US20160243617A1

US20160243617A1 - Manufacture of near-net shape titanium alloy articles from metal powders by sintering with presence of atomic hydrogen

Info

Publication number: US20160243617A1
Application number: US14/584,176
Authority: US
Inventors: Orest M. Ivasishin; Dmitro G. Savvakin; Vladimir S. MOXON; Vladimir A. DUZ; Mykola M. GUMENYAK
Original assignee: Advance Materials Products Inc
Current assignee: Advance Materials Products Inc
Priority date: 2007-06-11
Filing date: 2014-12-29
Publication date: 2016-08-25
Also published as: WO2016109431A1

Abstract

Disclosed herein is a process that includes:

- (a) forming a powder blend by mixing Commercially Pure (C.P.) titanium powder, one or more hydrogenated titanium powders containing around 3.4 to around 3.9 weight % of hydrogen (e.g., hydrogenated titanium powders available or referred to nominally as “titanium hydride” or TiH₂), and one or more hydrogenated titanium powders containing around 0.2 to around 3.4 weight % of hydrogen, or a mixture of the hydrogenated titanium powders without the C.P. titanium powder,
- (b) consolidating the powder blend by either compacting the powder blend using die pressing, direct powder rolling, cold isostatic pressing, impulse pressing, metal injection molding, other room temperature consolidation method, or combination thereof, at a pressure in the range of around 400 to around 960 MPa, or loose sintering, to provide a green compact having a density lower than that of a green compact formed from only C.P. titanium powder, such that the subsequent sintering of said green compacts is promoted by an increased hydrogen content retained in the green compact which provides emission of hydrogen and a high partial pressure during subsequent cleaning and sintering steps,
- (c) heating the green compact to a temperature ranging from around 100° C. to around 250° C. at a heating rate≦around 15° C./min, thereby releasing absorbed water from the titanium powder, and holding the green compact at this temperature for a holding time ranging from around 10 to around 360 min, wherein the holding time and a thickness of the green compact are such that there is around 20 to around 24 min of holding time per every 6 mm of the thickness of the green compact,
- (d) forming β-phase titanium and releasing atomic hydrogen from the hydrogenated titanium by heating the green compact to a temperature of around 400 to around 600° C. in an atmosphere of hydrogen emitted by the hydrogenated titanium and holding the green compact at this temperature for around 5 to around 30 min thereby forming and releasing reaction water from the hydrogenated titanium powder,
- (e) reducing surface oxides on particles of the titanium powder by contact with atomic hydrogen released by heating of the green compact to a temperature of around 600 to around 700° C. and holding at this temperature for a holding time of around 30 to around 60 min sufficient to transform β-phase titanium into α-phase titanium while preventing dissolution of oxygen in the metallic body of the titanium particles and simultaneously providing maximum cleaning of titanium powders before forming closed pores,
- (f) diffusion-controlled chemical homogenizing of the green compact and densification of the green compact by heating to around 800 to around 850° C. at a heating rate of around 6 to around 8° C./min, followed by holding at this temperature for 30-40 min resulting in complete or partial dehydrogenation and more active shrinkage of titanium powder formed from the initial hydrogenated titanium powder to form a cleaned and refined compact,
- (g) heating the cleaned and refined green compact in vacuum at a temperature in the range of around 1000 to around 1350° C., and holding the cleaned and refined green compact at such temperature for at least around 30 minutes, thereby sintering titanium to form a sintered dense compact, and
- (h) cooling the sintered dense compact to form a sintered near-net shaped article.

Description

This application is a continuation-in-part of U.S. Ser. No. 11/811,578, filed Jun. 11, 2007, the entire contents of which are incorporated herein by reference.

BACKGROUND

1. Field
Disclosed herein are methods and compositions related to powder metallurgy of titanium and titanium alloys, as well as methods of using these compositions in aircraft, automotive, Naval applications, oil equipment, chemical apparatus, and other industries. More particularly, there is disclosed herein methods for the manufacture of near-net shape titanium articles from sintered elemental and alloyed powders.
2. Description of Related Art
Titanium alloys are known to exhibit light weight, high resistance to oxidation or corrosion, and the highest specific strength (the strength-to-weight ratio) of all metals except beryllium. Articles of titanium alloys have been produced by melting, forming, and machining processes, or by certain powder metallurgy techniques. However, the first method is not cost effective (although it provides high levels of desired properties of titanium alloys). The second method is cost effective but as previously implemented cannot completely realize all of the desirable advantages of titanium alloys.
Various processes have been developed during the last four decades for the fabrication of near-net shape titanium articles from powders with desirable density and mechanical properties. The use of elemental powder mixtures, control of the particle size distribution, vacuum sintering, hot isostatic pressing, and special surface finishing are among those new developments. But all of these processes, as well as conventional powder metallurgy techniques, impose certain limitations with respect to the characteristics of the produced titanium alloys.
For example, the method described in U.S. Pat. No. 4,432,795 (the contents of which are incorporated herein by reference) includes grinding particles of light metals to a median particle size of less than 20 μm, mixing them with particles of titanium based alloys having a median particle size larger than 40 μm, and compacting the mixture by molding and sintering at temperatures less than that of a formation of any liquid phase. This method allows the manufacture of the alloy having a density close to the theoretical value. However, the resulting alloy, contaminated by oxygen, iron, and other impurities, also exhibits insufficient mechanical properties.
U.S. Pat. No. 4,838,935 (the contents of which are incorporated herein by reference) discloses the use of titanium hydride together with titanium powder in the primary mixture before molding and sintering to form tungsten-titanium sputtering targets. The molded article is heated in a hot-press vacuum chamber to a temperature sufficient for the dehydration of TiH₂to remove gases. Then, the article is heated to a second temperature of 1350-1500° C. while maintaining the pressure and vacuum. This method cannot completely prevent the oxidation of highly-reactive titanium powders during the second heating, because hydrogen is permanently outgassing from the working chamber. Also, the method does not provide sufficient cleaning of titanium powder that resulted in deviations of final products from AMS and ASTM specifications. In addition, this method is not suitable for powdered mixtures containing low-melting metal and phases.
A preliminary partial sintering of titanium and titanium hydride powders with at least one powdered additive of alloying metals (selected from powdered Ni, Al, Cu, Sn, Pd, Co, Fe, Cr, Mn, and Si) is disclosed in U.S. Pat. No. 3,950,166 (the contents of which are incorporated herein by reference). The “mother” alloy obtained in such a way is pulverized and remixed with at least one of powdered titanium or titanium hydride, and optionally with powdered metals such as Mo, V, Zr, and Al—V alloys to achieve the final composition of titanium alloy. This mixture is molded in a predetermined shape and sintered at 1000-1500° C. in a vacuum. While the preliminary sintering partially resolves one technical problem (how to improve uniform distribution of alloying components), the process generates another problem (oxidation of the “mother” powder during pulverization).
Several attempts have been made to improve the density and purity of sintered titanium alloys that involve using titanium hydride as the raw material, together with other alloying powders, e.g., in U.S. Pat. No. 3,472,705, which relates to the production of niobium-titanium or niobium-zirconium superconducting strips. This method includes vacuum heating and sintering accompanied with permanent outgassing, where the heating is used to decompose the hydride to metal before sintering. As a result, the “cleaning effect” of hydrogen is not fully obtained, and partial oxidation reoccurs after the removal of hydrogen from the vacuum chamber. Thus, the method does not provide an effective improvement of mechanical properties of sintered alloys, in spite of any sintering that may be promoted by thermal dissociation of titanium hydride.
A particular process for use of titanium hydride powders combined with master alloy powders or elemental powders has been described in U.S. Patent Application Publication No. 2003/0211001 (the entire contents of which are incorporated herein by reference). However, this publication does not describe a process wherein Commercially Pure (C.P.) titanium powder can be used.
Other known processes for making near-net shape titanium alloys from metal powders have the same drawbacks: (a) insufficient purity and low mechanical properties of sintered titanium alloys, (b) irregular porosity and insufficient density of sintered titanium alloys, and (c) low reproduction of mechanical properties that depend on the purity of raw materials. Indeed, the association of the use of hydrides with increased porosity is so well established that hydrides are specifically disclosed as useful when porous bodies are desirable, as in U.S. Pat. No. 4,560,621.

