innovative non-kroll process for hydrogenated titanium ... · products to a level suitable for...

Innovative Non-Kroll Process for Hydrogenated Titanium Powder Production

V.S.Moxson1, V.A.Duz1, G.I. Abakumov1, O.M.Ivasishin2,

C.Lavender3

1 ADMA Products, Inc., USA 2 Institute for Metal Physics, NAS of Ukraine 3 Pacific Northwest National Laboratory, USA

INSTITUTE FOR METAL PHYSICS

NATIONAL ACADEMY

OF SCIENCES OF UKRAINE

ADMA Products, Inc. Copyright ©2011


Powder Metallurgy (PM) approach is a viable

and promising route for cost-effective

fabrication of titanium alloys.

• Solid-State Powder Metallurgy is a mature

industry for other metals, such as stainless

steels, copper, brass and aluminum alloys

($25 billion total world market with >$5 billion

total U.S. market, versus only $5 million U.S.

domestic market for titanium in 2010).

• The limitations in manufacturing the titanium

powder metallurgy components were mostly

associated with a lack of low cost and good

quality titanium powder


Issues that have hindered titanium powder

metallurgy industry development

1. Chemistry issues:

• High impurities content – the need to remove

Chlorine, Magnesium, Sodium (only melting can

remove impurities)

• High oxygen content (related to high surface area of

titanium powders) - 0.20% O max per AMS 4928L

2. Properties issues:

• Inferior Low Cycle Fatigue and fatigue related

properties, inferior fracture toughness

• “Weld-ability” Issues


• ADMA Reduces Raw Material Cost Low cost Innovative Ti powder production technology (U.S. Patent 6,638,336 B1)

• ADMA Reduces High Processing Cost Blended Elemental Powder Metallurgy Approach (US Patent 7,993,577 B2)

Cost-Effective

TiH2 Powder

Simple

Consolidation Sinter

Finished Products

with

Excellent Mechanical

Properties

Low Cost Ti Alloy Components through Solid State

Powder Metallurgy Processing

Titanium Powder Production Modified Kroll Process

(U.S. Patent No. 6,638,336 B1)

Hydrogenated titanium powders are produced in two basic stages:

• titanium tetrachloride reduction with magnesium;

• titanium sponge purification by vacuum distillation and

hydrogenation;

Hydrogenated powder Hydrogenated

Ti sponge

(Modified Kroll process)

Hydrogenated Ti sponge crushing

MgCl2 TiCl4

Reduction Vacuum distillation & Hydrogenation

TiCl4 + 2Mg = Ti + 2MgCl2

Ti sponge block

(Kroll process)

Hydrogen Vacuum

Argon

TiH2

Ti + H2 = TiH2


Use of hydrogen considerably reduces vacuum distillation time, increases furnace output,

reduces electric power consumption, labor input, and reduces production costs

Non-Kroll Process (U.S. Patent Application No. 12/655,937)

Hydrogenated titanium powders are produced in two basic stages:

1. Titanium tetrachloride reduction with magnesium and hydrogen;

• hydrogen intensifies the reduction process and makes it shorter;

• Hydrogen increases magnesium utilization

• Hydrogen increases efficiency of vacuum distillation process

2. titanium sponge purification by vacuum distillation and

hydrogenation;

Hydrogenated Ti sponge

(Non-Koll process)

TiCl4

Mg + H2 Reduction Vacuum distillation &

Hydrogenation

Hydrogen Vacuum

Argon

TiH2

Ti + H2 = TiH2

MgCl2


TiCl4 + [H2]+ Mg TiHx + MgCl2

[H2]

Advantages of ADMA TiH2 Powder Production

Process Over Conventional Technology Use of hydrogen considerably reduces reduction time and vacuum

distillation time (as compared to the conventional Kroll Process)

increases furnace output, reduces electric power consumption

lower labor input

lower production costs

reduces titanium loss


Use of hydrogen considerably

reduces vacuum distillation

time


simplify the comminution

process (boring, shearing,

crushing)


reduces reduction time


Hydrogenated Ti Powder Production

Lab-scale unit for hydrogenated Ti powder production

at ADMA Products, Inc.

