders, the rate of the compositional shift toward a Bi-rich composition was much slower. The liquid phase remained at a hypoeutectic Sn-Bi composition estimated at 80 wt pct Sn, while the mixture maintained a melting point of 139 °C.     

The effect of low gold concentrations on the creep of eutectic tin-lead joints

The effects of low Au concentrations on the creep properties of a eutectic Sn/Pb alloy were investigated. Creep testing was performed on double-shear specimens of fine-grained, eutectic Sn/Pb joints with Au concentrations of 0, 0.2, 1.0, and 1.5 wt pct Au at 90 °C, 0, 0.2, and 1.0 wt pct Au at 65°C, and 0.2 wt pct Au at 25 °C. In the absence of Au, the creep of finegrained eutectic Sn/Pb is dominated by grain-boundary sliding at high homologous temperature and intermediate stress. The addition of 0.2 wt pct Au or more suppressed this mechanism; the high-stress, bulk-creep mechanism was dominant at all stresses tested. Higher concentrations of Au increased porosity within the joints. The porosity decreased joint strength. During failure, the crack path followed softer regions of the joint; cracks propagated through Pb-rich islands or along Sn/Sn grain boundaries.     

Unidirectionally solidified Ti−TiB and Ti−Ti5Si3 eutectic composites

Induction melting and electron beam melting techniques were employed in the production of unidirectionally solidified eutectic composites of Ti-1.7 wt pct B and Ti-8.5 wt pct Si. The grown eutectics were reinforced by 7.7 volume pct of TiB fibers and 31 volume pct of Ti₅Si₃ fibers respectively. Controlled dendritic solidification of a hypereutectic composition of Ti-12 wt pct Si was also accomplished. Tensile, compressive, creep, and stress rupture specimens were cut from the eutectic composites and tested with reinforcing fibers parallel to the load axis. Ti?TiB eutectic was found to have less than the critical volume fraction of fibers necessary for reinforcement, while Ti?Ti₅Si₃ composite attained a compressive yield strength of 275,000 psi and a compressive Young's modulus of 30×10⁸ psi after heat treatment. The 500 and 4000 hr stress rupture properties of Ti?Si eutectic were superior to commercial titanium alloys at 1000° and 1200°F. The minimum creep rate of Ti?Ti₅Si₃ eutectic composite was lower than all other titanium alloys at 1000°F. Tensile, compressive, and creep properties of the Ti-8.5 wt pct Si eutectic are discussed in terms of the current theories of composite behavior.     

Experimental Determination of the Austenite + Liquid Phase Boundaries of the Fe-C System

Differential thermal analysis has been employed to achieve an accurate determination of the solidliquid equilibria for γ-Fe at temperatures between 1147 °C and 1430 °C and compositions in the range 1.5 to 4.42 wt pct C. Several small but significant changes to the established phase diagram have been proposed. In particular, the liquidus in the vicinity of the eutectic has been raised by approximately 15 °C and the temperature of the graphite eutectic lowered to 1150.5 °C. Consequently, the eutectic compositions have been increased to 4.39 and 4.42 wt pct C for the graphite and cementite eutectics, respectively. The possibility of some modification to the γ-solidus has also been suggested, and a revised phase diagram is presented.     

Solidification in the system Al-Ge-Si: The phase diagram,coring patterns,eutectic growth,and modification

In the ternary system Al-Ge-Si, the binary eutectic reactions, L (liquid) ⇔ (Al) + (Si) and L ⇔ (Al) + (Ge) are connected by a monovariant valley, L ⇔ (Al) + (SiGe), falling from 578 °C at 12.7 wt pct Si to 424 °C at 53 wt pct Ge. The binary, solid eutectic surface extends from the Al corner of the ternary phase diagram (1.65 wt pct Si to 5.2 wt pct Ge) across to the continuous (SiGe) solid solution which contains very little Al: several tie triangles, L-(A1)-(SiGe), have been determined using thermal analysis and electron microprobe analysis (EMPA). Optical and scanning electron microscopy (SEM) examination reveals that coring in the normal (SiGe) phase is discontinuous, showing composition banding, which indicates that stationary 111 facets of the solid solution were exposed to the liquid for extended periods up to 500 seconds; details of this interrupted coring were quantified by EMPA. Similar, smaller, and more gradual variations could also be detected in the (Al) matrix, and these compositional fluctuations are considered to reflect discontinuities in the local eutectic growth rates. Modification and twin-ning, induced by Na, are observed in both Al-Si and Al-Ge but decrease progressively with Ge content; coring in the modified ternary alloys is more continuous.     