SUMMARY

As a result of the drawbacks of the techniques described above, there remains a need in the art for processes that will increase the mechanical properties, particularly strength and plasticity, of near-net shape articles manufactured by sintering titanium alloys from elemental and/or alloyed metal powders. In order to obtain a high level of mechanical properties, any oxidation or contamination of powdered components must be prevented during heating and sintering.
There also remains a need in the art for processes that provide low porosity and high-density structures of sintered titanium alloys to achieve the densities close to the theoretical value.
There remains a need in the art for processes that provide cost-effective manufacture of near-net shape articles using one-run heating and sintering of powdered titanium alloys.
Finally, there remains a need in the art for processes of sintering titanium and titanium alloy powders mixed and compacted with a titanium hydride (TiH₂containing over 3.4 weight % hydrogen) powder and hydrogenated titanium powders containing less than 3.4 weight % of hydrogen) which provide both low content of all impurities and improved mechanical properties of the final product in order to meet requirements of such industrial specs as AMS and ASTM.
Some or all of the needs described above can be met by the methods described herein, and by the near-net shape sintered titanium articles that result therefrom. The disclosed methods relate to embodiments of processes for the manufacture of near-net shape titanium articles from sintered powders containing commercially pure (C.P.) titanium and/or hydrogenated titanium powders, and/or titanium alloys with all required alloying elements. The embodiments of the methods disclosed herein resolve many or all of the problems related to high impurities, insufficient strength, irregular porosity, insufficient density, and cost reductions that have been described above, and that have not been solved by prior processes.
The embodiments of the methods described herein overcome these problems by sintering in the presence of atomic hydrogen emitted by the hydrogenated titanium powders.
In one embodiment, the process includes:
(a) forming a powder blend by mixing (1) Commercially Pure (C.P.) titanium powder, and (2) one or more of (i) one or more hydrogenated titanium powders containing around 3.4 to around 3.9 weight % of hydrogen (e.g., hydrogenated titanium powders available or referred to nominally as “titanium hydride” or TiH₂), and (ii) one or more hydrogenated titanium powders containing around 0.2 to around 3.4 weight % of hydrogen,
(b) consolidating the powder blend by either compacting the powder blend using die pressing, direct powder rolling, cold isostatic pressing, impulse pressing, metal injection molding, other room temperature consolidation method, or combination thereof, at a pressure in the range of around 400 to around 960 MPa, or loose sintering, to provide a green compact having a density lower than that of a green compact formed from only C.P. titanium powder, such that the subsequent sintering of said green compacts is promoted by an increased hydrogen content retained in the green compact which provides emission of atomic hydrogen and a high partial pressure during subsequent cleaning and sintering steps,
(c) heating the green compact to a temperature ranging from around 100° C. to around 250° C. at a heating rate≦around 15° C./min, thereby releasing absorbed water from the titanium powder, and holding the green compact at this temperature for a holding time ranging from around 10 to around 360 min, wherein the holding time and a thickness of the green compact are such that there is around 20 to around 24 min of holding time per every 6 mm of the thickness of the green compact,
(d) forming β-phase titanium and releasing atomic hydrogen from the hydrogenated titanium by heating the green compact to a temperature of around 400 to around 600° C. in an atmosphere of hydrogen emitted by the hydrogenated titanium and holding the green compact at this temperature for around 5 to around 30 min thereby forming and releasing reaction water from the hydrogenated titanium powder,
(e) reducing surface oxides on particles of the titanium powder by contact with atomic hydrogen released by heating of the green compact to a temperature of around 600 to around 700° C. and holding at this temperature for a holding time of around 30 to around 60 min sufficient to transform β-phase titanium into α-phase titanium while preventing dissolution of oxygen in the metallic body of the titanium particles and simultaneously providing maximum cleaning of titanium powders before forming closed pores,
(f) diffusion-controlled chemical homogenizing of the green compact and densification of the green compact by heating to around 800 to around 850° C. at a heating rate of around 6 to around 8° C./min, followed by holding at this temperature for 30-40 min resulting in complete or partial dehydrogenation and more active shrinkage of titanium powder formed from the initial hydrogenated titanium powder to form a cleaned and refined compact,
(g) heating the cleaned and refined green compact in vacuum at a temperature in the range of around 1000 to around 1350° C., and holding the cleaned and refined green compact at such temperature for at least around 30 minutes, thereby sintering titanium to form a sintered dense compact, and
(h) cooling the sintered dense compact to form a sintered near-net shaped article.
In another embodiment, the process includes:
(a) forming a powder blend by mixing two or more hydrogenated titanium powders containing around 0.2 to around 3.9 weight % of hydrogen,
(b) consolidating the powder blend by either compacting the powder blend using die pressing, direct powder rolling, cold isostatic pressing, impulse pressing, metal injection molding, other room temperature consolidation method, or combination thereof, at a pressure in the range of around 400 to around 960 MPa, or loose sintering, to provide a green compact having a density lower than that of a green compact formed from only C.P. titanium powder, such that the subsequent sintering of said green compacts is promoted by an increased hydrogen content retained in the green compact which provides emission of atomic hydrogen and a high partial pressure during subsequent cleaning and sintering steps,
(c) heating the green compact to a temperature ranging from around 100° C. to around 250° C. at a heating rate≦around 15° C./min, thereby releasing absorbed water from the titanium powder, and holding the green compact at this temperature for a holding time ranging from around 10 to around 360 min, wherein the holding time and a thickness of the green compact are such that there is around 18 to around 24 min of holding time per every 6 mm of the thickness of the green compact,
(d) forming β-phase titanium and releasing atomic hydrogen from titanium hydride by heating the green compact to a temperature of around 400 to around 600° C. in an atmosphere of hydrogen emitted by the hydrogenated titanium and holding the green compact at this temperature for around 5 to around 30 min thereby forming and releasing reaction water from the hydrogenated titanium powder,
(e) reducing surface oxides on particles of the titanium powder by contact with atomic hydrogen released by heating of the green compact to a temperature of around 600 to around 700° C. and holding at this temperature for a holding time of around 30 to around 60 min sufficient to transform β-phase titanium into α-phase titanium while preventing dissolution of oxygen in the metallic body of the titanium particles and simultaneously providing maximum cleaning of titanium powders before forming closed pores,
(f) diffusion-controlled chemical homogenizing of the green compact and densification of the green compact by heating to around 800 to around 850° C. at a heating rate of around 6 to around 8° C./min, followed by holding at this temperature for a holding time of around 30 to around 40 min resulting in complete or partial dehydrogenation and more active shrinkage of titanium powder formed from the initial hydrogenated titanium powder to form a cleaned and refined compact,
(g) heating the cleaned and refined green compact in vacuum at a temperature in the range of around 1000 to around 1350° C., and holding the cleaned and refined green compact at such temperature for at least around 30 minutes, thereby sintering titanium to form a sintered dense compact, and
(h) cooling the sintered dense compact to form a sintered near-net shaped article.
The initial mixture of metal powders (the powder blend) can additionally comprise a powder prepared from underseparated titanium sponge, or alloying metal powders selected from master alloy powders, or alloy mixture of elemental powders, or pre-alloyed titanium powders, or combinations of these.
The powder blend can comprise, in addition to C.P. titanium powder, only the hydrogenated titanium powders containing different amount of hydrogen in the range of 0.2-3.9 wt. %. Alternatively, the powder blend may contain only the hydrogenated titanium powders, or may exclude the C.P. titanium powder, as indicated in the embodiment described above.
Further decreasing of the residual hydrogen content to below around 150 ppm may be achieved during subsequent high temperature processing (e.g., forging, rolling, hot isostatic pressing (HIP), extrusion, or combinations of these) followed by vacuum annealing at temperatures of around 700 to around 750° C.
In an alternative embodiment, formation of the β-phase titanium and releasing of atomic hydrogen from the hydrogenated titanium powder is carried out by slow heating, i.e., heating the green compact to a temperature ranging from about 250° C. to about 600° C. in an atmosphere of emitted hydrogen at the heating rate≦around 15° C./min to enhance the chemical reduction and cleaning effect of the emitted hydrogen and to release reaction water from titanium hydride and hydrogenated titanium powders.
In order to accumulate crystal defects for additional activation of sintering titanium particles, multiple initiation of alpha-beta-alpha phase transitions in titanium green compact is carried out by thermal cycling at temperatures in the range of around 800 to around 900° C.
As indicated above, in a particular embodiment, consolidating of the powder blend can result from compaction, or from loose sintering. Loose sintering can be used without use of room temperature consolidation. In this case, a 40% to 90% dense sintered preform is further processed by high temperature deformation (forging, rolling, extrusion, etc.) to reach the required full theoretical density, which can be followed by the appropriate annealing or other stress relief operations. Cleaning of titanium particles by emitted atomic hydrogen is facilitated in the loose-sintered green compact due to the developed porosity of the material.
In a particular embodiment, the dehydrogenation taking place during sintering operations may be disrupted at a temperature above around 800° C. before the completion of hydrogen evacuation in order to reserve residual hydrogen, which can be useful or necessary for reducing the deformation forces, grain refinements, and/or other positive effects such as additional cleaning of sintered titanium article during subsequent hot processing by forging, rolling, HIP, and/or extrusion.
The embodiments disclosed herein are particularly useful when forming parts having complex shapes, in particular when forming shapes with variations in their thickness that are being compacted in the thickness direction, and when the difference in green densities are very pronounced and cannot be avoided, because the use of hydrogenated titanium powders allows the disclosed process to reach near full density during sintering, which is impossible to achieve when non hydrogenated titanium powder is used.
The hydrogenated titanium powders are present in an amount of 10-90 wt. % of the powder blend, while other titanium powders (C.P. titanium powder, underseparated titanium powder, etc.) is present in an amount of 5-20 wt. % of the powder blend. These titanium powders may be also hydrogenated prior to the blending operation.
In particular embodiments, the resulting sintered near-net shape titanium article desirably contains less than 0.2 wt. % of oxygen, less than 0.006 wt. % of hydrogen, less than 0.05 wt. % of chlorine, less than 0.05 wt. % of magnesium, less than 10 ppm of sodium, and desirably has a final porosity less than 1.5% at pore sizes less than 20 microns. This low interstitial content achieved by our process makes the resulting titanium and titanium alloys weldable, which was not achievable by prior art.
In particular embodiments, initial heating is desirably performed at a slow rate, e.g., at a rate of ≦15° C./min.
The embodiments described herein are desirable because they can provide a method to manufacture near-net shape sintered titanium articles in a cost-effective way as a result of performing all process operations within one thermal cycle for one furnace run. This is, at least in part, the result of control of the purity and mechanical properties of sintered titanium alloys using (a) particularly desirable thermal processing of titanium, and hydrogenated titanium powders and control of atomic hydrogen emitted from the hydrogenated powders during heating in vacuum, (b) control of open porosity and hydrogen cleaning of titanium and titanium alloy particles at different steps of the thermal cycle during the sintering process, and (c) control of alpha-beta transformation of titanium in conjunction with porosity, cleaning, and densification of green compact depending on the presence, pressure, and activity of emitted hydrogen in the furnace chamber during the heating and sintering.

