ADMA Process for Hydrogenated Titanium Powder Productionc.ymcdn.com/sites/ · ADMA Process for Hydrogenated Titanium Powder Production ... ADMA Process for Hydrogenated Titanium Powder

Vladimir Duz, Director, R&D October 6-9, 2013 • Caesars Palace, Las Vegas, Nevada, USA

ADMA Process for Hydrogenated Titanium Powder Production

ADMATALTM

Vladimir Duz, Vladimir S. Moxson,

Andrei G. Klevtsov, Viktor Sukhoplyuyev

ADMA Products, Inc., USA

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Conventional Processes of Titanium Metal Manufacturing

1910 - Sodium Reduction (Hunter Process)

4Na (liquid) + TiCl4 (gas) = 4NaCl (liquid) + Ti (solid) (700-800oC)

High price (sodium, high energy consumption of the electrolysis of NaCl)

Honeywell/UTAH (high purity targets);

1938 - Magnesium Reduction (Kroll Process)

2Mg (liquid) + TiCl4 (gas) = 2MgCl2 (liquid) + Ti (solid) (800-850oC)

The Kroll Process displaced the Hunter Process and continues to be the dominant technology for the production of titanium metal (TIMET, ATI, and others)

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Conventional Technology (Kroll Process)

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Kroll’s Process: TiCl4 (gas) + 2Mg (liquid) Ti (sponge, solid) + 2MgCl2 (liquid)

The key challenge of Kroll’s process is to remove MgCl2 entrained in the Ti sponge The sponge is very strong and cannot be easily crushed to “release” the entrained MgCl2 and aid in its removal. The main drawback of Kroll’s process is that the cycle time, i.e. purification of Ti sponge by vacuum distillation can exceed 4-5 days.

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1960s - Metal hydride reduction (MHR) – attempts to use hydrogen to improve efficiency of reduction process (Polema-Tulachermet/ADMA)

TiO2 (liquid) + 2CaH2 (gas) = Ti (solid) + 2CaO (liquid) + H2 (gas) (1100-1200oC)

• This method of the titanium powder production does not require titanium tetrachloride (TiCl4) to be produced.

• As a result the powders contain low amount of chloride. • The pre-alloyed titanium powder can be produced

Metal Titanium Powder Manufacturing

Ti Fe Ni C N O H Ca Si Cl

base 0.11 0.07 0.03 0.06 0.19 0.34 0.04 0.05 0.004

Ti Al V Ca N O H Cl

base 4.65 3.8 0.06 0.06 0.20 0.3 0.003

Chemical composition of CP Titanium powder (wt.%)

Chemical composition of pre-alloyed Ti-6Al-4V powder (wt.%)

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P/M Titanium alloy parts manufactured in millions of pieces by ADMA Products Inc. from Metal Hydride Reduced powder using (late 1980s)

Failed because of HIGH COST • Calcium consumption is the double of Magnesium consumption • High cost of Calcium

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Extensive review of various routes of titanium powder production indicates that magnesium-hydrogen reduction followed by hydrogenation may be the most cost effective approach to produce the high quality titanium powder.

ADMA Low Cost Innovative Ti powder Production Technology (U.S. Patent , 8,007, 562 B2)

The powder production technology developed by ADMA is based on breaking up the ductile titanium sponge mass upon its saturation with hydrogen, and converting it into extremely brittle titanium hydride powder (TiH2) .

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U.S. Patent No. 8,007, 562 B2

Hydrogenated Titanium powder

Hydrogenated Ti sponge

MgCl2 TiCl4

Magnesium-Hydrogen Reduction of TiCl4

Vacuum distillation & Hydrogenation

Hydrogen Vacuum

Argon

Ti sponge block (Kroll

process)

TiH2

TiCl4 (gas) + (1-2)H2 (gas) + (1-2)Mg (liquid) = TiH2 (sponge, solid) + (1-2)MgCl2 (liquid) + (0-2)HCl (gas)

ADMA’s proposed process can transform the Ti production because it overcomes the technical challenges of the Kroll’s process by partially replacing molten Mg with H2 gas as a reducing agent to produce TiH2 instead of Ti

H2

Mg

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Advantages of ADMA TiH2 Powder Production Process Over Conventional Technology

• Use of hydrogen can shorten the time for removal of MgCl2 by vacuum distillation process by 80%

• Use of hydrogen completely eliminates the comminution process (cutting, boring, shearing, crushing) of Ti sponge block

• Use of hydrogen reduces reduction time and increases Mg utilization

Cost of ADMA TiH2 powder is considerably lower than cost of conventional Ti sponge

Hydrogenated powder Hydrogenated

Ti sponge Hydrogenated Ti sponge crushing

MgCl2 TiCl4 Hydrogen Vacuum Argon

TiH2

Ti sponge block (Kroll

process)

• TiH2 sponge mass can be ground to powder in same retort, transported and packed under argon or vacuum

H2

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U.S. Patent No. 8,388,727 B2

Manufacturing of titanium hydride powder using titanium slag or synthetic rutile as raw material, while hydrogen, titanium tetrachloride, titanium trichloride, titanium dichloride, and hydrogen chloride are participate as intermediate reactor products.

