Differential scanning calorimetry and electron diffraction investigation on low-temperature aging in Al-Zn-Mg alloys

Differential scanning calorimetry (DSC) has been combined with transmission electron microscopy (TEM) to investigate the low-temperature decomposition processes taking place in an Al-5 wt pct Zn-1 wt pct Mg alloy. It was confirmed that two types of GP zones, i.e., GP(I) (solute-rich clusters) and GP(II) (vacancy-rich clusters), formed independently during decomposition of the supersaturated solid solution. The GP(I) zones form at a relatively low aging temperature and dissolve when the aging temperature is increased. The GP(II) zones are stable over a wider range of temperatures. To investigate the nature of the zones in the Al-Zn-Mg alloy, differential scanning calorimetry and transmission electron microscopy have also been carried out on binary Al-Zn alloys containing 5 wt pct and 10 wt pct Zn. In these Al-Zn alloys, GP zones formed rapidly during quenching, and they gave rise to characteristic electron diffraction patterns identical to those from GP(II) in the Al-Zn-Mg alloy system, implying that GP(II) zones in Al-Zn-Mg alloys are very similar to the zones formed in binary Al-Zn alloys. Thus, it is likely that GP(II) zones in Al-Zn-Mg alloys are zinc-rich clusters. In the Al-5 wt pct Zn-1 wt pct Mg alloy, both GP(I) and GP(II) were found to transform to η′ and/or η particles during heating in the differential scanning calorimeter. The η′ was also observed to form after prolonged isothermal aging of the Al-Zn-Mg alloy at 75 °C or after short aging times at 125 °C.     

A transmission electron microscopy investigation of the early stages of precipitation in an Al-Zn-Mg alloy

The growth of spherical precipitates in an Al-5 wt pct Zn-2 wt pct Mg alloy was monitored by hardness measurements and transmission electron microscopy. The growth of precipitates from 15 to 80Å in diameter was followed for various aging times at temperatures of 30, 70, 100, and 150°C. For short times at low aging temperatures precipitate growth followed at _1/9 law, whereas growth at longer times, or higher temperatures, followed at _1’3 law. Various contrast experiments lead to the conclusion that the precipitates produced at all but the shortest aging times at the lowest aging temperatures have a hexagonal structure and are spherical precursors of the η′ phase. The advantages and disadvantages associated with the various imaging techniques for small precipitates utilized in this study are discussed.     

A transmission electron microscopy investigation of the early stages of precipitation in an Al-Zn-Mg alloy

The growth of spherical precipitates in an Al-5 wt pct Zn-2 wt pct Mg alloy was monitored by hardness measurements and transmission electron microscopy. The growth of precipitates from 15 to 80Å in diameter was followed for various aging times at temperatures of 30, 70, 100, and 150°C. For short times at low aging temperatures precipitate growth followed at _1/9 law, whereas growth at longer times, or higher temperatures, followed at _1’3 law. Various contrast experiments lead to the conclusion that the precipitates produced at all but the shortest aging times at the lowest aging temperatures have a hexagonal structure and are spherical precursors of the η′ phase. The advantages and disadvantages associated with the various imaging techniques for small precipitates utilized in this study are discussed. Formerly Research Assistant, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA. 02139     

Creep of zirconium and zirconium alloys

Cumulative zirconium and zirconium alloy creep data over a broad range of stresses (0.1 to 115 MPa) and temperatures (300 °C to 850 °C) were analyzed based on an extensive literature review and experiments. Zirconium obeys traditional power-law creep with a stress exponent of approximately 6.4 over stain rates and temperatures usually associated with the conventional “five-power-law” regime. The measured activation energies for creep correlated with the activation energies for zirconium self-diffusion. Thus, dislocation climb, rather than the often assumed glide mechanism, appears to be rate controlling. The common zirconium alloys (i. e., Zircaloys) have higher creep strength than zirconium. The stress exponents of the creep data in the five-power-law regime were determined to be 4.8 and 5.0 for Zircaloy-2 and Zircaloy-4, respectively. The creep strength of irradiated Zircaloy appears to increase relative to unirradiated material. It was found that the creep behavior of zirconium was not sensitive to oxygen in the environment over the temperature range examined.     