BRIEF DESCRIPTION OF DRAWINGS

The embodiments described herein can be understood by reference to the accompanying drawings, which are intended to be illustrative, rather than limiting.

FIG. 1 is a graph showing the relationship between compaction pressure used to produce a green compact, and the relative density of the sintered articles prepared from Ti powder alone and from Ti powder combined with hydrogenated titanium powder according to an embodiment disclosed herein.

FIG. 2 is a graph showing the relationship between change in free energy and temperature for different hydrogen pressures during sintering according to an embodiment disclosed herein.

FIG. 3 is a schematic diagram illustrating two mechanisms for disappearance of oxide films on surfaces of particles of Ti metal and hydrogenated titanium.

FIG. 4 is a graph showing mass spectrometry curves that illustrate the relationship between released water, hydrogen emission, and temperature for processing according to embodiments disclosed herein.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

The methods described herein can be more clearly understood by reference to the following description of specific embodiments and examples, which are intended to illustrate, rather than limit, the scope of the appended claims.
As used herein, the terms “around” or “about” in connection with a numerical value denote a deviation from the numerical value of ±5%. As used herein, the term “hydrogenated titanium powders” includes titanium powders having hydrogen contents ranging from about 0.2 to about 3.9 wt %. This includes hydrogenated titanium particles nominally described as “titanium hydride” or “TiH₂”, as well as other hydrogenated titanium particles having hydrogen contents within the indicated range, and combinations thereof, unless otherwise indicated. For example, this terminology can include hydrogenated titanium powder containing hydrogen in an amount ranging from 0.2 wt % up to and including 3.4 wt %, as well as hydrogenated titanium powder containing hydrogen in an amount above 3.4 wt % and up to and including 3.9 wt %, the latter being sometimes denominated as “titanium hydride” or “TiH₂powder.”
As described above, the methods disclosed herein relate generally to the manufacture of sintered titanium and titanium alloys using elemental metal powders and titanium hydride and/or hydrogenated titanium powders as raw materials. It has been found that the atomic hydrogen emitted from titanium hydride and hydrogenated titanium powders before formation of molecular hydrogen plays a very important role in chemical reduction and cleaning of the titanium particles with respect to oxygen and other impurities such as chlorine, magnesium, sodium, and in preventing oxidation during heating and sintering, as well.
Previously known methods, as described above, have not been able to determine the desirable process steps and parameters described herein in order to provide effective action of emitted atomic hydrogen and control of porosity and densification of compacted titanium particles to reach maximum possible density, purity, and mechanical properties of final sintered articles. Previous methods described above have used permanent outgassing of the vacuum chamber during heating and sintering. As a result, a complete reaction between metal powders in green titanium compacts with hydrogen is not achieved, and the final structure of the sintered alloy contains oxides, other impurities, and irregular porosity.
In particular embodiments described herein, one or more of the hydrogenated titanium powders used was compacted to a relatively low density in the green samples (3.06 g/cm³) as compared to green samples prepared from titanium powder alone (3.47 g/cm³). However, after sintering, the converse was true, and the C.P.-Ti samples produced using hydrogenated titanium powder had a higher density (4.43 g/cm³, i.e. 98.2%) than those sintered from Ti powder alone (4.37 g/cm³, 97.0%). This result confirms the advantage of using hydrogenated titanium powders to form the powder blend with respect to achieving higher sintered density, as shown in FIG. 1, and is contrary to what would have been expected based on, e.g., U.S. Pat. No. 4,560,621. Similar results were obtained for Ti-6Al-4V compositions prepared according to the methods disclosed herein. The influence of the emitted hydrogen on sintered density becomes clear from an analysis of the effects of hydrogenated titanium upon compaction and heating processing stages of the disclosed methods, which determines final density.
The emitted atomic hydrogen beneficially affects sintering kinetics, helps to reduce any oxides that are usually located on the surface of powder particles, and by doing so, is cleaning inter-particle interfaces and enhancing the diffusion between all components of the powder mixture.
We discovered from our experimental studies that the positive effect of emitted hydrogen in titanium sintering can be significantly enhanced by the control of pressure, temperature and time within the sintering process. In particular, we found that the best reduction of surface titanium oxides by emitted atomic hydrogen occurs at particular combinations of the hydrogen pressure and temperature, as shown in FIG. 2.
In FIG. 2, all pressure-temperature combinations below the line of ΔG=0 provide reduction of titanium oxide, while there is no reduction reaction by the emitted atomic hydrogen at the pressure-temperature combinations above this line. This means that permanent outgassing during sintering with titanium hydride (which has been used in prior art methods described above) may result in ineffective reduction of surface titanium oxides from titanium particles, and as a result, in the presence of excessive or undesirably amounts of oxygen in the final sintered product.
Without wishing to be bound by any theory, it is believed that a characteristic feature of the hydrogenated titanium powders used in the methods disclosed herein is the ability to undergo a dehydrogenation process, i.e. a process of hydrogen evolution from the material, and the resulting significant shrinkage during vacuum heating above 320° C. The temperature interval of dehydrogenation and corresponding changes in the phase composition depend on the heating rate and the rate of hydrogen evacuation from the heating chamber. Relatively slow heating (e.g., a heating rate of ≦15° C./mm (preferably ˜7° C./mm) led to a phase change represented by TiH₂→β→α and which is a consequence of phase transformations, and completion of dehydrogenation at a temperature of about 800° C. The intensity of hydrogen evolution varied within the mentioned temperature range and was determined by diffusion rate of hydrogen in the phases towards the powder particle surface. The most intensive dehydrogenation with evolution of a major portion of hydrogen from the material was observed within a temperature range of about 400 to about 600° C., and is believed to be due to the formation of the β-phase, in which hydrogen diffusivity is the fastest. Decreases in hydrogen concentration are believed to lead to the α-phase formation at temperatures of about 600 to about 650° C. as a final product of dehydrogenation, and to the evolution of a small portion of residual hydrogen from the α phase at further heating up to 800° C.
Significant volume changes in the material that occur during dehydrogenation resulted in a much more considerable shrinkage of compacts prepared using hydrogenated titanium powder as compared to compacts prepared using only titanium metal powder. Shrinkage of compacts prepared using hydrogenated titanium powder is determined by dehydrogenation (below 800° C.) and sintering of powders and the contribution of the latter becomes apparent at the final stage of dehydrogenation and at higher temperatures. By contrast, the volume changes observed for compacts prepared using only titanium metal powders were determined by the mechanism of powder sintering only.
