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TITANIUM ALLOYS are classified into Effects of Alloying Elements on a/b strengthened by solution/aging heat treatments
three groups with the following properties: Transformation but can be stress-relief annealed; properties
may be modified by morphology changes in the
Alpha alloys microstructure.
Alloying elements have several purposes: Alpha-beta alloys are two-phase mixtures
a. Non-heat-treatable for significant stren-
with room-temperature stability. The a/b alloys
gthening To stabilize the crystallographic form, a or are the most common and most versatile of the
b. Very weldable b, so they can exist and/or coexist at tem- three alloy types. The phase composition, grain
c. Low-to-medium strength peratures above or below 882 C (1620 F), size, and phase distribution can be manipulated
d. Good notch toughness the transus temperature by heat treatment for mechanical property
e. Good ductility To strengthen by interstitial and solid- enhancements, including higher tensile and fatigue
f. Excellent cryogenic properties solution hardening strength. Typical heat treatments for a/b titanium
g. Good high-temperature creep strength To act as precipitation-hardening agents to alloys are summarized in Table 2 (Ref 2–4).
h. Oxidation resistance strengthen by heat treatment Commercial beta alloys are metastable.
Alpha-beta alloys
They are defined as alloys that can retain
Alloying elements are classified as a or b sta- 100% b at room temperature. Significant
a. Heat treatable to varying extents, depend- strengthening can be brought about via solution
bilizers that shift the transus temperature up or
ing on alloy treatment and aging.
down, depending on alloying addition.
b. Weldable, with reduced ductility in the Beta-Transus Temperature. Table 3 lists the
Alpha stabilizers, such as oxygen, nitrogen,
weld zone
carbon, and aluminum, raise the a/b transfor- effects of commercial titanium alloys on the
c. Medium-to-high strength; generally good b-transus temperature (Ref 2). It clearly illustrates
mation temperature.
property combinations the significant effect of alloy composition on
Beta stabilizers, including chromium, iron,
d. Good hot forming ability b-transus temperature. Due to minor variations
molybdenum, vanadium, and niobium, lower
e. Poor cold forming ability in chemistry, titanium producers include b-transus
the a/b transus temperature, allowing some
f. Creep strength lower than many a alloys
b-phase retention at room temperature. Zirco- temperature with mill certifications. See the sec-
nium and tin essentially have no effect on the tion “Appendix A—Methods for Determination
Beta and near-beta alloys a/b transformation temperature. of the b-Transus Temperature” in this article.
Table 1 (Ref 1) lists common a/b stabilizers. Effect of Oxygen and Iron. Oxygen and
a. Heat treatable
Alpha and near-alpha titanium alloys con- iron are two of the most potent strengthening
b. Weldable; welding process and properties
are alloy and process dependent tain primarily a stabilizers, with less than ~2% b additions. For commercially pure (CP) grades,
stabilizers. These alloys cannot be significantly they must be near the specified maxima to meet
c. Medium-to-high strength
strength levels.
d. Damage tolerance is generally lower than
For hardenable grades:
a/b alloys; excellent solution-annealed
Table 1 Common a and b stabilizers Oxygen probably should be near the specified
cold forming ability
Alloying Approximate range,
element wt% Effect on structure
maximum to achieve specified strength levels
Pure titanium and titanium alloys are allo- in solution-treated and aged Ti-6Al-4V. The
tropic. Pure titanium reversibly transforms from Aluminum 3–8 a stabilizer hardenability is limited by thickness. If frac-
Tin 2–4 a stabilizer
a, the hexagonal close-packed crystallographic Vanadium 2–15 b stabilizer ture toughness is a key property, it may be
form stable at room temperature, to b, the body- Molybdenum 2–15 b stabilizer desirable to reduce the oxygen to a maximum
centered cubic crystallographic form stable Chromium 2–12 b stabilizer of 0.13%, with a reduction in mechanical
above 882 C (1620 F), which is the transus Copper ~2 b stabilizer properties.
Zirconium 2–5 a and b strengthener Iron and other b-alloy additions must be
temperature for commercially pure titanium. It Silicon 0.05–0.5 Improves creep
remains as stable b to the melting point. When resistance kept relatively low to optimize creep and
cooled below the transus temperature, it reverts Source: Ref 1 stress-rupture properties. Iron typically is
back to a, the hcp form. less than 0.05%.