Phase equilibria and thermodynamic properties of the Cu<Subscript>2</Subscript>O-CaO-Na<Subscript>2</Subscript>O system in equilibrium with copper

The liquidus surfaces of the Cu₂O-CaO, Cu₂O-Na₂O, and Cu₂O-CaO-Na₂O phase diagrams in equilibrium with metallic Cu were measured by thermal analysis at compositions varying from approximately 0 to 35 wt pct Na₂O and 0 to 15 wt pct CaO. Solubilities in the solid binary terminal solutions were also measured by wavelength dispersive X-ray spectrometer analysis. Copper oxide activities in binary liquid slags were determined from the measured oxygen content of the metallic copper equilibrated with the slags. The ternary system is a simple eutectic system. No ternary compounds were observed. The Cu₂O-CaO binary eutectic was measured at 1140 °C±10 °C at 10±1 wt pct CaO and the Cu₂O-Na₂O binary eutectic was measured at 803 °C±15 °C at 28±2 wt pct Na₂O. The liquid slag was thermodynamically modeled with the modified quasi-chemical model, while the solid Cu₂O-rich solution was treated as Henrian ideal. All data from the present work and from the literature (phase diagrams and activities) for the binary systems were evaluated simultaneously by least-squares optimization in order to obtain the best model parameters. With only these binary parameters, the calculated ternary liquidus surface is in very good agreement with the measurements. Finally, using the model, the liquidus projection of the Cu₂O-CaO-Na₂O system in equilibrium with Cu was calculated as well as the oxygen content of the equilibrated Cu as a function of slag composition.     

Tempering behavior of iron-carbon sputter deposits with 0 to 5 wt pct C

Iron-carbon sputter deposits with 0.06, 0.18, 0.66, 2, 3, and 5 wt pct C were tempered at temperatures from 100° to 550°C. The 0.06, 0.18, and 0.66 wt pct C sputter deposits were similar to severely cold-worked martensite, both as-deposited and in tempering response. Specifically, these three deposits were much harder than water quenched steels of the same composition, and the deposit hardnesses decreased less than martensite hardnesses on tempering below 400°C. The hardnesses of the 2 and 3 wt pct C deposits increased 40 to 50 Dph units upon tempering at low temperatures (150° to 250°C) and decreased for higher tempering temperatures. The hardness of the 5 wt pct C deposit remained constant (920 Dph) after tempering at 150°C, but increased to 1170 Dph upon tempering at 250°C when monoclinic Hägg carbide (Fe₅C₂) formed. Cementite (Fe₃C) was the only other carbide detected in the tempered deposits, and it formed only at 475°C and above. The columnar grains of the sputter deposits transformed to equiaxed grains upon tempering above 250°C. This change in grain structure was due to recovery and not recrystallization. Some grain growth occurred in the 0.06, 0.18, 0.66, and 2 wt pct C deposits above 300°C, but the grain size of the 3 and 5 wt pct C deposits remained submicron. The hardnesses of the deposits after tempering at 550°C increased with carbon content, the 5 wt pct C deposit having the highest hardness (960 Dph) and the 0.06 wt pct C deposit the lowest (360 Dph).     

Solid solutions in sputter-deposits of iron with 0 to 5 Wt Pct C

Supersaturated iron-carbon solid solutions containing 0.06, 0.18, 0.66, 2, 3, and 5 wt pct C were produced by sputter-deposition at 6° to 21°C. Homogeneous deposits of the same carbon composition as the multiphase source materials were produced by high rate (up to 0.0004 in. per hr) sputtering techniques and were 0.005 to 0.027 in. thick. The microhardnesses of the deposits were higher than the hardnesses of martensite with the same carbon content. The hardness increased rapidly from 680 Dph for 0.06 wt pct C content to an unusually high maximum of 1240 Dph at 2 wt pct C and then decreased slowly to 920 Dph at 5 wt pct C. The 0.06, 0.18, and 0.66 wt pct C deposits were bcc, and the 2 and 3 wt pct C deposits were bct. The tetragonality of the 5 wt pct C deposit was detected only after tempering at 150°C. Lattice parameterc/a ratios for the tetragonal deposits were lower than expected from extrapolated martensite data, and they corresponded to the equationc/a=1.06+0.019 (wt pct C). Nevertheless, thec/a ratio of 1.10 for 5 wt pct C deposit was higher than previously observed for martensite. No evidence of a martensitic transformation was found in the microstructures, which typically consisted of 0.5 to 1.0 μ diam columnar grains. Hardness data from tempered eposit samples and the lack of tetragonality of the low carbon deposits indicated that autotempering occurred during sputter-deposition.     

