powder metallurgy of titanium · powder metallurgy of titanium vlad a. duz1, v. s. moxson1 orest m....
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Powder Metallurgy of Titanium Vlad A. Duz1, V. S. Moxson1
Orest M. Ivasishin2
1 ADMA Products, Inc, 1890 Georgetown Road, Hudson, Ohio 44236, USA2 National Academy of Science of Ukraine, 36 Vernadsky Str. Kiev 03142, Ukraine
TITANIUM 2009September 13-16, 2009
Waikoloa, Hawaii
Motivation for Powder Metallurgy Approach to Produce Titanium and Titanium Alloy
Components
Titanium alloys are attractive materials for many structural applications due to:
‐ high strength
‐ low density
‐ good corrosion resistance
BUT: high cost restricts their applicationBUT: high cost restricts their application
The main trend in titanium material science is to expand application of titanium alloys by development of new technologies that provide significant cost reduction
Why Does Titanium Presently Cost So Much?
FINISHED SHEET
CASTING
ANNEAL
ROLL
ANNEAL
RE-ROLL
ANNEAL
SPONGE
ETC.
TiCl4 reduction
EB or VA melting
High extracting costsHigh extracting costs• strong bonding between titanium
and oxygen;
• requirements to get relatively low levels of other elements;
High processing costsHigh processing costs• high temperature processing
requires conditioning prior to further fabrication (surface regions contaminated at the processing temperatures, and surface cracks, both of which must be removed);
FORGINGMACHINING
EXTRUSION etc.
INGOT
•• Reducing High Extracting CostsReducing High Extracting CostsInnovative Ti powder production technologiesInnovative Ti powder production technologies
Achieving Much Lower Cost
•• Reducing High Processing CostReducing High Processing CostBlended Elemental Powder Metallurgy ApproachBlended Elemental Powder Metallurgy Approach
Cost-Effective
Ti PowderSimple
Consolidation SinterFinished Products
with Good Mechanical
Properties
Block crushing Sponge hydrogenation
Hydrogenated sponge crushing
Powder dehydrogenation
H D H P r o c e s s
Titanium Powder Production
Ti sponge block
(Kroll process)
Hydrogenated Ti sponge block
(Modified Kroll process)
Hydrogenated Ti sponge block crushing
Titanium Powder ProductionADMA Process
HydrogenVacuum
Argon
MgCl2TiCl4
(U.S. Patent No. 6,638,336 B1)(U.S. Patent No. 6,638,336 B1)
Reduction
Vacuum distillation
Hydrogenation
Ti sponge block
(Kroll process)
Hydrogenated Ti sponge block
(Modified Kroll process)
vs
≈
≈
ADMA Process vs Kroll Process
High-Dense (98-99%) Blended Elemental P/M Titanium Alloy Parts
Blends based on Ti powder: post-sintering working operations (HIP or hot deformation) are necessary
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 press-and-sinter approach (without HIP)
Ti, Alloying ElementsPowders
Powder Blend
BE Compact(NNS)
ComponentComponent
HIPHIP
Low Porous Component
BlendingBlending
CompactionCompaction
SinteringSintering
IncreaseIncreasein costin cost
• Specific mechanism of compaction → optimized green porosity
• Shear type phase transformation TiH2→Ti (β or α) → high density of crystal lattice defects
• Surface self reducing by atomic hydrogen
Faster sintering, higher sintered density, lower impurity content
TiH2
Influence of Compaction Pressure
Density: To attain sufficient sintered density compaction pressure value is not critical parameter for titanium hydride powder contrary to titanium powder.
This unique feature of the titanium hydride approach is attributed to compaction mechanism of low strength and brittle hydride particles.
300 400 500 600 700 800 900 100090
92
94
96
98
100
TiH2
Rel
ativ
e de
nsity
,%
Compaction pressure, MPa
99%
Ti
TiH2 – based compacts:-Fine crushed hydride fragments;-Fine pores independently on pressure applied
Pores are easy to heal upon sintering → high sintered density
Ti – based compacts:-Deformed ductile particles;-Relatively coarse pores (size depends on pressure applied);
Pores partially survived upon sintering
Residual Hydrogen
Hydrogen content is reduced to safe level 20-60 ppm even at production of components with large cross-sections
Ti-6Al-4V billet 8.50” x 12.0” x 52.0”725 lbs
Chemistry of Commercially Available Hydrogenated Titanium Powder
3.900.09-0.10
0.011-0.013
0.005-0.008
0.0410.054-0.073
0.054Powder-150 µm
3.850.06-0.08
0.0130.0080.0520.0620.05Hydrogenated Sponge
HONCNiFeCl
TiH2 spongeTiH2 powder (-100 mesh)
grinded at ADMA Products, Inc.