Mechanical Property Control of a/b ductility, and a wide range of mechanical prop- be transformed from a coarse acicular a to a fine
Alloys. Table 4 is a partial list of mechanical erty combinations due to larger amounts of acicular a or to a martensitic microstructure sim-
property and elemental composition for tita- retained b. The mechanical properties and ilar to steels or globular structure that results in
nium a/b-stabilized alloys (Ref 1). microstructure of Ti-6Al-4V can be manipu- different mechanical property combinations.
One popular commercial alloy is Ti-6Al-4V, lated easily by mechanical deformation and heat An example of microstructural modification
an a/b-stabilized alloy with good strength, good treatment combinations. The microstructure can is hot forging at temperatures within the a/b
zone to produce fine equiaxed a coexisting
with transformed acicular a from original b.
Table 2 Typical heat treatments for a-b titanium alloys Slightly lower strength can be improved by
varying the solution heat treatment, cooling
Heat treatment Heat treatment cycle Microstructure
rate, and aging conditions. Maximum fracture
Duplex anneal Solution treat at 50–75 C (90–135 F) below Primary a toughness, with somewhat reduced ductility
Tb(a). Air cool. Age for 2–8 h at 540–675 C Primary a + Widmanstätten or colony a/b regions and fatigue strength, occurs when the forging
(1000–1250 F)
Solution treat and Solution treat at ~40 C (70 F) below Tb. Water Primary a temperature is raised completely in the b zone.
age quench(b). Age for 2–8 h at 535–675 C Primary a + Widmanstätten or colony a/b regions However, there must be sufficient deformation
(995–1250 F) After aging, it should be primary a and transformed b. to obtain uniform properties throughout the
Beta anneal Solution treat at ~15 C (30 F) above Tb. Air Widmanstätten or colony a + b structure part.
cool. Stabilize at 650–760 C (1200–1400 F)
for 2 h Reasons for Heat Treatment. Heat treat-
Beta quench Solution treat at ~15 C (30 F) above Tb. Water a0 (not tempered until after aging) ments are conducted for a number of reasons:
quench. Temper at 650–760 C (1200–1400 F) Tempered a0 (Widmanstätten structure)
for 2 h To reduce residual stresses developed during
Recrystallization 925 C (1700 F) for 4 h. Cool at 50 C/h Equiaxed a fabrication
anneal (90 F/h) to 760 C (1400 F). Air cool b at grain-boundary triple points To optimize ductility, machinability, and
Mill anneal a/b hot work plus anneal at 705 C (1300 F) for Incompletely recrystallized a
30 min to 3 h. Air cool Small volume fraction of b particles dimensional and structural stability
To optimize mechanical properties, includ-
(a) Tb is the b-transus temperature for the particular alloy in question. (b) In more heavily b-stabilized alloys such as Ti-6Al-2Sn-4Zr-6Mo or Ti-6Al-
6V-2Sn, solution treatment is followed by air cooling. Subsequent aging causes precipitation of a phase to form an a/b mixture. Source: Ref 2–4 ing strength, ductility, fracture toughness,
Commercially pure titanium Ti-5.8Al-4Sn-3.5Zr-0.7Nb- 1045 1915 Ti-4Al-4Mo-4Sn-0.5Si (IMI 551) 1050 1920
0.5Mo-0.3Si (IMI 834) Ti-5Al-2Sn-2Zr-4Mo-4Cr (Ti-17) 900 1650
0.25 O max 910 1675 Ti-6Al-2Nb-1Ta-0.8Mo 1015 1860 Ti-7Al-4Mo 1000 1840
0.40 O max 945 1735 Ti-0.3Mo-0.8Ni (Ti code 12) 880 1615 Ti-6Al-2Sn-2Zr-2Mo-2Cr-0.25Si 970 1780
Ti-8Mn 800(c) 1475(d)
a and near-a alloys a-b alloys
b or near-b alloys
Ti-5Al-2.5Sn 1050 1925 Ti-6Al-4V 1000(a) 1830(b)
Ti-8Al-1Mo-1V 1040 1900 Ti-6Al-7Nb (IMI 367) 1010 1850 Ti-13V-11Cr-3Al 720 1330
Ti-2.5Cu (IMI 230) 895 1645 Ti-6Al-6V-2Sn (Cu + Fe) 945 1735 Ti-11.5Mo-6Zr-4.5Sn (Beta III) 760 1400
Ti-6Al-2Sn-4Zr-2Mo 995 1820 Ti-3Al-2.5V 935 1715 Ti-3Al-8V-6Cr-4Zr-4Mo (Beta C) 795 1460
Ti-6Al-5Zr-0.5Mo-0.2Si (IMI 685) 1020 1870 Ti-6Al-2Sn-4Zr-6Mo 940 1720 Ti-10V-2Fe-3Al 805 1480
Ti-5.5Al-3.5Sn-3Zr-1Nb-0.3Mo- 1015 1860 Ti-4Al-4Mo-2Sn-0.5Si (IMI 550) 975 1785 Ti-15V-3Al-3Cr-3Sn 760 1400
0.3Si (IMI 829)
Note: These temperatures are nominal and will vary from ingot to ingot. (a) ±20. (b) ±30. (c) ±35. (d) ±50. Source: Ref 2, 3
Unalloyed grades
ASTM grade 1 240 35 170 25 0.03 0.10 0.015 0.20 0.13 ... ... ... ... ...
