Pei Sun

Powder metallurgy of titanium – past, present, and future

ABSTRACT Powder metallurgy (PM) of titanium is a potentially cost-effective alternative to conventional wrought titanium. This article examines both traditional and emerging technologies, including the production of powder, and the sintering, microstructure, and mechanical properties of PM Ti. The production methods of powder are classified into two categories: (1) powder that is produced as the product of extractive metallurgy processes, and (2) powder that is made from Ti sponge, ingot, mill products, or scrap. A new hydrogen-assisted magnesium reduction (HAMR) process is also discussed. The mechanical properties of Ti-6Al-4V produced using various PM processes are analyzed based on their dependence on unique microstructural features, oxygen content, porosity, and grain size. In particular, the fatigue properties of PM Ti-6Al-4V are examined as functions of microstructure. A hydrogen-enabled approach for microstructural engineering that can be used to produce PM Ti with wrought-like microstructure and properties is also presented. Abbreviations: AM: additive manufacturing; ARC: Albany Research Center; BE: blended elemental; BUS: broken-up structure; CCGA: close-coupled gas atomisation; CHIP: CIP-sinter-HIP; CIP: cold isostatic pressing; CP-Ti: commercially pure Ti; DRTS: direct reduction of Ti-slag; CSIR: Council for Scientific and Industrial Research (South Africa); CSIRO: Commonwealth Scientific and Industrial Research Organization (Australia); EIGA: electrode induction gas atomisation; EMR: electronically mediated reduction; FFC: Fray, Farthing, and Chen; GA: gas atomisation; GIF: gaseous isostatic forging; GSD: granulation-sintering-deoxygenation; HAMR: hydrogen-assisted magnesium reduction; HDH: hydride–dehydride; HIP: hot isostatic pressing; HSPT: hydrogen sintering and phase transformation; MA: master alloy; MER: Materials & Electrochemical Research Corporation (US); MHR: metal hydride reduction; MIM: metal injection molding; OM: optical microscope; OS: Ono and Suzuki; PA: pre-alloyed; P/C: performance to cost ratio; PIF: pneumatic isostatic forging; PM: powder metallurgy; PREP: plasma rotating electrode process; PP: post-processing; PS: press and sinter; QIT: Quebec Iron & Titane, Inc. (Canada); SEM: scanning electron microscope; SPS: spark plasma sintering; SOM: solid oxide membrane; THP: thermohydrogen processing; TMP: thermomechanical processing; UFG: ultrafine grain; UGS: upgraded titanium slag; UTS: ultimate tensile strength; USTB: University of Science and Technology Beijing (China); VA: vacuum atomisation; VHP: vacuum hot pressing; WP: wrought process; YS: yield strength

Thermodynamic Destabilization of Ti-O Solid Solution by H2 and Deoxygenation of Ti Using Mg

Reactive metals including Ti, Zr, Hf, and V, among others, have a strong chemical affinity to oxygen, which makes them difficult to produce and costly to use. It is especially challenging to produce pure or metal alloy powders of these elements when extremely low oxygen content is required, because they have high solubility for oxygen, and the solid solution of these metals with oxygen is often more stable thermodynamically than their oxides. We report a novel thermochemical approach to destabilize Ti(O) solid solutions using hydrogen, thus enabling deoxygenation of Ti powder using Mg, which has not been possible before because of the thermodynamic stability of Ti(O) solid solutions relative to MgO. The work on Ti serves as an example for other reactive metals. Both analytical modeling and experimental results show that hydrogen can indeed increase the oxygen potential of Ti-O solid solution alloys; in other words, the stability of Ti-O solid solutions is effectively decreased, thus increasing the thermodynamic driving force for Mg to react with oxygen in Ti. Because hydrogen can be easily removed from Ti by a simple heat treatment, it is used only as a temporary alloying element to destabilize the Ti-O systems. The thermodynamic approach described here is a breakthrough and is applicable to a range of different materials. This work is expected to provide an enabling solution to overcome one of the key scientific and technological hurdles to the additive manufacturing of metals, which is emerging rapidly as the future of the manufacturing industry.