A study of stress-corrosion in Al-Zn-Mg alloys

This study of Al-Zn-Mg alloys was undertaken to establish the specific combination of mechanical and thermal conditions which is necessary for stress-corrosion susceptibility to occur in these alloys. The work included a study by electron transmission microscopy of the microstructure of this alloy system. A new mechanism is proposed to account for the observations made. It suggests that the high corrosion potential at grain boundaries in stress-corrosion susceptibile Al-Zn-Mg alloys is due to segregation of zinc and magnesium. By taking precautions to reduce this segregation, the stress-corrosion life can be increased.     

Joint effect of scandium,chromium, and zirconium on the aging and recrystallization of aluminum alloys

Metallography and electrical resistivity and hardness measurements are used to study the aging and recrystallization of Al-rich Al-Sc-Cr-Zr alloys with 0.1–0.4% Sc, 1.0% Cr, and 0.2% Zr. During aging at 350°C, the hardness of the alloys is found to increase substantially even after 0.5-h aging as compared to that of the deformed state. Variations of the hardness and electrical resistivity of all alloys exhibit similar behavior; however, the higher the scandium content in the alloys, the higher the strengthening effect reached after aging for 2–4 h. Combined small scandium, chromium, and zirconium additions to aluminum are shown to increase its recrystallization temperature; therewith, the effect of scandium on the increase in the temperatures of the onset and finish of recrystallization is more substantial.     

Al-Zn-Mg系铝合金应力腐蚀性能

研究了热处理制度和时效工艺的改变对Al-Zn-Mg系铝合金的组织结构、力学性能和应力腐 蚀性能的影响。研究结果表明:高温预析出可以改变Al-Zn-Mg系铝合金晶界的析出相大小和分 布,从而改善其抗应力腐蚀性能;在T6和T612种人工时效条件下,预析出的合金的抗应力腐蚀 性能均好于无预析出的合金。在自然时效状态下,引入超声波,对无预析出合金的应力腐蚀性能 进行了初步探索,发现超声波可以提高合金的抗应力腐蚀性能,而对合金的硬度无影响。     

Mechanisms of corrosion fatigue crack propagation in Al-Zn-Mg alloys

Corrosion fatigue crack propagation tests were performed on commercial 7075 alloys. Testing was done in a 3.5 pct sodium chloride solution under constant impressed potential and under reversed anodic-cathodic current conditions. Results indicated that a cathodic potential of -1.400 V vs SCE was sufficient to reduce corrosion fatigue crack growth rates to the level observed in dry argon. By alternately impressing anodic and cathodic currents, it was shown that anodic potentials enhance the crystallographic dependence of the fracture mode, resulting in brittle striations, while cathodic potentials result in ductile striations formed by shear. Modification of the alloy chemistry and lower impurity content resulted in a two-fold reduction in crack growth rates. Thermomechanical treatment of these alloys to refine the grain size proved detrimental. Adding an inhibitor to the sodium chloride solution was found to be the most effective means for reducing corrosion fatigue crack growth rates. A model for the environment-surface interaction is suggested.     

Influence of aging on transformation characteristics in shape memory CuZnAl alloys

Shape memory alloys exhibit superelasticity when they are deformed in a temperature range where the thermoelastic martensite forms on application of a strain. The martensite persists upon removal of the applied strain, and the alloy recovers the original shape on heating over the reverse-transformation temperature after removing the strain. The β-phase CuZnAl alloys have β-type superlattice in the parent case, and M9R or M18R martensites occur on quenching the alloys from the homogenization temperature. The basal plane of martensite is exposed to hexagonal distortion with martensitic transformation as well as the monoclinic distortion in the crystal structure, and splittings are observed in some selected diffraction-peak pairs due to the differences in atom sizes in lattice points. These pairs have a great importance as ordering criteria and satisfy a special relation between Miller indices. The present text reports the variation of the differences in interplane spacings (Δd) between some selected planes upon the further aging at room temperature at which alloys are fully martensitic. The decrease of Δd during the aging implies that the monoclinic distortion decreases. The mass increases are caused by the oxidation upon heating the alloys at high temperatures close to the betatizing temperature at free atmosphere.     

形变对铁铜合金时效析出的影响

对铁铜合金分别进行50%和80%冷变形,利用金相显微镜以及高分辨投射电镜研究形变热处理过程中的微观组织与沉淀析出,分析形变量对时效析出的影响.结果表明:变形有助于第二相的析出,大的冷变形量时沉淀相粒子形成的速率更快,所占体积分数更大.优先析出为富铜过渡相,这种富铜过渡相所形成的GP区对合金起强化作用,其后随时效时间延长这种富铜相逐渐转转变成ε-Cu.     