Powder metallurgy, especially blended elemental powder metallurgy (BEPM) approach at which alloying elements are added to titanium powder as elemental or master alloy powders enables significant reduction in the cost
Benefits of P/M Processing
• Fewer steps• No extensive secondary machining• Low buy-to-use ratio: scrap rate ≤ 2%• Direct alloying• Rapid manufacturing cycle• Uniform properties in longitudinal and transverse
directions• No texture developed• Integral processing of composites, laminates or
functionally gradient plate• More energy efficient
Processing Steps for the B/E Ti Alloy Parts Production
Powder Raw Material
RollingFlat (foil, sheet, plate)
Round (bar, rod)
Post-ProcessingOutside vendors
Titanium Powder Metallurgy ProcessesADMA’s captive
Die Press
Direct Powder Rolling
Cold IsostaticPressing
Vacuum Sintering
Finished product
Forging
Extrusion
Flowform
HIP
Die-Press + Sinter
Low-Cost Room Temperature Consolidation
P/M Titanium Alloy Components
Die Pressing
Sintering
Near Net ShapeNear Net Shape
Die Pressing + SinteringDie Pressing + Sintering
Bal3.50 –4.50
5.50 –6.75
0.300.40 max
0.0150.100.04ASTM B 817-98, Type I
Bal4.236.320.13-0.260.050.00140.0140.019P/M Ti-6Al-4V
TiVAlOFeHCN
Composition, %Material
Direct Powder Rolling + Sinter
Low-Cost Room Temperature Consolidation
Relative Cost Factors for Conventional and PM Processing of 1” Ti Alloy Plate
PM Ti Alloy PlateWrought Ti Alloy Plate
Raw materialcostManufacturingcost
67%33%
Delivery:Delivery: -- 5050--80 weeks80 weeks Delivery:Delivery: -- 4 weeks4 weeks
Production of Solid State Titanium Plate:Direct Powder Rolling
Comparison of the conventional sheet process with the direct powder rolling process for Ti-6Al-4V alloy
Conventional
INGOT
FINISHED SHEET
FORGING
ANNEAL
ROLL
ANNEAL
RE-ROLL
ANNEALETC.
ETC.
AlloyingPowders
Direct Powder RollingElementalTi Powder BLEND
FINISHED SHEET
POWDER ROLLING
RE-ROLL
SINTER
ANNEAL
Direct Powder Rolling of Ti Alloy Foil, Sheet, and Plate at ADMA
0.25” thick plate
0.010” thick Ti foil
Porous Titanium, Zirconium, Niobium, and Stainless Steel Plates
Life support systems for various applications
Cold Isostatic Pressing + Sinter
Low-Cost Room Temperature Consolidation
Titanium or Titanium AlloyCold Cold IsostaticIsostatic Pressing + SinteringPressing + Sintering
Cold Isostatic Pressing
Sintering
Post-processing
Forging
Extrusion
Flowform
HIPRollingFlat (foil, sheet, plate)
Round (bar, rod)
P/M Ti-6Al-4V billets produced by low cost CIP/Sinter/Forging approach
Cold Isostatic Pressing
Sintering
Forging
P/M Ti-6Al-4V Armor Plates from Hydrogenated Ti powder
0.75” thick 0.50” thick
Cold Isostatic Pressing
Sintering
Rolling
L – LongitudinalLT – Long transverseST – Short transverse
L
LT
ST
ASTM E8 ROOM TEMPERATURE TENSILE TEST
P/M Ti-6Al-4V Armor Plate from Hydrogenated Ti powder
Bal.0.010.295<0.0050.0300.00170.070<0.0010.0104.286.04
TiSiONaNHFeClCVAl
Elements, %
P/M Ti-6Al-4V
-
10
110,000
120,000
MIL-DTL-46077F
253634R. A., %
101515ELONGATION, %
120,000138,000138,0000.2% YS (PSI)
130,000154,500154,000UTS (PSI)
ASTM B265
Sample 2Sample 1
P/M Ti and Ti alloy Hollow Pre-forms for Tubes and Pipes
CIP
VacuumSintering
ADMA Hydrogenated Ti Powder
Flowform
Ti Grade 2 –ADMA’s Preforms Flowformed into 4” schedule 10 Pipe - 86% wall reduction during flowforming
1694,000110,000ADMA P/M Grade 2
Elongation,%
Yield Strength, psi
Ultimate Strength,psi
Material
Flowformed titanium pipe Preforms
• Titanium pipe system saves 178,000 lbs. per LPD compared to Cu-Ni pipe system Ship improving fuel efficiency and reducing life cycle maintenance cost of the pipe system
• It is estimated that a titanium piping system could save $17M per ship (LPD) considering life cycle savings, NAVSEA Carderock1
Courtesy Dynamic Flowform Inc.