ASTM grade 4 550 80 480 70 0.05 0.10 0.015 0.50 0.40 ... ... ... ... ...
a and near-a alloys
Ti-5Al-2.5Sn 790 115 760 110 0.05 0.08 0.02 0.50 0.20 5 2.5 ... ... ...
Ti-8Al-1Mo-1V 900 130 830 120 0.05 0.08 0.015 0.30 0.12 8 ... ... 1 1V
Ti-2.25A1-11Sn-5Zr-1Mo 1000 145 900 130 0.04 0.04 0.008 0.12 0.17 2.25 11.0 5.0 1.0 0.2 Si
Ti-6A1-2Sn-4Zr-2Mo 900 130 830 120 0.05 0.05 0.0125 0.25 0.15 60 2.0 4.0 2.0 0.08 Si
a-b alloys
H-6A1-4V(a) 900 130 830 120 0.05 0.10 0.0125 0.30 0.20 60 ... ... ... 4.0V
Ti-6A1-2Sn-4Zr-6Mo(b) 1170 170 1100 160 0.04 0.04 0.0125 0.15 0.15 60 2.0 4.0 6.0 ...
Ti-3A1-2.5V(c) 620 90 520 75 0.015 0.05 0.015 0.30 0.12 3.0 ... ... ... 2.5V
b alloys
Ti-3A1-8V-6Cr-4Mo-4Zr(a) 900 130 830 120 0.03 0.05 0.020 0.25 0.12 3.0 ... 4.0 4.0 6.0 Cr, 8.0 V
Ti-15V-3Cr-3A1-3Sn(b) 1000 145 965 140 0.05 0.05 0.015 0.25 0.13 3.0 3.0 ... ... 3.0 Cr. 15 V
Ti-10V-2Fe-3A1 1170 170 1100 160 0.05 0.05 0.015 2.2 0.13 3.0 ... ... ... 10.0 V
(a) Mechanical properties in annealed condition. Solution treatment and aging will increase strength. (b) Mechanical properties in solution treated and aged condition and not normally in annealed condition. The mechanical
properties may be sensitive to section size and processing methods. (c) Primarily a tubing alloy that may be cold drawn to strengthen. Source: Ref 1
fatigue strength, and high-temperature creep recrystallization heat treatments. This straightening, asymmetric machining of plates
strength includes texture strengthening, a deforma- and forgings, and welding/cooling operations.
To reduce chemical attack in corrosive tion process for creating preferential grain Stress-removal prevents distortion by main-
environments orientations with isotropic mechanical taining shape stability. It eliminates the
To stabilize and prevent distortion after properties. It includes warm/cold deforma- Bauschinger effect: lower compressive or tensile
machining and fabricating operations. This tion processes such as forging, rolling, yield strength, lower tensile yield strength if
potential distortion could be a result of extrusion, and wire and tube drawing. Most deformed in compression, and vice versa. The
machining stresses, thermal stresses due to thermomechanical processing is done to ultimate strength will not be affected.
heat treatment, and stresses induced by minimize texture effects. Stress-relief annealing is optional and depen-
straightening operations, even minor ones. The heat treatment method incorporated dent on the application. In many cases, it can be
depends on the design purpose of the alloy eliminated by incorporating low-stress second-
(Table 5, Ref 2, 3). ary operations. An example of a low-stress oper-
ation is careful machining using low-to-
Alloy Types and Heat Treatment moderate cuts with uniform stock removal that
Response Stress-Relief Anneal may not induce additional residual stress.