The V-VO phase system

A phase diagram is proposed for the V-VO system based on melting point determinations, differential thermal analyses, metallographic observations, and X-ray parametric measurements. A eutectic reaction occurs at 1640°C and 29 at. pct O. The intermediate phases V₉O and V₂O form peritectoidally at 510° and 1185°C, respectively, while V₄O forms by a peritectic reaction at 1665°C. The VO phase melts congruently at 1790°C. The terminal solubility of oxygen in vanadium increases from 3.2 at. pct at room temperature to a maximum of 17.0 at. pct at the peritectic temperature. There is also extensive solid solubility associated with each of the intermediate phases. Two martensite-like phases form in alloys in the composition range 6 to 9 at. pct O upon quenching from above the 510°C peritectoid horizontal.     

INCONEL 718: A solidification diagram

As part of a program studying weldability of Ni-base superalloys, results of an integrated analytical approach are used to generate a constitution diagram for INCONEL 718^* in the temperature range associated with solidification. Differential thermal analysis of wrought material and optical and scanning electron microscopy, electron probe microanalysis, and analytical electron microscopy of gas tungsten arc welds are used in conjunction with solidification theory to generate data points for this diagram. The important features of the diagram are an austenite (γ)/Laves phase eutectic which occurs at ≈19.1 wt pct Nb between austenite containing ≈9.3 wt pct Nb and a Laves phase which contains ≈22.4 wt pct Nb. The distribution coefficient for Nb was found to be ≈0.5. The solidification sequence of INCONEL 718 was found to be (1) proeutectic γ, followed by (2) a γ/NbC eutectic at ≈1250°C, followed by (3) continued γ solidification, followed by (4) a γ/Laves phase eutectic at ≈1200°C. An estimate of the volume fraction eutectic is made using the Scheil solidification model, and the fraction of each phase in the eutectic is calculatedvia the lever rule. These are compared with experimentally determined values and found to be in good agreement.     

Influence of Cobalt on Bainite Formation Kinetics in 1 Pct C Steel

The effect of cobalt on bainite kinetics formation in a 1C-1.5Si wt pct steel is investigated. Two laboratory casts were manufactured with no or 2.5Co wt pct. Bainite transformation kinetics at 493 K, 523 K, and 573 K (220 °C, 250 °C, and 300 °C) were measured using dilatometry. Careful control of the alloy composition, in particular with respect to carbon content, allowed unambiguous identification of the expected accelerating effect of Co. This effect was quantified and compared to that of other possible alloying additions. It is shown that Co has an acceleration effect of around 18 to 29 pct (per wt pct added) for bainite formation between 220 °C and 300 °C. Comparison with published data indicates that this influence is orders of magnitude smaller than that achieved through reduction of C, Mn, or Cr. The influence on hardness is quantified and shown to be significant, and possible origins for hardening are discussed.     

Equilibrium solid solubility of silicon in silver

The equilibrium solubility of silicon in silver was measured in the range between 300 °C and the eutectic temperature using both an electron microprobe and the evolution of electrical resistivity of a near-eutectic Ag-4 wt pct Si alloy. The silver matrix was found to dissolve up to 0.93 at. pct Si, at 836 °C. The resistivity was found to increase on average by 4.31 μΩcm/at. pct solute content of Si in the silver matrix. The solubility of silicon in silver is well described by an Arrhenius-type equation, with an apparent enthalpy of mixing of 74.7 kJ/mol and a prefactor of 30.6 (3060 at. pct). This finite terminal solubility of silicon in silver can account for a discrepancy between the calculated and experimental silver-silicon binary-phase diagrams, as present in the literature.     

Fatigue of Ni-Ai-Mo aligned eutectics at elevated temperatures

The elevated-temperature mechanical behavior of two aligned eutectics (Ni-8.1 wt pct Al-26.4 wt pct Mo and Ni-6.3 wt pct Al-31.2 wt pct Mo) has been investigated utilizing monotonic and cyclic testing in vacuum. Tensile yield strength and fatigue resistance increased from 25 to 725 °C, but then were reduced at 825 °C. The fatigue lives of specimens tested at 725 °C decreased sharply with decreasing frequency. A shift from surface to internal crack initiation was observed upon increasing the test temperature from 725 to 825 °C. Stage II crack propagation was observed at both temperatures, in contrast to stage I cracking at 25 °C. The test results are compared to those for other nickel and cobalt-base aligned eutectics to show that the frequency effect on fatigue life is not limited to the Ni-AI-Mo system. formerly Graduate Assistant in the Department of Materials Engineering, Rensselaer Polytechnic Institute     