Blended Elemental P/M Ti-6Al-4V Billets for Extrusion
CIP
VacuumSintering
Extrusion
Canless Extrusion Process Development for Blended-Elemental Powder-Based Titanium
Ti-6AL-4V Alloy
The Boeing Company (Phantom Works)ADMA Products, Inc.
Plymouth Engineered Shapes, Inc.RTI International Metals, Inc.
ADMA-fabricated Ti-6AL-4V blended elemental powder-based billets were extruded successfully by Plymouth Engineered Shapes, Inc. and RTI International Metals, Inc.
Extrusions up to 27-foot long 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 is a non-issue in this process.
36’-Long Extrusions Cut-up for Shipping and Laboratory Characterization
17.414..5141.5129.0Ingot Based
16.915.8149.6136.5ADMA P/M
Elastic Modulus, MSiElongation, %Yield Strength, (ksi)Ultimate Strength, (ksi)Ti-6Al-4V
Canless Extrusion Process Development for Blended-Elemental Powder-Based Titanium Ti-6AL-4V Alloy
(Boeing/ADMA)
RTI, International Metals, Inc.RTI, International Metals, Inc.
Plymouth Engineered Shapes, Inc.Plymouth Engineered Shapes, Inc.
Boeing–Obtained Results of Chemical Analyses of Extruded Parts Showed Blended Elemental Powder-Based Parts Conforming to
Ti-6Al-4V Except for Oxygen Content
* All samples were analyzed at Durkee Testing Laboratories, Inc. Los Angeles, CA, using emission spectroscopy and inert gas fusion method. The Laboratory Purchase Order Number is 315427 to AMS 4934D and 4935G. and the Lab. Log Number 207616A.
Ti0.400.100.0050.101250.050.200.303.504.50
5.506.75
Min.Max.
AllExtrusionTi-6AL-4V AMS 4934
Ti<0.40<0.10<0.0050.02340.010.200.183.966.22R4B4Back (Rear End)
Ti<0.40<0.10<0.0050.02240.010.200.184.026.10R4M2Middle
Ti<0.40<0.10<0.0050.02250.010.200.173.945.88R4F2Front Ingot-Based Billet R4
Extruded at Same
Temperature as R2
Ti<0.40<0.10<0.0050.013320.020.290.154.206.22R2B4Back (Rear End)
Ti<0.40<0.10<0.0050.013070.020.290.154.126.52R2M2Middle
Ti<0.40<0.10<0.0050.012440.020.290.154.016.55R2F2Front R2 Extrusion Beta-Extruded
at Lower Temperature
Ti<0.40<0.10<0.0050.013790.020.330.194.036.30R1B4Back (Rear End)
Ti<0.40<0.10<0.0050.013940.020.350.144.136.32R1M2Middle
Ti<0.40<0.10<0.0050.012490.020.350.144.156.36R1F2Front R1 Extrusion Beta-Extruded
At High Temperature
Extrusions
Ti<0.40<0.10<0.0050.01690.010.370.154.336.13Billet # 5Billet End OD Sample
As-SinteredTi Billet CIP/Sintered
Bal.
[%]
OET
[%]
OEE
[%]
Y
[%]
C
[%]
H
ppm
N
[%]
O
[%]
Fe
[%]
V
[%]
AL
[%]
Chemical Element Weight PercentSample Identifi-cation
Sample Position Within
Extrusion Along 8’length
Extrusion Process
Tempera-ture/ Regime
Material Product
Form
Table - Results of chemical analyses* of blended-elemental powder-based titanium Ti-6AL-4V extrusions per 787 Part DWG # BAC 1670-157 extruded by RTI International Metals, Inc. per AMS 4934G and 4935G.