Other positive effects of using hydrogenated titanium powders in the powder blend and compacting the blend are (a) relative independence of final (sintered) density on the green density in different cross-sections of the sintered article, (b) the possibility of varying shrinkage to get the precise desired final article dimensions at near full theoretical density, and (c) the ability to have compaction stresses relaxed in more ductile titanium powder.
We also found that effectiveness of hydrogen cleaning depends on: (a) the state of oxygen in the titanium particles and (b) the type of porosity of the green compact that interacts with emitted atomic hydrogen. We found that the decrease of oxygen content by hydrogen reduction is especially important for powder material in which surface area is highly developed. On the other hand, this mechanism cannot decrease oxygen content if oxygen is in solid solution. FIG. 3 schematically illustrates a competition between two processes involving oxide films on the powder surfaces−either to be reduced by hydrogen or to be dissolved through diffusion of oxygen into the powder interior volume.
We found that the second process proceeds in vacuum at temperatures roughly above 700° C., but in this case oxygen goes inside and remains in the material. As a result, the first process (reducing by hydrogen) should proceed before the oxide dissolution. Therefore it is important to have hydrogen release from the powder particles and the respective reaction of oxide reducing before the oxide film dissolution in the titanium particle body. Control of the sintering thermal cycle by control of the heating rate and of the holding step in the temperature range of about 400 to about 600° C. significantly improve cleaning of oxygen from the particles of the titanium green compact.
The second feature of the hydrogen cleaning process occurring in the methods disclosed herein is transformation of open porosity to closed porosity. It has been found that this also happens at temperatures of around 700° C. After this, products of reacting hydrogen with surface impurities will be located inside of the titanium material, and either the reaction will stop due to excessive pressure in the closed pore, or the reaction products will dissolve themselves in titanium instead of reacting with hydrogen at the surface. This relates especially to magnesium and magnesium chloride impurities that should evaporate at the higher temperature of sintering.
As a result, the transformation of open porosity to closed porosity should be delayed until as late as possible in order to reach a high grade of cleaning of all impurities. This can be done by control of the heating rate at a temperature below 700° C. to reserve a part of the hydrogen for reacting at higher temperatures and providing holding steps at temperatures below those at which closing of pores occurs.
One more very important feature of using hydrogenated titanium powders as described herein is the release of H₂O that we observed within the interval of hydrogen emission illustrated by FIG. 4. FIG. 4, shows mass-spectrometry curves of H₂O and H₂gas release upon heating of titanium metal powdered compacts (curve Ti) and compacts prepared from hydrogenated titanium powders (curve TiH₂). A low-temperature H₂O peak is present for both the TiH₂and Ti compacts and, without wishing to be bound by theory, is believed to be related to the atmospheric moisture absorbed on the powders. However, another H₂O peak was observed in the curve for the TiH₂compact above 400° C., but absent from the curve for the Ti compact. The emission of H₂O during hydrogen evolution (indicated by the third curve) can be explained by the reduction of surface oxide scales and cleaning of the powder particle surfaces by emitted atomic hydrogen evolved according to the reaction: TiO₂+4H→Ti+2H₂O.
The dehydrogenation during the heating step, with the resulting phase transformations, volume changes, and reduction of surface oxides, is a distinct feature of the use of hydrogenated titanium powders as described herein, and has beneficial consequences which affect the sintering and properties of final material.
The alpha-beta phase transformations and significant shrinkage due to decrease in hydrogen concentration results in an increased amount of crystal lattice defects, and, hence, activation of diffusion processes. The high specific surface area of hydrogenated titanium powders that are crushed upon compaction also contributes to an acceleration of diffusion and improved sintering at further heating. Moreover, a cleaning effect of hydrogen evolved has two useful consequences.
The oxide scales at powder surfaces are effective barriers for diffusion, which can prevent or limit the sintering of compacted particles. For titanium powder, sintering becomes possible above ˜700° C. when dissolution of TiO₂scales occurs due to diffusion of oxygen atoms from the surface deep into the titanium. For hydrogenated titanium powders, hydrogen leaving a particle reduces the surface oxide scales (at least partially) before their dissolution and diffusion into the titanium particle, thus promoting a mass transfer between particles and decreasing oxygen content in dehydrogenated titanium.
As a positive effect of all these factors, dehydrogenation as described herein resulted in the formation of highly activated titanium and its improved sintering as compared to a common Ti powder. It can be seen from FIG. 1 that above 800° C., when dehydrogenation is already completed, the initially hydrogenated compact demonstrated noticeably more active shrinkage than the sample made from titanium metal powder. It is believe that first diffusion contacts between hydrogenated titanium particles formed under heating already at 710° C., i.e. before the dehydrogenation completion.
In order to enhance the above mentioned effect of alpha-beta phase transformation, we have found that thermal cycling in the temperature range of about 800 to about 900° C. is advantageous. Without wishing to be bound by theory, it is believed that this helps to accumulate crystal defects for additional activation of sintering titanium particles.
In addition, we found that methods for hot processing of the sintered titanium compact, such as forging, rolling, HIP, and/or extrusion, followed by vacuum annealing at temperatures of around 700 to around 750° C., results in further decrease of the content of residual hydrogen to below 150 ppm.
Optionally, the powder blend can comprise only hydrogenated titanium powders having the hydrogen contents described above, i.e., that contain different amounts of hydrogen in the range of 0.2-3.9 wt. %, for example, a powder blend that comprises three hydrogenated titanium powders with 0.2 wt. % of hydrogen, 2.0 wt. % of hydrogen, and 3.8 wt. % of hydrogen, respectively. During processing according to the embodiments described herein, it is believed that a powder having the lowest content of hydrogen becomes pure titanium powder due to dehydrogenation at an early point of the sintering process.
The embodiments of the process of the manufacture of net-shape titanium and titanium alloy articles described herein and the effects and features of sintering titanium particles in presence of atomic hydrogen that we found experimentally allow the manufacture of sintered titanium and titanium alloy articles with extremely low content of oxygen, hydrogen, and other impurities that meet industrial requirements of ASM and ASTM specifications, e.g.: less than 0.2 wt. % of oxygen, less than 0.006 wt. % of hydrogen, less than 0.05 wt. % of chlorine, less than 0.05 wt. % of magnesium, and wherein the resulting sintered titanium article has a final porosity less than 1.5% at pore sizes less than 20 microns. Low interstitial content made these titanium and titanium alloys weldable, which was not enabled in previously produced powder metallurgy alloys.
The resulting sintered articles have high mechanical properties such as tensile strength, yield strength, and elongation meet or exceed the requirements of the above specifications as indicated in the examples.
The foregoing examples of the invention are illustrative and explanatory. The examples are not intended to be exhaustive and serve only to show the possibilities of the technology disclosed herein.