Constitution of the Lead-Tin-Strontium System up to 36 Atomic Percent Sr

The constitution of the Pb-Sn-Sr system from the Pb-Sn binary up to 36 at. pct Sr was determined by differential thermal analysis, metallography, microprobe analysis, and X-ray diffraction. Pb₃Sr forms a continuous series of solid solutions with Sn₃Sr, and is referred to here as the8 phase. Sn₄Sr was the only other intermetallic phase found and is designated here as γ. A eutectic-like trough is formed between (Pb) and δ. It originates at 1.0 at. pct Sr and 324.5 °C (the (Pb)/Pb₃Sr eutectic) and falls monotonically to ~75 at. pct Pb, 24.5 at. pct Sn, and 0.45 at. pct Sr at 283 °C. At 283 °C, a Class II, four-phase reaction occurs: L + δ→ (Pb) + γ. A eutectic-like trough between (Pb) and γ falls from the four-phase plane at 283 °C to the ternary eutectic at ~26 at. pct Pb, ~74 at. pct Sn and <0.3 at. pct Sr at 182 °C. The ternary eutectic reaction is L → (Pb) + (Sn) + γ.     

Application of MIVM for Pb-Sn System in Vacuum Distillation

The activity coefficients of components of the Pb-Sn binary alloy system were calculated based on the molecular interaction volume model (MIVM). A significant advantage of this model lies in its ability to predict the thermodynamic properties of liquid alloys using only two binary infinite activity coefficients. Based on the MIVM, the vapor-liquid phase equilibrium of the Pb-Sn alloy system in vacuum distillation has been predicted using the activity coefficients of Pb and Sn. The results showed that the content of tin in the vapor phase was 0.008?wt?pct, while in the liquid phase, it was 83?wt?pct at 1173?K (900?°C); it reached 0.022?wt?pct in the vapor phase, while in the liquid phase, it was 92?wt?pct at 1223?K (950?°C); and it was 0.052?wt?pct in the vapor phase, while in the liquid phase, it was 97.88?wt?pct at 1273?K (1000?°C). The content of tin in the vapor phase increased with the distillation temperature increasing. Experimental investigations into the separation of Pb and Sn from the Pb-Sn alloy by vacuum distillation were carried out for the proper interpretation of the results of the model. The influence of the distillation time (20 to 80?minutes) and the distillation temperatures of 1173?K, 1223?K, and 1273?K (900?°C, 950?°C, and 1000?°C) on the separating effect was also studied. The experimental results showed that the content of tin in the vapor phase was 0.085?wt?pct, while in liquid phase, it was 83?wt?pct under the operational conditions of distillation temperature of 1173?K (900?°C), evaporation time of 20?minutes, and chamber pressure of 20?Pa; it reached 0.18?wt?pct in the vapor phase, while in the liquid phase, it was 92?wt?pct at 1223?K (950?°C), 20?minutes, and 20?Pa; and it was 0.35?wt?pct in the vapor phase, while in the liquid phase, it was 97.88?wt?pct at 1273?K (1000?°C), 20?minutes, and 20?Pa. In all these experiments, it was observed that the content of tin in the vapor phase increased as the distillation time and temperatures were increased. The experimental results are in good agreement with the predicted values of the MIVM for the Pb-Sn binary system.     

An investigation of the high-temperature and solidification microstructures of PH 13-8 Mo stainless steel

Differential thermal analysis (DTA), high-temperature water-quench (WQ) experiments, and optical and electron microscopy were used to establish the near-solidus and solidification microstructures in PH 13-8 Mo. On heating at a rate of 0. 33 °C/s, this alloy begins to transform from austenite to δ-ferrite at ≈1350 °C. Transformation is complete by ≈1435 °C. The solidus is reached at ≈1447 °C, and the liquidus is ≈1493 °C. On cooling from the liquid state at a rate of 0. 33 °C/s, solidification is completed as δ-ferrite with subsequent transformation to austenite beginning in the solid state at ≈1364 °C. Insufficient time at temperature is available for complete transformation and the resulting room-temperature microstructure consists of matrix martensite (derived from the shear decomposition of the austenite) and residual δ-ferrite. The residual δ-ferrite in the DTA sample is enriched in Cr (≈16 wt pct), Mo (≈4 wt pct), and Al (≈1. 5 wt pct) and depleted in Ni (≈4 wt pct) relative to the martensite (≈12. 5 wt pct Cr, ≈2 wt pct Mo, ≈1 wt pct Al, ≈9 wt pct Ni). Solid-state transformation of δσ γ was found to be quench-rate sensitive with large grain, fully ferritic microstructures undergoing a massive transformation as a result of water quenching, while a diffusionally controlled Widmanstätten structure was produced in air-cooled samples.     