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

* Average from 11 production runs

Impurities on TiH2 Powder Surface (photo-electron spectroscopy)


Mass Spectroscopy of Gases Emitted from the Compact

(Room Temperature)

Mass number

H2

H2O

CO + N2

CO2

C3H4 + Ar

HCl

CH4 + O

OH


Mass Spectroscopy of Gases Emitted (450oC)

Mass number

H2 H2O

CO + N2

CO2 C3H4 + Ar

HCl

CH4 + O

OH


Emission of gases in the temperature range of hydrogen emission

resulting from the reaction of hydrogen with impurities

Chlorine

MgCl2 + 2H = 2HCl + Mg

Cl2 + H2 = 2HCl


Possibility to reduce the chlorine content in sintered

products to a level suitable for welding without melting

0 200 400 600 800

100

120

140

160

180

200

220

240

H2O (TiH

2)

H2 in

ten

sity

, arb

. un

its

H2O

inte

nsi

ty, a

rb. u

nits

Temperature, oC

H2

H2O (Ti)

0

5000

10000

15000

20000


Oxygen

Desorption of moisture

Reduction of surface oxide (TiO2)

by atomic hydrogen

Reduction of surface oxide by atomic hydrogen decreases the oxygen

content in P/M products to the level of AMS specifications


Advantages of Titanium Hydride Powder

Lower cost

Lower flammability

Higher resistance to oxidation

Lower impurity content (Cl, O, Mg, C) in sintered

products

Activated surface due to removing of surface oxides


High Density (98-99%) Blended Elemental

P/M Titanium Alloy Parts

Employment of TiH2 instead of Ti powder

allows attainment of 99% density and

mechanical properties equivalent to those of

ingot materials with most cost-effective

room temperature compaction and sinter

approach (without HIP)

Ti, Alloying Elements

Powders

Powder Blend

BE Compact

(NNS)

Component

HIP

Low Porous Component

Blending

Compaction

Sintering

Specific mechanism of compaction

optimized green porosity

Shear type phase transformation TiH2Ti

( or ) high density of crystal lattice

defects

Reduction of surface oxides by atomic

hydrogen evolving from titanium

Faster sintering,

higher sintered

density, lower

impurity content

TiH2

Eventually the hydrogen is completely removed

from material during sintering

Processing Steps for the B/E Ti Alloy Parts

Production

Powder

Rolling Flat (foil, sheet, plate)

Round (bar, rod)

Post-Processing Outside vendors ADMA Titanium P/ M “in house” Processes

Die Press

Direct Powder

Rolling

Cold Isostatic

Pressing

Vacuum

Sintering

Finished

product

Forging

Extrusion

Flowform

HIP

Vacuum

Sintering


Titanium and Titanium Alloys Components

Die-press/Sinter

Material Density, % YS, ksi UTS, ksi El. % RA, %

CP-Ti, as-sintered 98.5 63 74 26 37

Ti-6Al-4V, as -sintered 99.0 126 142 12 30

Ti-6Al-4V, STMB348 Grade 5 - 120 130 10 25

Ti-5553, sintered + heat treated 98.5 174 189 6,8 10,3

Ti-5553, BMS7-360 specification - 170 180 5 -

Ti-1023, sintered + heat treated 98.0 161 181 5,2 11,0

Ti-1023, AMS 4984 specification - 160 173 4 -

Die Pressing

Sintering


Direct Powder Rolling of Ti Alloy Foil, Sheet, and

Plate at ADMA



Porous Plates for High Efficient, on-Line Membrane

Air Dehumidifier

DOE/ADMA/PNNL/TEES TAMY

Reduce HVAC energy consumption

by removing moisture without

water condensation:

> 50% more energy-efficient

than conventional air conditioning

$4.3M three year ARPA-E Program


Low-oxygen P/M Ti-6Al-4V CIP/Sinter Pre-forms

Cold Isostatic Pressing

Sintering

Rolling Forging

Extrusion

Hydrogen content is reduced to safe level 20-60 ppm

even at production of components with large cross-

sections


P/M Ti-6Al-4V Armor Plates

CIP/Sinter/Hot Rolling

P/M Ti-6Al-4V Ultimate Tensile Strength, ksi

Yield Strength, ksi

Elongation,

%

Reduction of Area, %

0.75” thick 139 – 147 126 – 136 16 – 17 32 – 36

0.50” thick 142 – 151 129 – 132 15 – 18 33 – 39

ASTM 130 120 10 25

Room Temperature Tensile Properties

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

CIP/Sinter 5.88 4.23 0.076 0.010 0.008 0.158 0.0054 Bal. <0.10 <0.40

ASTM/AMS 5.5 – 6.75 3.5-4.5 0.30 0.080 0.050 0.20 0.0125 Bal. <0.10 <0.40


Sintering

Rolling


P/M Ti-6Al-4V Commander’s Hatch

CIP/Sinter/Forging

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

CIP/Sinter 6.16 4.21 0.080 0.009 0.021 0.179 0.0018 Bal. <0.10 <0.40

ASTM/AMS 5.5 – 6.75 3.5-4.5 0.30 0.080 0.050 0.20 0.0125 Bal. <0.10 <0.40

Room Temperature Tensile Properties P/M Ti-6Al-4V Ultimate Tensile

Strength, ksi Yield Strength,

ksi Elongation,

%

Reduction of Area, %

1.375” thick 144 – 149 132 – 136 14.0 – 15.5 34 – 38

ASTM 130 120 10 25


Sintering

Forging


Ti-6Al-4V UTS (ksi) 0.2% YS (ksi) % El. % RA

ADMA P/M 156 - 157 134 – 135 12 - 13 28

Ingot Based 140 - 142 125 – 127 12 27

Extrusion Process for BE P/M Ti-6AL-4V Alloy

Extrusions up to 27-foot length were fabricated and analyzed at front, mid-length, and back and found to be uniform with respect to oxygen content & microstructure. Longer and larger cross-section fabrication can be performed.

36’-Long

Extrusions Cut-up

for Shipping and

Laboratory

Characterization

RTI, International Metals, Inc.

Plymouth Engineered Shapes, Inc.

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

CIP/Sinter 6.2-6.4 4.04-4.30 0.15 0.01 0.01 0.26 0.007-0.050 Bal. <0.10 <0.40

ASTM B348 5.5-6.75 3.5-4.5 0.40 0.08 0.05 0.20 0.0150 Bal <0.10 <0.40


Powder Metallurgy Ti alloy Round Bars


Sintering

Extrusion Rolling

Rotary Forging

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

ADMA P/M 6.16 4.32 0.08 0.018 0.029 0.19 0.006 Bal. <0.10 <0.40

Ingot based 6.34 4.05 0.16 0.020 0.007 0.20 0.007 Bal <0.10 <0.40

ASTM B348 5.5-6.75 3.5-4.5 0.40 0.08 0.05 0.20 0.0150 Bal <0.10 <0.40

Ti-6Al-4V Ultimate

Strength, ksi

Yield Strength,

ksi

Elongation, % Reduction of

Area, %

ADMA P/M 148 – 152 143 – 145 19.8 - 22.8 28.2 - 28.3

Ingot Based 144 - 150 140 – 144 19.4 - 21.1 26.9 - 27.6

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

Room Temperature Tensile Properties


CONCLUSIONS

1. Innovative low cost magnesium reduction process for manufacturing the

hydrogenated titanium powder was developed

2. The cost-effective Blended Elemental (BE) PM technology has been used

for manufacturing the nearly fully dense titanium alloys by room

temperature consolidation (die-pressing, CIP, direct powder rolling)

followed by sintering.

3. High temperature post processing such as rolling, forging, extrusion

were used to produce the various components from P/M C.P. Ti and Ti-

6Al-4V alloy and the alloys produced by these post-processing

operations exhibited the mechanical properties at least equal to those

obtained on the identical alloys produced by conventional ingot

metallurgy.


Pilot Scale Unit for Manufacturing of Hydrogenated Titanium Powder (660 lbs/cycle)

ADMA received a 2010 Defense Appropriations Act Congressional award of $1.2 M to increase production

of Hydrogenated Titanium Powder

The first funds under the FY 2010 Congressional award became available in June 2011

Within one year of “breaking ground” an ADMA “pilot” scale production facility will begin producing of

hydrogenated titanium powder (660 lbs per cycle)


Thank You for Your Attention

INSTITUTE FOR METAL PHYSICS

NATIONAL ACADEMY

OF SCIENCES OF UKRAINE

innovative non-kroll process for hydrogenated titanium ... · products to a level suitable for...

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