Example 1

A powder blend of three hydrogenated titanium powders containing different amount of hydrogen was used: (1) 25% of hydrogenated titanium powder containing 0.5 wt. % of hydrogen, particle size <45 microns, (2) 25% of hydrogenated titanium powder containing 2 wt. % of hydrogen, particle size <100 microns, and (3) 50% of titanium hydride TiH₂powder containing 3.8 wt. % of hydrogen, particle size <120 microns. These powders were mixed together, and the obtained mixed powder was compacted at 720 MPa to a low density green compact of 3.05 g/cm³.
The green compact, having the thickness 12 mm, was heated to 250° C. at a slow heating rate of ˜7° C./min and held at this temperature for 40 min to release absorbed water from the titanium powder. Then, heating was continued at the heating rate of ˜22° C./min to a temperature in the range of 480-500° C. in the atmosphere of emitted hydrogen, and held at this temperature for 30 min to form β-phase titanium and to release reaction water from the hydrogenated titanium powders.
Almost complete reduction of surface oxides of the green compact particles by emitted atomic hydrogen was carried out by further heating the green compact to a temperature of 630° C. and holding at this temperature for 45 min, when the green compact still had open porosity structure. At the same time, β-phase titanium was transformed to α-phase titanium.
Further, the diffusion-controlled chemical homogenization was carried out by heating of green compact to 820° C. with a heating rate of 7° C./min and holding at this temperature for 30 min, which resulted in densification of the green compact to a density of 4.44 g/cm³due to completion of dehydrogenation and active shrinkage of the green compact.
Then, heating of the cleaned and refined green compact was continued in a vacuum of 10⁻⁴Torr at a heating rate of 5-10° C./min to a temperature 1220° C., followed by holding at this temperature for 3.5 hours to form a sintered dense compact, and finally, cooling the sintered compact was done to obtain a flat titanium plate.
The titanium plate was hot rolled to the thickness of 8 mm, followed by vacuum annealing at 750° C. for 1.5 hours.
The measured contents of impurities in the final product were the following:
oxygen <0.15 wt. %,
hydrogen <0.005 wt. %,
chlorine <0.001 wt. %,
magnesium <0.003 wt. %,
sodium <10 ppm.
Standard specimens for mechanical testing were cut and machined from the titanium plate, which has a refined microstructure. Mechanical properties of the manufactured titanium plate were found to be: ultimate tensile strength 552-571 MPa, yield strength 489-510 MPa, and 21-23% elongation.