Thermomechanical treatments on high strength Al-Zn-Mg(-Cu) alloys

An investigation was carried out to determine the metallurgical properties of Al-Zn-Mg and Al-Zn-Mg-Cu alloy products processed according to newly developed Final Thermomechanical Treatments (FTMT) of T-AHA type. The results show that these cycles can be utilized to produce wrought products of high purity Al-Zn-Mg(-Cu) alloys characterized by equivalent toughness and ductility and much higher strength than conventionally processed commercial purity materials. Based on transmission electron microscopy studies, it was found that such improved behavior of FTMT material is attributable to the superposition of hardening effects, from aging precipitation and from dislocations. Preliminary stress-corrosion and fatigue tests indicate that these properties are not substantially influenced by T-AHA thermomechanical process. Further work is needed in this area, in order to better understand the directions to follow for developing better alloys.     

Influence of gold content on copper oxidation from silver-gold-copper alloys

In the final stages of the smelting of copper anode slimes, a silver alloy, known as “doré,” is produced. Oxidation refining is used to remove copper since this element interferes with subsequent electroparting of the small amounts of gold and platinum group metals in the doré. The gold content of doré can be greatly increased by gold scrap additions and this may affect the minimum achievable copper content of doré. In this work, silver-gold-copper alloys were oxidized by injecting pure oxygen at 1100 °C in the absence of any slag cover. For the gold contents expected in practice, the equilibrium copper content of the doré did not increase significantly as the gold content increased. However, at the other extreme of composition, the equilibrium copper content was a very strong function of the silver content of the gold bullion. The activity coefficient of copper in silver-gold alloys was calculated and compared to those predicted from a ternary subregular solution model of the system Ag-Au-Cu. Satisfactory agreement was found.     

Microstructure study on the effect of titanium in the aging treatment of an Al-Zn-Mg alloy

A study has been made of the effect of Ti additions on the microstructure in two stage and single stage aging of an Al-5 Zn-2 Mg alloy. The influence of aging treatment was examined for alloys with and without Ti addition. The alloys were solution heat treated at 510°C, air cooled then aged at various temperatures below the GP zone solvus for short times before aging above the GP zone solvus at 200°C. The Ti addition alloy yields a small precipitate free zone (PFZ ∼ 0.3 μ) and a higher density of precipitate near the edge of the PFZ than in the midgrain region. The ternary alloy without Ti addition produces a wide range of PFZ sizes (0.4 to 4 μ) depending upon the aging temperature below the GP zone solvus. Significant changes in the morphology of the matrix precipitate, the amount of grain boundary precipitate, and the width of the PFZ, were observed in single stage aging at 200°C as a result of the Ti addition. These results could be explained in terms of Ti interacting with vacancies or solute atoms, causing the changes in the vacancy and/or solute concentration profiles. A model based upon solute and vacancy concentrations coupled with a time at temperature effect has been developed to allow the interpretation of the observed two-stage aging results in an Al-Zn-Mg alloy. Formerly Graduate Research Assistant, Materials Engineering, Rensselaer Polytechnic Institute, Troy, New York.     

The embrittlement of Al-Zn-Mg and Al-Mg alloys by water vapor

Al4.5Zn1.5Mg and Al5Mg were reacted in water-vapor saturated air (WVSA) at 120°C and tensile tested. After an initial loss of ductility with exposure time, probably caused by hydrogen embrittlement of the grain boundaries, between 15 hours and 25 hours exposure the mechanical properties of Al4.5Zn1.5Mg improved, this effect being due both to a reduced corrosion activity of the grain boundaries in producing embrittling hydrogen at the external surface and to grain boundary MgZn₂ precipitates acting as hydrogen traps. After 25 hours exposure water was shown to penetrate the grain boundaries, and a layered corrosion product identified as the aluminum hydroxides boehmite and diaspore was formed. This resulted in a marked fall of ductility. Re-solution heat treatment and reaging partially recovered the mechanical properties of Al4.5Zn1.5Mg if the exposure time was less than 50 hours, and would not recover properties for longer exposure times. Small additions (0.1 pct) of iron and nickel to Al4.5Zn1.5Mg lessened the grain boundaries’ sensitivity to corrosive attack whereas the addition of 0.1 pct copper did not. Also, the former two additions did not cause the relative ductility increase during 15 to 25 hours exposure in WVSA at 120°C shown by Al4.5Zn1.5Mg. It is proposed that these elements alter the magnesium segregation levels at the grain boundaries which in turn affects their electrochemical attack.