Avoiding the Stress-Relief Anneal. Size,
Titanium heat treatment produces phase All titanium and titanium alloys can be stress thickness, and secondary operations determine
transformations from one crystallographic form relieved without adversely affecting strength or if stress-relief annealing is necessary. For
to another. The heat treatment response is a ductility to decrease undesirable residual stress example, Ti-6Al-4V thin compressor disk rings
critical factor that determines how quickly the from prior fabrication. These include nonuniform were machined without a stress-relief anneal.
heat treatment affects mechanical properties. It hot forging or deformation, cold forming and They conformed to all dimensional require-
depends on a combination of factors, including: ments due to management of residual stresses
in upstream operations. However, the same thin
Elemental composition rings of the same alloy processed at higher
Thermomechanical processing experienced Table 6 Stress-relief time and temperature
machining rates induced additional residual
by the material for pure titanium and titanium alloys
stress that had to be stress relieved. Additional
Heat treatment sequence Temperature stress relief was required.
Cooling rate between heat treatment cycles Alloy
C
F Time, h Combining Stress-Relief Anneal with Solu-
Commercially pure 480–595 900–1100 0.25–4 tion Treating and Aging. In many cases, the
These factors affect both temperature and titanium (all grades) additional stress-relief step can be combined
time for the a-to-b and/or b-to-a transforma- with the standard annealing, solution treating,
a or near-a titanium alloys
tions to occur and subsequent a precipitation, and aging or hardening steps. However, it is
which provides the strengthening. Ti-5Al-2.5Sn 540–650 1000–1200 0.25–4
Ti-8Al-1Mo-1V 595–705 1100–1300 0.25–4 alloy dependent and will not occur in Ti-6Al-4V
Strengthening and Hardening Heat Treat- Ti-2.5Cu (IMI 230) 400–600 750–1110 0.50–24 at 538 C (1000 F), but it is suitable for b
ments. Strengthening and hardening of tita- Ti-6Al-2Sn-4Zr-2Mo 595–705 1100–1300 0.25–4 alloys or a heavily b-stabilized a/b alloy.
nium and its alloys involve a combination of Ti-6Al-5Zr-0.5Mo-0.2Si 530–570 980–1050 24–48
Table 6 is a list of recommended times and
heat treatments: (IMI 685)
Ti-5.5Al-3.5Sn-3Zr- 610–640 1130–1190 1–3 temperatures for stress relieving titanium and
Solid-solution strengthening strengthens the 1Nb-0.3Mo-0.3Si titanium alloys. For effective stress relief, higher
(IMI 829) temperature requires shorter time, and lower
alloy by increasing the b content along with Ti-5.8Al-4Sn-3.5Zr- 625–750 1160–1380 1–3
temperature requires longer time (Ref 2, 3).
rapid cooling, which either retains b or results 0.7Nb-0.5Mo-0.3Si
(IMI 834) Overaging reduces strength but can increase
in a martensitic transformation, either of
Ti-6Al-2Nb-1Ta-0.8Mo 595–650 1100–1200 0.25–2 ductility and toughness. Aging time is additive.
which will create a fine precipitate during Ti-0.3Mo-0.8Ni 480–595 900–1100 0.25–4 For best stress relief during high-stress cold
aging, resulting in strengthening. (Ti Code 12)
Reduce or enlarge grain size by recrystalli- work operations and overage prevention, a
a-b titanium alloys series of partial stress-relief heat treatments at
zation after mechanical deformation, fol-
Ti-6Al-4V 480–650 1100–1200 1–4 different temperature and time combinations is
lowed by additional deformation and Ti-6Al-7Nb (IMI 367) 500–600 930–1110 1–4 suggested (Fig. 1, Ref 2, 5, 6).