Example 2

A powder blend of two types of powders was used: (1) 20% of CP titanium powder, which does not contain hydrogen at all, particle size <150 microns, and (2) 80% of titanium hydride TiH₂powder containing 3.5 wt. % of hydrogen, particle size <100 microns.
These powders were mixed together, and the obtained mixed powder was compacted at 780 MPa to a low density green compact of 3.24 g/cm³.
The green compact having the thickness 24 mm was heated to 230° C. at a slow heating rate of ˜7° C./min and held at this temperature for 80 min to release absorbed water from the powder. Then, heating was continued at the heating rate of ˜22° C./min to 560-580° C. in the atmosphere of emitted hydrogen and held at this temperature for 25 min to form β-phase titanium and release reaction water from the powder.
Almost complete reduction of surface oxides of green compact particles by emitted atomic hydrogen was carried out by further heating the green compact to 700° C. and holding at this temperature for 35 min when the green compact still had open porosity structure. At the same time, β-phase was transformed to α-phase titanium.
Further, the diffusion-controlled chemical homogenization was carried out by heating of green compact to 830° C. with the rate of 7° C./min and holding at this temperature for 20 min that was resulted in densification of green compact to 4.41 g/cm³due to complete dehydrogenation and active shrinkage of compact containing both titanium and titanium hydride components.
Then, heating of the cleaned and refined green compact was continued in vacuum of 10⁻⁴Torr at the rate of 5-10° C./min to the temperature 1240° C. followed by holding at this temperature for 4 hours to form a sintered dense compact, and finally, cooling the sintered compact was done to obtain a flat titanium plate.
The titanium plate was hot rolled to the thickness of 20 mm followed by vacuum annealing at 720° C. for 3.5 hours.
Measured contents of impurities in the final product were the following:
oxygen <0.14 wt. %,
hydrogen <0.006 wt. %,
chlorine <0.001 wt. %,
magnesium <0.004 wt. %,
sodium <10 ppm.
Standard specimens for mechanical testing were cut and machined from the titanium plate, which has a refined microstructure. Mechanical properties of the manufactured titanium plate were: ultimate tensile strength 567-582 MPa, yield strength 498-526 MPa, and 18-20% elongation.

Example 3

A powder blend of three types of powders was used: (1) 70 wt. % of titanium hydride powder TiH₂containing 3.8 wt. % of hydrogen and having particle size less than 120 μm, (2) 20% wt. % of CP titanium powder, which does not contain hydrogen, particle size <150 microns, and (3) 10 wt. % of the 60Al-40V master alloy powder having particle size <65 μm.
These powders were mixed together, and the obtained mixed powder was compacted at 960 MPa to a low density green compact of 3.46 g/cm³.
The green compact having the thickness 16 mm was heated to 250° C. at a slow heating rate of ˜7° C./min and held at this temperature for 50 min to release absorbed water from the powders. Then, heating was continued at a heating rate of ˜20° C./min to 580-600° C. in the atmosphere of emitted atomic hydrogen and held at this temperature for 30 min to form β-phase titanium and release reaction water from the powder.
Almost complete reduction of surface oxides of green compact particles by emitted hydrogen was carried out by further heating the green compact to 680° C. and holding at this temperature for 50 min when the green compact still had open porosity structure. At the same time, β-phase titanium was transformed to α-phase titanium.
Further, the diffusion-controlled chemical homogenization was carried out by heating of green compact to 850° C. with the rate of 7° C./min and holding at this temperature for 30 min that was resulted in densification of green compact to 4.47 g/cm³due to complete dehydrogenation and active shrinkage of the compact containing both titanium and hydrogenated titanium components.
Then, heating of the cleaned and refined green compact was continued in vacuum of 10⁻⁴Torr at the rate of 5-10° C./min to the temperature 1250° C. followed by holding at this temperature for 4.5 hours to form a sintered dense compact, and finally, cooling the sintered compact was done to obtain a flat titanium plate.
The titanium alloy Ti-6Al-4V plate was hot rolled to the thickness of 12 mm followed by vacuum annealing at 750° C. for 3 hours.
Measured contents of impurities in the final product were the following:
oxygen <0.15 wt. %,
hydrogen <0.0055 wt. %,
chlorine <0.001 wt. %,
magnesium <0.004 wt. %,
sodium <10 ppm.
Standard specimens for mechanical testing were cut and machined from the titanium alloy plate, which has a refined microstructure. Mechanical properties of the manufactured titanium plate were: ultimate tensile strength 979-1041 MPa, yield strength 889-910 MPa, and elongation at break 15-18%. Due to low content of contaminants, the resulting titanium alloy plate is weldable using both GTAW and GMAW arc welding technique.

Example 4

A powder blend of two types of powders was used: (1) 20 wt. % of underseparated titanium powder containing 2.0% chlorine and 0.8% of magnesium and having particle size <100 μm, and (2) 80 wt. % of titanium hydride TiH₂powder containing 3.9 wt. % of hydrogen, particle size <100 microns.
These powders are blended for 6 hours, and the obtained mixed powder was compacted at 400 MPa to a low density green compact of 3.18 g/cm³.
The green compact having a thickness 20 mm was heated to 250° C. at a slow heating rate of ˜7° C./min and held at this temperature for 70 min to release absorbed water from titanium powder. Then, the net-shaped green compacts were exposed to a temperature of 350° C. for 60 min during heating in vacuum furnace for evacuation of chlorine and magnesium from the material.
Further, heating was continued at the heating rate of ˜16° C./min to 400-420° C. in the atmosphere of emitted hydrogen and held at this temperature for 30 min to form β-phase titanium and release reaction water from the powder.
Almost complete reduction of surface oxides of green compact particles by emitted atomic hydrogen was carried out by further heating the green compact to 600-610° C. and holding at this temperature for 45 min when the green compact still had open porosity structure. At the same time, β-phase titanium was transformed to α-phase titanium.
Further, the diffusion-controlled chemical homogenization was carried out by heating of green compact to 800-820° C. with a heating rate of 6-7° C./min and holding at this temperature for 30 min that was resulted in densification of green compact to 4.42 g/cm³due to complete dehydrogenation and active shrinkage of compact containing both titanium and hydrogenated titanium components.
Then, heating of the cleaned and refined green compact was continued in vacuum of 10⁻⁴Torr at the rate of 5-10° C./min to the temperature 1350° C. followed by holding at this temperature for 2 hours to form a sintered dense compact, and finally, cooling the sintered compact was done to obtain a flat titanium plate.
The titanium plate was hot rolled to the thickness of 15 mm followed by vacuum annealing at 750° C. for 3 hours.
Measured contents of impurities in the final product were the following:
oxygen <0.16 wt. %,
hydrogen <0.005 wt. %,
chlorine <0.0015 wt. %,
magnesium <0.0048 wt. %,
sodium <10 ppm.
Standard specimens for mechanical testing were cut and machined from the titanium plate. Mechanical properties of the manufactured titanium plate were: ultimate tensile strength 558-575 MPa, yield strength 461-494 MPa, and elongation at break 21-23%. Due to low content of contaminants, the resulting titanium plate is weldable using both GTAW and GMAW arc welding technique.