* All samples were analyzed at Durkee Testing Laboratories, Inc. Los Angeles, CA, using emission spectroscopy and inert gas fusion method. The Laboratory Purchase Order Number is 315427 to AMS 4934D and 4935G. and the Lab. Log Number 207616A.
Ti0.400.100.0050.101250.050.200.303.504.50
5.506.75
Min.Max.
AllExtrusionTi-6AL-4V AMS 4934
Ti<0.40<0.10<0.0050.02340.010.200.183.966.22R4B4Back (Rear End)
Ti<0.40<0.10<0.0050.02240.010.200.184.026.10R4M2Middle
Ti<0.40<0.10<0.0050.02250.010.200.173.945.88R4F2Front Ingot-Based Billet R4
Extruded at Same
Temperature as R2
Ti<0.40<0.10<0.0050.013320.020.290.154.206.22R2B4Back (Rear End)
Ti<0.40<0.10<0.0050.013070.020.290.154.126.52R2M2Middle
Ti<0.40<0.10<0.0050.012440.020.290.154.016.55R2F2Front R2 Extrusion Beta-Extruded
at Lower Temperature
Ti<0.40<0.10<0.0050.013790.020.330.194.036.30R1B4Back (Rear End)
Ti<0.40<0.10<0.0050.013940.020.350.144.136.32R1M2Middle
Ti<0.40<0.10<0.0050.012490.020.350.144.156.36R1F2Front R1 Extrusion Beta-Extruded
At High Temperature
Extrusions
Ti<0.40<0.10<0.0050.01690.010.370.154.336.13Billet # 5Billet End OD Sample
As-SinteredTi Billet CIP/Sintered
Bal.
[%]
OET
[%]
OEE
[%]
Y
[%]
C
[%]
H
ppm
N
[%]
O
[%]
Fe
[%]
V
[%]
AL
[%]
Chemical Element Weight PercentSample Identifi-cation
Sample Position Within
Extrusion Along 8’length
Extrusion Process
Tempera-ture/ Regime
Material Product
Form
Table - Results of chemical analyses* of blended-elemental powder-based titanium Ti-6AL-4V extrusions per 787 Part DWG # BAC 1670-157 extruded by RTI International Metals, Inc. per AMS 4934G and 4935G.
Boeing–Obtained Results of Tensile Properties in Extruded Parts Showed B-E Powder-Based Properties Superior to Ingot-Based Same Alloy
17.414.5129141.5IngotB-E 6%
Stronger16.915.8136.5149.6PowderOverall Average Properties (36 Tests)
17.614126.4138.6BackIngot/ Beta
17.514.5125.6139Mid spanIngot/ Beta
Same Temp. as
for R2
17.414.5129.0141.51715134.9146.8FrontIngot/ BetaR416.915.5139.3152.4BackB-E / Beta
1716137.2150Mid spanB-E / Beta
Same Temp. as
for R4
16.915.5138.8151.316.815139.8151.4FrontB-E / BetaR217.215.5134.4147.2BackB-E / Beta
16.215.5140.7153.5Mid spanB-E / Beta
Highest Extrusion
Temp.
16.815.2139.2151.917.114.5142.6155FrontB-E / BetaR117.116137149.3BackB-E/ α−β
16.816135.9148.7Mid spanB-E/ α−β
Lowest Extrusion
Temp.
17.016.0136.9149.417.116137.8150.3FrontB-E/ α−βP-317.615.5138.3150.4BackB-E/@ β tr.
17.315.5136149.8Mid spanB-E/@ β tr.
Extruded at Beta Transus
17.115.8137.0150.116.416.5136.8150FrontB-E/@ β tr.P-21716.5129.7144.9BackB-E / Beta
16.216.5130.1144.6Mid spanB-E / Beta
Beta Extrusion
16.616.3130.4145.116.516131.3145.9FrontB-E / BetaP-1
Notes on
Extrusion Tempera-
tures
Elastic Modulus
[Msi]
E%[%]
0.2%
σY[ksi]
UTS[ksi]
Elastic Modulus
[Msi]
E%[%]
0.2%
σY[ksi]
UTS[ksi]
Test SpecimenLocation
within Extrusion
Material: Powder
or Ingot / Extrusion Process
Part ID
Table 1 – Comparison of room-temperature tensile properties of extruded product forms from Blended elemental ADMA-Consolidated hydride/dehydride powder subsequently extruded by RTI and Plymouth (with final product containing 3000 ppm oxygen) versus ingot-based extrusions (with 2000 ppm Oxygen maximum)
17.414.5129141.5IngotB-E 6%
Stronger16.915.8136.5149.6PowderOverall Average Properties (36 Tests)
17.614126.4138.6BackIngot/ Beta
17.514.5125.6139Mid spanIngot/ Beta
Same Temp. as
for R2
17.414.5129.0141.51715134.9146.8FrontIngot/ BetaR416.915.5139.3152.4BackB-E / Beta
1716137.2150Mid spanB-E / Beta
Same Temp. as
for R4
16.915.5138.8151.316.815139.8151.4FrontB-E / BetaR217.215.5134.4147.2BackB-E / Beta
16.215.5140.7153.5Mid spanB-E / Beta
Highest Extrusion
Temp.