Ti-6Al-6V-2Sn 480–650 900–1200 1–4
(Cu + Fe)
For example, five partial time-temperature
Ti-3Al-2.5V 540–650 1000–1200 0.25–2 stress-relief heat treatments were included in
Table 5 Design purpose of titanium alloys Ti-6Al-2Sn-4Zr-6Mo 595–705 1100–1300 0.25–4 the cold work sequence on Ti-6Al-4V to pre-
Ti-4Al-4Mo-2Sn-0.5Si 600–700 1110–1290 2–4 vent overaging. The partial treatments ranged
Alloy Design purpose (IMI 550)
Ti-5Al-2Sn-2Zr-4Mo-4Cr (Ti-17) Higher strength than Ti-4Al-4Mo-4Sn-0.5Si 600–700 1110–1290 2–4
Ti-6Al-2Sn-4Zr-6Mo Ti-6Al-4V in heavy (IMI 551)
sections Ti-5Al-2Sn-4Mo-2Zr- 480–650 900–1200 1–4
Ti-6Al-2Sn-4Zr-2Mo Higher creep resistance 4Cr (Ti-17)
Ti-6Al-5Zr-0.5Mo-0.2Si Ti-7Al-4Mo 480–705 900–1300 1–8
Ti-6Al-2Nb-1Ta-1Mo Higher fracture Ti-6Al-2Sn-2Zr-2Mo- 480–650 900–1200 1–4
toughness and stress- 2Cr-0.25Si
corrosion resistance Ti-8Mn 480–595 900–1100 0.25–2
Ti-6Al-4V-ELI(a) Higher fracture b or near-b titanium alloys
toughness and stress-
corrosion resistance Ti-13V-11Cr-3Al 705–730 1300–1350 0.25–0.50
Ti-5Al-2.5Sn, Ti-2.5Cu Easier weldability Ti-11.5Mo-6Zr-4.5Sn 720–730 1325–1350 0.25–0.50
Ti-6Al-6V-2Sn, Ti-6Al-4V Good combination of (Beta 111)
properties at moderate Ti-3Al-8V-6Cr-4Zr-4Mo 705–760 1300–1400 0.17–0.25
strength (Beta C)
Ti-10V-2Fe-3Al High-strength forging Ti-10V-2Fe-3A 675–705 1250–1300 0.50–2
Ti-15V-3Al-3Cr-3Sn 790–815 1450–1500 0.25–0.50
alloy Fig. 1 Relationship between time and relief of residual
Source: Ref 2, 3 stress at various temperatures for Ti-6Al-4V.
(a) ELI, extra-low interstitial. Source: Ref 2, 3
Source: Ref 2, 3, 5, 6
from 50 h at 260 C (500 F) to 5 min at 620 C not fully annealed, there may be microstructural b-transus temperature but at the sacrifice of ten-
(1150 F) (Fig. 1). indications of nonuniform prior work. sile strength, fatigue strength, and ductility.
Cooling-Rate Effect. The cooling rate is crit- Duplex-Anneal Multiple Property Enhan- Higher temperatures produce more lamellar a
ical. Slow cooling from the stress-relief temper- cement. Duplex annealing is a heat treatment phase with increased creep, toughness, and
ature by furnace or air cooling, particularly in process for improving multiple properties, such reduced fatigue crack growth rate (da/dN).
the 480 to 315 C (900 to 600 F) range, is nec- as creep resistance and fracture toughness, by The cooling rate is critical for controlling the
essary for preventing residual-stress concentra- microstructural combinations: coarseness of transformed b phase.
tion. Faster cooling by air, oil, or water Some typical heat treatment temperatures for
quenching can reduce production time but is Process Method maximum creep resistance and stability for
not recommended due to distortion. Solution High into the a-b range near-a alloys Ti-8Al-1Mo-1V and Ti-6Al-2Sn-
The effect of faster cooling rates on distor- annealing 4Zr-2Mo in relation to the b-transus tempera-
tion is alloy and shape dependent. It was found Stabilization 8 h at 595 C (1100 F) to a minimum of ture are:
that very fast air cooling of Ti-6Al-4V thin or annealing 56 C (100 F) above the maximum
anticipated service temperature
complexly shaped parts causes distortion during Temperature
b-transus
machining by residual-stress concentration. Alloy
C
F temperature
Effect of Stress-Relief Temperature on
Mechanical properties can be enhanced in Ti-8Al-1Mo-1V 25–55 50–100 Heat treat below
Phase Change. Stress-relief heat treatments Ti-6Al-2Sn- 15–25 25–50 Heat treat below
for a and a/b alloys require balance and con- specific ways by creating a variety of phase 4Zr-2Mo
trol. The temperature must be high enough to shapes, sizes, and distributions. Separate phase
stress relieve but low enough to prevent a pre- morphologies can be created by different
cipitation by strain aging and recrystallization. annealing processes. By combining duplex pro- Forgings of these alloys should be held at the
The selected annealing temperature and cooling cesses, the microstructure of the alloy can be aforementioned temperatures for 1 h nominal,
rate for the alloy and shape should be proven by designed with several mechanical property then air or fan cooled depending on section
experience or experimentation to not cause enhancements, such as: size. Time at temperature also depends on sec-
distortion. tion size; one must assure the temperature is
Stress Relief of Simple and Complex Property enhancement Microstructure uniform throughout the thickness.