Example 5

A powder blend of three types of base powders were used: (1) Crushed hydrogenated titanium sponge TG-110 grade of Zaporozhye Titanium & Magnesium Corp., Ukraine, (2) Titanium hydride TiH₂powder produced by a new “Non-Kroll” process combining reduction and distillation (ADMA hydrogenated powder), and (3) CP titanium powder manufactured by dehydration of TiH₂. All powders had particle size <100 microns, at the average particle size of 40 microns. Titanium hydride powder contained 3.5% of hydrogen.
These powders were mixed together at the weight ratio of hydrogenated titanium powder (crushed hydrogenated titanium sponge and titanium hydride) to CP titanium of 90% to 10%.
The obtained mixed powder was compacted at 640 MPa to a low density green compact of 3.15 g/cm³, which is significantly less than that of compacts produced only from CP titanium powder.
The green compact having the thickness 18 mm was heated to 250° C. at a slow heating rate of ˜7° C./min and held at this temperature for 60 min to release absorbed water from the powder. Then, heating was continued at the heating rate of ˜17° C./min to 550-570° C. in the atmosphere of emitted hydrogen and held at this temperature for 30 min to form β-phase titanium and release reaction water from the powder.
Almost complete reduction of surface oxides of the powder by emitted atomic hydrogen was carried out by further heating the green compact to 650° C. and holding at this temperature for 60 min when the green compact still had open porosity structure. At the same time, β-phase titanium was transformed to α-phase titanium.
Further, the diffusion-controlled chemical homogenization was carried out by heating of green compact to 840° C. with the rate of 7° C./min and holding at this temperature for 30 min that resulted in densification of the green compact to 4.43 g/cm³due to complete dehydrogenation and active shrinkage of the compact containing both CP titanium powder and hydrogenated titanium component.
Then, heating of the cleaned and refined green compact was continued in vacuum of 10⁻⁴Torr at the rate of 5-10° C./min to the temperature 1250° C. followed by holding at this temperature for 4 hours form a sintered dense compact, and finally, cooling the sintered compact was done to obtain a flat titanium plate.
The titanium plate was hot rolled to the thickness of 12 mm followed by vacuum annealing at 750° C. for 2 hours.
Measured contents of impurities in the final product were the following:
oxygen 0.158 wt. %,
hydrogen 0.0054 wt. %,
chlorine <0.001 wt. %,
magnesium 0.004 wt. %,
sodium <10 ppm.
Standard specimens for mechanical testing were cut and machined from the titanium plate. Mechanical properties of the manufactured titanium plate were: ultimate tensile strength 544-580 MPa, yield strength 449-467 MPa, and elongation at break 20-21%.

Example 6

A powder blend of four types of powder was used: (1) 20 wt. % of underseparated titanium powder containing 2.0% chlorine and 0.8% of magnesium and having particle size <100 μm, (2) 20 wt. % of underseparated and hydrogenated titanium powder containing 2% of hydrogen, (3) 20 wt. % of C.P. titanium powder, (4) 30 wt. % of titanium hydride TiH₂powder containing 3.4% of hydrogen, particle size <100 microns, and (5) 10 wt. % of the 60Al-40V master alloy powder having particle size <65 μm.
These powders are blended for 6 hours, and the obtained mixed powder was compacted at 800 MPa to a low density green compact of 3.51 g/cm³.
The green compact having a thickness of 20 mm was heated to 250° C. at slow heating rate ˜7° C./min and held at this temperature for 70 min to release absorbed water from the powder. Then, net-shaped green compacts were exposed at 350° C. for 60 min during heating in vacuum furnace for evacuation of chlorine and magnesium from the material.
Further, heating was continued at the heating rate of ˜16° C./min to 500-520° C. in the atmosphere of emitted hydrogen and held at this temperature for 30 min to form β-phase titanium and release reaction water from the powder.
Almost complete reduction of surface oxides of green compact particles by emitted atomic hydrogen was carried out by further heating the green compact to 630-650° C. and holding at this temperature for 40 min when the green compact still had open porosity structure. At the same time, β-phase titanium was transformed to α-phase titanium.
Further, the diffusion-controlled chemical homogenization was carried out by heating of green compact to 820-840° C. with the rate of 6-7° C./min and holding at this temperature for 30 min that was resulted in densification of green compact to 4.44 g/cm³due to complete dehydrogenation and active shrinkage of compact containing both titanium and hydrogenated titanium components.
Then, heating of the cleaned and refined green compact was continued in vacuum of 10⁻⁴Torr at the rate of 5-10° C./min to a temperature of 1300° C. followed by holding at this temperature for 2 hours to form a sintered dense compact, and finally, cooling the sintered compact was done to obtain a flat titanium plate.
The titanium plate was hot rolled to the thickness of 15 mm followed by vacuum annealing at 750° C. for 3 hours.
Measured contents of impurities in the final product were the following:
oxygen <0.15 wt. %,
hydrogen <0.005 wt. %,
chlorine <0.0015 wt. %,
magnesium <0.0044 wt. %,
sodium <10 ppm.
Standard specimens for mechanical testing were cut and machined from the titanium plate. Mechanical properties of the manufactured titanium plate were: ultimate tensile strength 968-1033 MPa, yield strength 881-904 MPa, and elongation at break 15-17%.
The invention have been thus explained and described by reference to certain specific embodiments and examples, it will be appreciated that these specific embodiments and examples are illustrative, rather than limiting of the appended claims.

Claims

1. A method for the manufacture of near-net shape titanium and titanium alloy articles from metal powders by sintering in the presence of atomic hydrogen comprising:

(a) forming a powder blend comprising mixing (1) Commercially Pure (C.P.) titanium powder, and (2) one or more of (i) one or more hydrogenated titanium powders containing around 3.4 to around 3.9 weight % of hydrogen, and (ii) one or more hydrogenated titanium powders containing around 0.2 to around 3.4 weight % of hydrogen,

(b) consolidating the powder blend by either compacting the powder blend using die pressing, direct powder rolling, cold isostatic pressing, impulse pressing, metal injection molding, other room temperature consolidation method, or combination thereof, at a pressure in the range of around 400 to around 960 MPa, or loose sintering, to provide a green compact having a density lower than that of a green compact formed from only C.P. titanium powder, such that the subsequent sintering of said green compacts is promoted by an increased hydrogen content retained in the green compact which provides emission of hydrogen and a high partial pressure during subsequent cleaning and sintering steps,

(c) heating the green compact to a temperature ranging from around 100° C. to around 250° C. at a heating rate around 15° C./min, thereby releasing absorbed water from the titanium powder, and holding the green compact at this temperature for a holding time ranging from around 10 to around 360 min, wherein the holding time and a thickness of the green compact are such that there is around 18 to around 24 min of holding time per every 6 mm of the thickness of the green compact,