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Advantages of ADMA Process for Hydrogenated Titanium Powder Production

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U.S. Patent No. 8,388,727 B2

• Titanium slag or synthetic rutile can be used as raw materials

• Decreased consumption of magnesium (use of titanium trichloride (TiCl3) and titanium dichloride (TiCl2) instead of titanium tetrachloride (TiCl4)).

• Improved ecology (use of HCl for chlorination instead of Cl2)

• Process can be continuous or semi-continuous depending on starting raw material

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ADMA Titanium Hydride Powder Production

Lab-scale unit for hydrogenated Ti powder production at ADMA Products, Inc. (Hudson, OH)

In 2010 ADMA received $1.4M Congressional award under the 2009 Defense Appropriations Act to begin production of hydrogenated titanium powder in the USA.

Material Fraction of total mass of specified impurities, %

Fe N C O H Ti

ADMA TiH2 powder 0.03 – 0.16 0.030 0.010 0.063 3.80-3.85 Bal

ASTM B348 Grade 2 0.300 0.030 0.080 0.250 0.015 Bal

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ADMA Titanium Hydride Powder Production Pilot Scale Unit (Twinsburg, OH )

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The Pilot Scale Unit will produce at least 240,000 lbs of ADMA TiH2 powder per year

This powder will be used for sales expansion and production of various titanium alloy components for critical applications, including aviation components.

In 2012 ADMA received a Defense Appropriations Act Congressional award of $1.2 M to increase production of Hydrogenated Titanium Powder

Vladimir Duz, Director, R&D October 6-9, 2013 • Caesars Palace, Las Vegas, Nevada, USA 13

Weapon Components Developments CIP/Sinter/Rotary Forging

0.875” Dia x 12ft long Ti-6Al-4V round bars

P/M Ti-6Al-4V UTS, ksi YS, ksi Elongation, % RA,%

ADMA TiH2 Powder 154 – 155 141 – 142 15.8 – 16.5 38 - 40

AMS 4928R 135 Min. 125 Min. 10 Min.

Room Temperature Tensile Properties

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ADMATALTM

Ti-6Al-4V Al V Fe C N O H Ti Other, Each Other, Total

ADMA TiH2 5.83 3.72 0.29 0.017 0.029 0.189 0.012 Bal. <0.10 <0.40

ASTM B348 5.5-6.75 3.5-4.5 0.40 0.08 0.05 0.20 0.015 Bal <0.10 <0.40

Chemical analysis of P/M Ti-6Al-4V CIP/Sinter/Rotary forged bars produced from ADMA TiH2 powder


Ti-6Al-4V Extruded shapes

Ti Alloy Components Manufactured Using the ADMA Hydrogenated Titanium Powder

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ADMATALTM

CP Ti tubes

Fasteners (washers, hexhuts etc.

Ti alloy billets, plates and bars

Vladimir Duz, Director, R&D October 6-9, 2013 • Caesars Palace, Las Vegas, Nevada, USA 15

ADMA Business Approach for High Scale Manufacturing of Low Cost Titanium and Titanium Alloy Components

• Phase I. Laboratory Scale Titanium Hydride Powder Production - completed. Objective - Production of hydrogenated titanium powders and demonstration of superior properties of Ti and Ti alloys produced from these powders by Low cost Solid State Processes;

• Phase II. Pilot Scale Hydrogenated Titanium Powder Production – completed. Design and manufacturing of larger scale powder production system (over 600 lb/cycle), manufacturing of various titanium alloy components for critical applications, getting the industry approval for the new powder and processes, and obtaining the orders from the aircraft companies;

• Phase III. Pilot Plant (2014-2015) Objective - achieve an annual capacity of 4mln lbs of TiH2 powder, and expand market penetration;

• Phase IV. Full scale Hydrogenated Titanium Powder production plant (44mln lbs) and market penetration to achieve the overall objectives of the Program – (2016-2017, Sheffield Village, OH)

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CONCLUSIONS 1. Innovative process for manufacturing the hydrogenated titanium powder

(TiH2) has been developed

2. Laboratory scale unit (10 lbs/run) for TiH2 powder production was built and installed at ADMA facility (Hudson, Ohio)

3. Pilot scale unit with a capacity of 660 lbs/run for TiH2 powder production has been built and installed at ADMA facility (Twinsburg, OH).

4. Chemistry of TiH2 powder produced at ADMA Products, Inc. meets the AMS, ASTM and Military standards requirements

5. Properties of Ti alloy parts manufactured from ADMA TiH2 powder by low-cost Blended Elemental Powder Metallurgy approach meet the requirements of AMS, ASTM and Military standards.

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ADMA Process for Hydrogenated Titanium Powder Productionc.ymcdn.com/sites/ · ADMA Process for Hydrogenated Titanium Powder Production ... ADMA Process for Hydrogenated Titanium Powder