Weldments. Simple weldments are defined Duplex anneal combined with thermome-
Maximized fracture resistance Lenticular or acicular
as continuous welds on continuous surfaces. a-phase shape chanical processing is a method to improve
Complex weldments are defined as multiple Maximized high-temperature Lenticular or lamellar fracture toughness, high-temperature creep
creep resistance a-phase shape strength, and plastic flow. An example is a ther-
welds on complex machined surfaces.
Simple CP titanium weldments usually do momechanical process developed by Froes and
not require a stress-relief anneal. However, Highberger for improving Ti-4Al-5Mo-1.5Cr
complex a and a/b alloy weldments do require The shapes listed in the table above can be (Corona 5) formability. Heat treatments are done
annealing for 1 to 4 h near the high end of maximized by a higher temperature above the in conjunction with these processes.
the temperature range (Table 6). After 1 h at the
recommended temperature, at least 70% of Table 7 Recommended annealing heat treatments for titanium and titanium alloys
the residual stress will be relieved (Ref 2). Temperature
Stress-relief annealing is recommended for Alloy
C
F Time, h Cooling method
CP titanium weldments operating at elevated Commercially pure titanium (all grades) 650–760 1200–1400 0.10–2 Air
temperatures. It prevents or reduces hydrogen
a or near-a titanium alloys
embrittlement by enhanced hydrogen migration
in high-temperature environments. Ti-5Al-2.5Sn 720–845 1325–1550 0.17–4 Air
Ti-8Al-1 Mo-1V 790(c) 1450(c) 1–8 Air or furnace
Ti-2.5Cu (IMI 230) 780–800 1450–1470 0.50–1 Air
Ti-6Al-2Sn-4Zr-2Mo 900(c) 1650(c) 0.50–1 Air
Annealing Practices for Mechanical Ti-6Al-5Zr-0.5Mo-0.2Si (IMI 685) (c) (c) ... ...
... ...
Property Enhancement Ti-5.5Al-3.5Sn-3Zr-1Nb-0.3Mo-0.3Si (IMI 829)
Ti-5.8Al-4Sn-3.5Zr-0.7Nb-0.5Mo-0.3Si (IMI 834)
(c)
(c)
(c)
(c) ... ...
Ti-6Al-2Nb-1Ta-0.8Mo 790–900 1450–1650 1–4 Air
Annealing heat treatments are used to a-b titanium alloys
enhance mechanical properties. They produce
Ti-6Al-4V 705–790 1300–1450 1–4 Air or furnace
higher fracture toughness and crack growth Ti-6Al-7Nb (IMI 367) 700 1300 1–2 Air
resistance, higher ductility, increased dimen- Ti-6Al-6V-2Sn (Cu + Fe) 705–815 1300–1500 0.75–4 Air or furnace
sional and thermal stability, and higher creep Ti-3Al-2.5V 650–760 1200–1400 0.5–2 Air
Ti-6Al-2Sn-4Zr-6Mo (c) (c) ... ...
resistance. These improvements generally are ... ...