(d) forming β-phase titanium and releasing emitted atomic hydrogen from the hydrogenated titanium by heating the green compact to a temperature of around 400 to around 600° C. in an atmosphere of hydrogen emitted by the hydrogenated titanium and holding the green compact at this temperature for around 5 to around 30 min thereby forming and releasing reaction water from the hydrogenated titanium powder,

(e) reducing surface oxides on particles of the titanium powder by contact with atomic hydrogen released by heating of the green compact to a temperature of around 600 to around 700° C. and holding at this temperature for a holding time of around 30 to around 60 min sufficient to transform β-phase titanium into α-phase titanium while preventing dissolution of oxygen in the metallic body of the titanium particles and simultaneously providing maximum cleaning of titanium powders before forming closed pores,

(f) diffusion-controlled chemical homogenizing of the green compact and densification of the green compact by heating to around 800 to around 850° C. at a heating rate of around 6 to around 8° C./min, followed by holding at this temperature for around 20 to around 40 min resulting in complete or partial dehydrogenation and more active shrinkage of titanium powder formed from the initial hydrogenated titanium powder to form a cleaned and refined compact,

(g) heating the cleaned and refined green compact in vacuum at a temperature in the range of around 1000 to around 1350° C., and holding the cleaned and refined green compact at such temperature for at least around 30 minutes, thereby sintering titanium to form a sintered dense compact, and

(h) cooling the sintered dense compact to form a sintered near-net shaped article.

2. The method according to claim 1, wherein the forming of the powder blend further comprises mixing a powder prepared from hydrogen-free underseparated titanium sponge with the other components of the powder blend.

3. The method according to claim 1, wherein the forming of the powder blend further comprises mixing a powder prepared from hydrogen-containing underseparated titanium sponge with the other components of the powder blend.

4. The method according to claim 1, wherein the forming of the powder blend further comprises mixing alloying metal powders selected from master alloy powders, alloy mixture of elemental powders, and pre-alloyed titanium alloy powders with the other components of the powder blend.

5. The method according to claim 1, wherein the powder blend only hydrogenated titanium powders containing around 3.4 to around 3.9 weight % hydrogen, and one or more hydrogenated titanium powders containing around 0.2 to around 3.4 weight % hydrogen.

6. The method according to claim 1, further comprising subjecting the sintered near-net shape article to hot processing selected from the group consisting of forging, rolling, hot isostatic pressing (HIP), extrusion, and combinations of these, followed by additional decreasing of the content of residual hydrogen to below around 150 ppm by vacuum annealing at temperatures from around 700 to around 750° C.

7. The method according to claim 1, wherein the forming of the β-phase titanium and the releasing of atomic hydrogen from hydrogenated titanium comprises heating the green compact to a temperature ranging from around 250° C. to around 600° C. in the atmosphere of the emitted hydrogen at a heating rate 15° C./min, whereby the chemical reduction and cleaning effect of hydrogen is enhanced and reaction water from the hydrogenated titanium and released.

8. The method according to claim 1, further comprising thermal cycling in the temperature range of around 800 to around 900° C., whereby multiple initiation of alpha-beta-alpha phase transitions in titanium green compact is carried out and crystal defects for additional activation of sintering titanium are accumulated.

9. The method according to claim 1, wherein the consolidating of the powder blend comprises loose sintering without compacting.

10. (canceled)

11. The method according to claim 1, wherein the green compact produced by consolidation and the sintered dense compact each have different cross-sections that vary in density.

12. The method according to claim 1, wherein the powder blend comprises hydrogenated titanium powders in an amount of around 10 to around 90 wt. % of the powder blend.

13. The method according to claim 1, wherein the sintered near-net shape article contains less than 0.2 wt. % of oxygen, less than 0.006 wt. % of hydrogen, less than 0.05 wt. % of chlorine, less than 0.05 wt. % of magnesium, less than 10 ppm of sodium, and has a final porosity less than around 1.5% at pore sizes less than 20 microns.

14. The method according to claim 1, wherein the forming of β-phase titanium and releasing hydrogen from hydrogenated titanium powder comprises heating at a rate that is faster than the heating rate used in the heating of the green compact.

15. The method according to claim 14, wherein said faster heating rate is ≧20° C./min.

16. A method for the manufacture of near-net shape titanium and titanium alloy articles from metal powders by sintering in the presence of atomic hydrogen comprising:

(a) forming a powder blend by mixing two or more hydrogenated titanium powders containing around 0.2 to around 3.9 weight % of hydrogen,

(c) heating the green compact to a temperature ranging from around 100° C. to around 250° C. at a heating rate 15° C./min, thereby releasing absorbed water from the titanium powder, and holding the green compact at this temperature for a holding time ranging from around 10 to around 360 min, wherein the holding time and a thickness of the green compact are such that there is around 18 to around 24 min of holding time per every 6 mm of the thickness of the green compact,

(d) forming β-phase titanium and releasing atomic hydrogen from titanium hydride by heating the green compact to a temperature of around 400 to around 600° C. in an atmosphere of hydrogen emitted by the hydrogenated titanium and holding the green compact at this temperature for around 5 to around 30 min thereby forming and releasing reaction water from the hydrogenated titanium powder,

(f) diffusion-controlled chemical homogenizing of the green compact and densification of the green compact by heating to around 800 to around 850° C. at a heating rate of around 6 to around 8° C./min, followed by holding at this temperature for a holding time of around 30 to around 40 min resulting in complete or partial dehydrogenation and more active shrinkage of titanium powder formed from the initial hydrogenated titanium powder to form a cleaned and refined compact,

17. A method for the manufacture of near-net shape titanium and titanium alloy articles from metal powders by sintering in the presence of atomic hydrogen comprising:

(a) forming a powder blend comprising mixing (1) underseparated titanium powder, and (2) one or more of (i) one or more hydrogenated titanium powders containing around 3.4 to around 3.9 weight % of hydrogen, and (ii) one or more hydrogenated titanium powders containing around 0.2 to around 3.4 weight % of hydrogen,

(b) consolidating the powder blend by either compacting the powder blend using die pressing, direct powder rolling, cold isostatic pressing, impulse pressing, metal injection molding, other room temperature consolidation method, or combination thereof, at a pressure in the range of around 400 to around 960 MPa, or loose sintering, to provide a green compact having a density lower than that of a green compact formed from only Commercially Pure (C.P.) titanium powder, such that the subsequent sintering of said green compacts is promoted by an increased hydrogen content retained in the green compact which provides emission of hydrogen and a high partial pressure during subsequent cleaning and sintering steps,

(d) forming β-phase titanium and releasing atomic hydrogen from the hydrogenated titanium by heating the green compact to a temperature of around 400 to around 600° C. in an atmosphere of hydrogen emitted by the hydrogenated titanium and holding the green compact at this temperature for around 5 to around 30 min thereby forming and releasing reaction water from the hydrogenated titanium powder,

18. A sintered near-net shaped article formed by the method of claim 1.

19. A sintered near-net shaped article formed by the method of claim 16.

20. A sintered near-net shaped article formed by the method of claim 17.