Effect of heat treatment on the microstructure,tensile properties,and fracture behavior of permanent mold Al-10 wt pct Si-0.6 wt pct Mg/SiC/10p composite castings

The present study was undertaken to investigate the effect of solution treatment (in the temperature range 520 °C to 550 °C) and artificial aging (in the temperature range 140 °C to 180 °C) on the variation in the microstructure, tensile properties, and fracture mechanisms of Al-10 wt pct Si-0.6 wt pct Mg/SiC/10_p composite castings. In the as-cast condition, the SiC particles are observed to act as nucleation sites for the eutectic Si particles. Increasing the solution temperature results in faster homogenization of the microstructure. Effect of solution temperature on tensile properties is evident only during the first 4 hours, after which hardly any difference is observed on increasing the solution temperature from 520 °C to 550 °C. The tensile properties vary significantly with aging time and temperature, with typical yield strength (YS), ultimate tensile strength (UTS), and percent elongation (EL) values of ∼300 MPa, ∼330 MPa, and ∼1.4 pct in the underaged condition, ∼330 MPa, ∼360 MPa, and ∼0.65 pct in the peakaged condition, and ∼323 MPa, ∼330 MPa, and ∼0.8 pct in the overaged condition. Prolonged solution treatment at 550 °C for 24 hours results in a slight improvement in the ductility of the aged test bars. The fracture surfaces exhibit a dimple morphology and cleavage of the SiC particles, the extent of SiC cracking increasing with increasing tensile strength and reaching a maximum in the overaged condition. Microvoids act as nucleation sites for the formation of secondary cracks that promote severe cracking of the SiC particles. A detailed discussion of the fracture mechanism is given.     

The solubility of the liquid oxysulfide phase in liquid Fe-O-S alloys

The solubility of the liquid oxide phase in liquid Fe-O alloys has been measured for the temperature range of 1378 to 1740 °C. Also the solubility of the liquid oxysulfide phase in liquid Fe-O-S alloys has been determined for the composition range of 0.08 to 0.30 wt pct oxygen and 0 to 0.5 wt pct sulfur. The oxygen content of liquid iron saturated with the liquid oxide phase is log O = ?6358/T + 2.76. The standard free energy for the formation of the oxide phase is: xFe(l) + O(pct) = Fe_xO(l); ΔG° = 242.4 ? 0.0829T + 166,990/T(kJ). The equation for the standard free energy in the temperature range of 1550 to 1650 °C may be written as: ?117.5 + 0.0496T (kJ). The effect of composition on temperature of saturation of liquid Fe-O-S alloys with the oxysulfide phase is:T(K) = ?6358/(log pct O ? 2.76) - (pct S)x [554 + 135.0(log O ? 2.77)]. The relationship applies for the composition range of 0.15 to 0.30 wt pct oxygen and 0.0 to 0.5 wt pct sulfur and temperatures from 1480 to 1680 °C.     

Effect of small additions of silver on the eutectic temperature in the lead-tin system

Recent work on the thermodynamic properties and phase diagram of the lead-tin system has provided an excellent opportunity to evaluate the lowering of the eutectic temperature by the addition of a small amount of silver. For these low silver content, ternary solders, the Pb-Sn eutectic temperature is decreased by 3.3 °C owing to the addition of 1 wt pct silver.     

The chromium-platinum constitution diagram

The system Cr?Pt has been investigated over the entire composition range by metallography, X-ray diffraction, and electron microprobe studies. There is only one intermediate phase and it has a Cr₃Si(A15)-type crystal structure. The fcc platinum terminal solid solution extends to 71 at. pct Cr at 1530°C and forms a congruent melting maximum at about 1790°C. Atomic ordering within this solid solution range begins at about 17 at. pct Cr and there is a continuous change from the Cu₃Au-type structure to the CuAu-type structure with increasing chromium content. Two eutectic reactions at 1530°C±10°C and at 1500°C ±10°C were indicated and there is evidence of a syntectic reaction at 1580°C±10°C. Platinum is soluble in the bcc chromium terminal solid solution up to about 10 at pct Pt at 1500°C but the solubility decreases rapidly at lower temperatures.