Ti-4Al-4Mo-2Sn-0.5Si (IMI 550) (c) (c)
obtained at the expense of other properties, so Ti-4Al-4Mo-4Sn-0.5Si (IMI 551) (c) (c) ... ...
the annealing cycle should be selected to meet Ti-5Al-2Sn-4Mo-2Zr-4Cr (Ti-17) (c) (c) ... ...
specifications for the application. Ti-7Al-4Mo 705–790 1300–1450 1–8 Air
Annealing heat treatments include: Ti-6Al-2Sn-2Zr-2Mo-2Cr-0.25Si 705–815 1300–1500 1–2 Air
Ti-8Mn 650–760 1200–1400 0.50–1 (d)
Mill annealing b or near-b titanium alloys
Duplex annealing Ti-13V-11Cr-3Al 705–790 1300–1450 0.17–1 Air or water
Recrystallization annealing Ti-11.5Mo-6Zr-4.5Sn (Beta III) 690–760 1275–1400 0.17–1 Air or water
Beta annealing Ti-3Al-8V-6Cr-4Zr-4Mo (Beta C) 790–815 1450–1500 0.17–1 Air or water
Ti-10V-2Fe-3Al (c) (c) ... ...
Ti-15V-3Al-3Cr-3Sn 790–815 1450–1500 0.08–0.25 Air
Recommended annealing treatments for sev-
eral alloys are given in Table 7 (Ref 2, 3). Note: Furnace cooling will result in parts free from residual stress and could have a negative impact on stress-corrosion resistance for a and a/b
alloys. (a) For sheet and plate, follow by heating at 790 C (1450 F), then air cool. (b) For sheet, follow by 0.25 h at 790 C (1450 F), then
Mill Anneal. Mill annealing is a general- air cool (plus 2 h at 595 C, or 1100 F, then air cool, in certain applications). For plate, follow by 8 h at 595 C (1100 F), then air cool.
purpose treatment given to all mill products. If (c) Not normally supplied or used in annealed condition (Table 6). (d) Furnace or slow cool to 540 C (1000 F), then air cool. Source: Ref 2, 3
High deformation combined with duplex Straightening, Sizing, and A wide range of strength levels can be
annealing produces a two-phase microstructure. Flattening obtained in a/b and b alloys by solution treating
Significant fracture toughness improvement followed by aging. The heat treat response of
occurs if both globular (or equiaxed) and fine len- titanium alloys is dependent on the instability
ticular (or acicular) a phase coexist. This phase Springback Effect. Straightening and flatten- of high-temperature b phase at lower tempera-
ing procedures for titanium alloys to meet tures. Heating an a/b alloy to the solution treat-
combination is not favorable for superplastic
dimensional requirements are difficult due to
deformation unless a fine lenticular a phase is ing temperature produces more b phase. The
springback caused by the higher yield strength
produced at the superplastic forming temperature. exception is Ti-2.5Cu alloys, where strengthen-
The combination of both globular and fine len- and higher modulus of elasticity of titanium and ing is by Ti2Cu precipitation similar to Guinier-
its alloys. It is not easily cold straightened like
ticular a phase produces significant improvements Preston zones in aluminum alloys. (It should be
softer, more pliable metals such as aluminum.
in superplastic formability and fracture toughness. noted that U.S. manufacturers normally do not
The globular a-phase shape optimizes high- Special methods such as creep flattening are add copper to titanium, although European
temperature plastic flow, making it suitable for required for close tolerance control. manufacturers use a copper-bearing alloy for
To overcome springback problems, straighten-
superplastic forming operations, while fine len- biomedical applications.)
ing, sizing, and flattening processes are conducted
ticular a phase precipitating between globular Mechanical property improvements are
a-phase grain boundaries maximizes fracture hot to utilize creep as the straightening mecha- obtained by heat treatment combinations that
toughness and fracture resistance without nism. For production efficiency, it usually is com- partition unstable b phase into different a-phase
bined with standard annealing and aging
affecting strength (Ref 7). forms by the solution treating, quenching, and
processes. Individual or fixtured parts self-
Froes and Highberger achieved this effect by aging sequence. Generally, the greater amount
the following operations: straighten by high-temperature creep at annealing of b phase or martensite forming on cooling,
and aging temperatures. Straightening is
the greater the hardenability.
improved by uniform slow cooling to below
Preparation for Heat Treatment. Titanium
Process Microstructure
315 C (600 F). Depending on the alloy, straight- components are cleaned and loaded onto fixtures
High deformation in a/b field Elongated lenticular grains ening time increases below 540 to 650 C (1000 to or racks with unrestricted access to the heating
(approximately 70% 1200 F).
strain) and quenching media. Thick and thin compo-
a/b heat treatment Globular or equiaxed a
Creep flattening is a method for flattening nents of the same alloy can be solution treated
approximately 300 C phase; high strain energy titanium sheets or plates by sandwiching them together. However, time at temperature is deter-
(540 F) below b transus in prior-lenticular between two clean, flat steel sheets in oxidizing,
at 800 C (1475 F) recrystallized a phase
mined by the thickest section. If the parts are
inert, and vacuum atmospheres. Preventative not symmetrical, solution treating a and a/b
converting to equiaxed or
globular low-energy form
measures to prevent possible bonding to the steel could result in distortion upon machining.