16.815.2139.2151.917.114.5142.6155FrontB-E / BetaR117.116137149.3BackB-E/ α−β
16.816135.9148.7Mid spanB-E/ α−β
Lowest Extrusion
Temp.
17.016.0136.9149.417.116137.8150.3FrontB-E/ α−βP-317.615.5138.3150.4BackB-E/@ β tr.
17.315.5136149.8Mid spanB-E/@ β tr.
Extruded at Beta Transus
17.115.8137.0150.116.416.5136.8150FrontB-E/@ β tr.P-21716.5129.7144.9BackB-E / Beta
16.216.5130.1144.6Mid spanB-E / Beta
Beta Extrusion
16.616.3130.4145.116.516131.3145.9FrontB-E / BetaP-1
Notes on
Extrusion Tempera-
tures
Elastic Modulus
[Msi]
E%[%]
0.2%
σY[ksi]
UTS[ksi]
Elastic Modulus
[Msi]
E%[%]
0.2%
σY[ksi]
UTS[ksi]
Test SpecimenLocation
within Extrusion
Material: Powder
or Ingot / Extrusion Process
Part ID
Table 1 – Comparison of room-temperature tensile properties of extruded product forms from Blended elemental ADMA-Consolidated hydride/dehydride powder subsequently extruded by RTI and Plymouth (with final product containing 3000 ppm oxygen) versus ingot-based extrusions (with 2000 ppm Oxygen maximum)
Boeing-Obtained Summary on Canless Air-Extruded Product Form
• Canless full-scale extrusion of blended elemental hydride/dehydride ADMA powder-based product form has been successfully demonstrated.
• Any residual hydrogen content within the final extruded parts was thermally degassed in vacuum down to 23-33 ppm.
• Preliminary encouraging powder-based extruded product form shows static tensile and fatigue S/N durability properties superior to ingot-based identically extruded product form.
• Further optimization should focus on reducing oxygen content in the final blended elemental powder based product down to 2000 ppm maximum for aerospace quality material.
Low-oxygen P/M Ti-6Al-4V Billets from Hydrogenated Ti Powder
Ti-6Al-4V billet 8.50” x 12.0” x 52.0”725 lbs
Low-oxygen P/M Ti-6Al-4V CIP/Sinter Pre-forms
Cold Isostatic Pressing
Sintering
RollingForging
Low-oxygen P/M Ti-6Al-4V CIP/Sinter pre-forms produced from ADMA Hydrogenated Ti powder
Extrusion
Blended Elemental P/M Ti alloy Round Bars
P/M Ti-6Al-4V Extrusion billets
P/M Ti-6Al-4V Rotary forged bars
Cold Isostatic Pressing
Sintering
Extrusion Rolling
Rotary Forging
P/M Ti-6Al-4V Extruded bars
10 Min.125 Min.135 Min.AMS 4928R
Ti-6Al-4V Ultimate Strength, ksi
Yield Strength, ksi
Elongation, %
Reduction of Area, %
ADMA P/M 148 – 152 142 – 145 19.8 - 22.8 28.2 - 28.3
Ingot Based 140 - 143 125 – 127 19.4 - 21.1 26.9 - 27.6
P/M Ti-6Al-4V Hot rolled bars
Conclusions
1. Cost-effective process has been developed for manufacturing the hydrogenated titanium powder.
2. Manufacturing of hydrogenated titanium powder possessing desirable hydrogen and impurity content has been developed in Ukraine in cooperation with ADMA Products, Inc.
3. Cost-effective processes have been developed for the production of titanium alloy components from hydrogenated titanium powder.
4. Mechanical properties of powder metallurgy titanium alloys produced from hydrogenated Ti powder meet or exceed the requirements of ASTM and AMS specifications.