New Powder Metallurgical Approach to Achieve High Fatigue Strength in Ti-6Al-4V Alloy

Recently, manufacturing of titanium by sintering and dehydrogenation of hydride powders has generated a great deal of interest. An overarching concern regarding powder metallurgy (PM) titanium is that critical mechanical properties, especially the high-cycle fatigue strength, are lower than those of wrought titanium alloys. It is demonstrated here that PM Ti-6Al-4V alloy with mechanical properties comparable (in fatigue strength) and exceeding (in tensile properties) those of wrought Ti-6Al-4V can be produced from titanium hydride powder, through the hydrogen sintering and phase transformation process. Tensile and fatigue behavior, as well as fatigue fracture mechanisms, have been investigated under three processing conditions. It is shown that a reduction in the size of extreme-sized pores by changing the hydride particle size distribution can lead to improved fatigue strength. Further densification by pneumatic isostatic forging leads to a fatigue strength of ~550 MPa, comparable to the best of PM Ti-6Al-4V alloys prepared by other methods and approaching the fatigue strengths of wrought Ti-6Al-4V alloys. The microstructural factors that limit fatigue strength in PM titanium have been investigated, and pathways to achieve greater fatigue strengths in PM Ti-6Al-4V alloys have been identified.

Hydrogen-enabled microstructure and fatigue strength engineering of titanium alloys

Traditionally, titanium alloys with satisfactory mechanical properties can only be produced via energy-intensive and costly wrought processes, while titanium alloys produced using low-cost powder metallurgy methods consistently result in inferior mechanical properties, especially low fatigue strength. Herein, we demonstrate a new microstructural engineering approach for producing low-cost titanium alloys with exceptional fatigue strength via the hydrogen sintering and phase transformation (HSPT) process. The high fatigue strength presented in this work is achieved by creating wrought-like microstructures without resorting to wrought processing. This is accomplished by generating an ultrafine-grained as-sintered microstructure through hydrogen-enabled phase transformations, facilitating the subsequent creation of fatigue-resistant microstructures via simple heat treatments. The exceptional strength, ductility, and fatigue performance reported in this paper are a breakthrough in the field of low-cost titanium processing.

Hydrogen sintering of titanium and its alloys

Hydrogen sintering and phase transformation (HSPT) is a press and sinter process used to produce titanium alloys with engineered microstructures in the as-sintered state. During HSPT, titanium alloys are sintered under a dynamically controlled hydrogen partial pressure. HSPT utilizes phase transformations in the Ti–H system to refine the microstructure during sintering. Therefore, this process is capable of producing titanium alloys with strength and ductility in the as-sintered state that exceed ASTM standards for wrought titanium. HSPT circumvents the energy-intensive thermomechanical work that is compulsory for other titanium production technologies without sacrificing mechanical properties. Therefore, the performance-to-cost ratio of titanium alloys produced by this method should be greatly increased versus wrought processing and traditional PM. It has been projected that HSPT offers about an 80% energy savings per ton of titanium alloy produced versus wrought processing.

Mechanisms of Hydrogen-Assisted Magnesiothermic Reduction of TiO2

Direct reduction of TiO2 powder has been attempted for decades by researchers in an effort to decrease titanium (Ti) metal production costs. The main objective has been to avoid energy-intensive steps involved in production of primary Ti by the Kroll process. The emerging hydrogen-assisted magnesiothermic reduction process, which uses Mg to directly reduce TiO2 powder under a H2 atmosphere, has been shown to have the potential to compete directly with the Kroll process. The present studies represent an effort to understand the reduction reaction mechanisms of this process. Phase transformations and the reaction pathways are examined by SEM/EDX analysis of partially reduced powder cross-sectional, X-ray diffraction, and other analytical techniques. The results show important morphological changes, the prominent intermediate and final phases under the H2 atmosphere, as well as the local deposition behavior of the MgO byproduct. The effect of the specific surface areas of the initial particles is also discussed.