ADMA Process for Hydrogenated Titanium Powder Production ADMATAL TM

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1 ADMA Process for Hydrogenated Titanium Powder Production ADMATAL TM Vladimir Duz, Vladimir S. Moxson, Andrei G. Klevtsov, Viktor Sukhoplyuyev ADMA Products, Inc., USA 1

2 Conventional Processes of Titanium Metal Manufacturing Sodium Reduction (Hunter Process) 4Na (liquid) + TiCl 4 (gas) = 4NaCl (liquid) + Ti (solid) ( o C) High price (sodium, high energy consumption of the electrolysis of NaCl) Honeywell/UTAH (high purity targets); Magnesium Reduction (Kroll Process) 2Mg (liquid) + TiCl 4 (gas) = 2MgCl 2 (liquid) + Ti (solid) ( o C) The Kroll Process displaced the Hunter Process and continues to be the dominant technology for the production of titanium metal (TIMET, ATI, and others) 2

3 Conventional Technology (Kroll Process) Kroll s Process: TiCl 4 (gas) + 2Mg (liquid) Ti (sponge, solid) + 2MgCl 2 (liquid) The key challenge of Kroll s process is to remove MgCl 2 entrained in the Ti sponge The sponge is very strong and cannot be easily crushed to release the entrained MgCl 2 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. 3 3

4 Metal Titanium Powder Manufacturing 1960s - Metal hydride reduction (MHR) attempts to use hydrogen to improve efficiency of reduction process (Polema-Tulachermet/ADMA) TiO 2 (liquid) + 2CaH 2 (gas) = Ti (solid) + 2CaO (liquid) + H 2 (gas) ( o C) This method of the titanium powder production does not require titanium tetrachloride (TiCl 4 ) to be produced. As a result the powders contain low amount of chloride. The pre-alloyed titanium powder can be produced Chemical composition of CP Titanium powder (wt.%) Ti Fe Ni C N O H Ca Si Cl base Chemical composition of pre-alloyed Ti-6Al-4V powder (wt.%) Ti Al V Ca N O H Cl base

5 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 5

6 ADMA Low Cost Innovative Ti powder Production Technology (U.S. Patent, 8,007, 562 B2) 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. 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 (TiH 2 ). 6

7 U.S. Patent No. 8,007, 562 B2 ADMA Process for Hydrogenated Titanium Powder Production 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 H 2 gas as a reducing agent to produce TiH 2 instead of Ti TiCl 4 (gas) + (1-2)H 2 (gas) + (1-2)Mg (liquid) = TiH 2 (sponge, solid) + (1-2)MgCl 2 (liquid) + (0-2)HCl (gas) Ti sponge block (Kroll process) H 2 MgCl 2 TiCl 4 Mg Vacuum Hydrogen Hydrogenated Ti sponge Argon TiH 2 Hydrogenated Titanium powder Magnesium-Hydrogen Reduction of TiCl 4 Vacuum distillation & Hydrogenation 7 7

8 Advantages of ADMA TiH 2 Powder Production Process Over Conventional Technology Ti sponge block (Kroll process) Hydrogenated Ti sponge MgCl 2 H 2 TiCl 4 Vacuum Hydrogen Argon TiH 2 Hydrogenated Ti sponge crushing Hydrogenated powder Use of hydrogen reduces reduction time and increases Mg utilization Use of hydrogen can shorten the time for removal of MgCl 2 by vacuum distillation process by 80% Use of hydrogen completely eliminates the comminution process (cutting, boring, shearing, crushing) of Ti sponge block TiH 2 sponge mass can be ground to powder in same retort, transported and packed under argon or vacuum Cost of ADMA TiH 2 powder is considerably lower than cost of conventional Ti sponge 8

9 U.S. Patent No. 8,388,727 B2 ADMA Process for Hydrogenated Titanium Powder Production 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. 9 9

10 U.S. Patent No. 8,388,727 B2 Advantages of ADMA Process for Hydrogenated Titanium Powder Production Titanium slag or synthetic rutile can be used as raw materials Decreased consumption of magnesium (use of titanium trichloride (TiCl 3 ) and titanium dichloride (TiCl 2 ) instead of titanium tetrachloride (TiCl 4 )). Improved ecology (use of HCl for chlorination instead of Cl 2 ) Process can be continuous or semi-continuous depending on starting raw material 10 10

11 ADMA Titanium Hydride Powder Production In 2010 ADMA received $1.4M Congressional award under the 2009 Defense Appropriations Act to begin production of hydrogenated titanium powder in the USA. Lab-scale unit for hydrogenated Ti powder production at ADMA Products, Inc. (Hudson, OH) Material Fraction of total mass of specified impurities, % Fe N C O H Ti ADMA TiH 2 powder Bal ASTM B348 Grade Bal 11

12 ADMA Titanium Hydride Powder Production Pilot Scale Unit (Twinsburg, OH ) In 2012 ADMA received a Defense Appropriations Act Congressional award of $1.2 M to increase production of Hydrogenated Titanium Powder The Pilot Scale Unit will produce at least 240,000 lbs of ADMA TiH 2 powder per year This powder will be used for sales expansion and production of various titanium alloy components for critical applications, including aviation components. 12

13 Weapon Components Developments CIP/Sinter/Rotary Forging ADMATAL TM Dia x 12ft long Ti-6Al-4V round bars Chemical analysis of P/M Ti-6Al-4V CIP/Sinter/Rotary forged bars produced from ADMA TiH 2 powder Ti-6Al-4V Al V Fe C N O H Ti Other, Each Other, Total ADMA TiH Bal. <0.10 <0.40 ASTM B Bal <0.10 <0.40 Room Temperature Tensile Properties P/M Ti-6Al-4V UTS, ksi YS, ksi Elongation, % RA,% ADMA TiH 2 Powder AMS 4928R 135 Min. 125 Min. 10 Min

14 ADMATAL TM Ti Alloy Components Manufactured Using the ADMA Hydrogenated Titanium Powder Ti-6Al-4V Extruded shapes CP Ti tubes Fasteners (washers, hexhuts etc. Ti alloy billets, plates and bars 14

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 ( ) Objective - achieve an annual capacity of 4mln lbs of TiH 2 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 ( , Sheffield Village, OH) 15 15

16 CONCLUSIONS 1. Innovative process for manufacturing the hydrogenated titanium powder (TiH 2 ) has been developed 2. Laboratory scale unit (10 lbs/run) for TiH 2 powder production was built and installed at ADMA facility (Hudson, Ohio) 3. Pilot scale unit with a capacity of 660 lbs/run for TiH 2 powder production has been built and installed at ADMA facility (Twinsburg, OH). 4. Chemistry of TiH 2 powder produced at ADMA Products, Inc. meets the AMS, ASTM and Military standards requirements 5. Properties of Ti alloy parts manufactured from ADMA TiH 2 powder by lowcost Blended Elemental Powder Metallurgy approach meet the requirements of AMS, ASTM and Military standards. 16