Age hardening in a-phase Precipitation of new fine sheets should be incorporated. A general rule is to allow 20 to 30 min per
region 200–400 C lenticular a-phase particles Vacuum creep flattening is a method for
(360–720 F) below b both at the globular a grain
25 mm (1 in.) of thickness to reach temperature,
producing stress-free flattened plates and sheets followed by the required soak time (Table 8).
transus. The age-hardening boundaries and in the b
rate is too slow at 200 C phase during the a + b
by a combination of creep with vacuum forming. Distortion of complex parts is minimized by
(360 F) below the b transformation while Titanium plates or sheets are placed on a large, first preheating them prior to furnace placement.
transus to be significant. cooling flat ceramic bed with embedded electric heating The solution treating temperature depends on the
elements. A plastic sheet, thermally insulated alloy type and practical considerations.
from the hot titanium parts to prevent melting, Alpha-Beta Alloys. The solution treatment
Recrystallization annealing improves frac- encapsulates the entire assembly. It is airtight- temperature for a/b alloys is based on the desired
ture toughness and crack growth resistance while sealed to the assembly frame with a vacuum con- mechanical properties after aging for the applica-
retaining good fatigue properties by heating into nection. Even though an expensive process, it tion. The solution treatment temperature alters
the upper end of the a-b range, holding, and very does work well. the quantity of b-phase, consequently altering
slow cooling. However, it is at the expense of As the plastic sheet is evacuated, the titanium the aging response time (Table 9).
somewhat lower tensile properties. plates or sheets on the ceramic bed are slowly Alpha-Beta and Beta Alloys Condition and
Beta annealing achieves maximum fracture heated to the annealing temperature. Atmo- Solution Heat Treatment. Alpha-beta alloys
toughness and crack growth resistance. Exces- spheric pressure pulls both the plastic and tita- are normally supplied in the annealed condition,
sive grain growth is prevented by heating to a nium sheets toward the bed, creep flattening the while b alloys are normally supplied in the solu-
temperature slightly higher than the b-transus titanium or titanium alloy to close tolerances. tion-treated condition. If reheating is required,
temperature. Annealing time is dependent on Slow cooling follows after the flattening soak times should be only as long as necessary
section thickness but should be long enough opertation. to complete the process. Solution treating tem-
for complete transformation. The time at tem- peratures for b alloys normally are above the b
perature after transformation should be mini- transus. Heating time is critical since growth
mized to control b grain growth. Maximum Solution Treating and Aging can proceed rapidly due to no second phase being
creep strength resistance for Ti-6Al-2Sn-4Zr- present to inhibit the grain growth of b-solution-
2Mo is obtained by b annealing when heat Solution Treatment. Solution treating of tita- treated alloys. As mentioned previously, the b
treating air frame components. nium alloys involves heating either slightly solution treatment normally is only approxi-
Stabilization Anneal and Cooling Rate. above, near, or slightly below the b-transus tem- mately 25 C (50 F) above the transus to mini-
Stabilization annealing stabilizes the micro- perature. Commercial b alloys generally are sup- mize grain growth.
structure. It reduces or eliminates residual stress plied in the solution-treated condition and then For high strength, solution treating is done
by cooling from above the b transus. age hardened after machining just prior to the high into the a/b field, normally 25 to 85 C (50
The cooling rate affects mechanical proper- final machining step, or following the final to 150 F) below the b-transus temperature of
ties. Slight increases in strength (up to 35 MPa, machining step and then chemically milled to the alloy. For high fracture toughness, improved
or 5 ksi) can be gained in Ti-6Al-4V and remove surface contamination following the crack growth, and/or improved stress-corrosion
Ti-6Al-6V-2Sn alloys by slow cooling at final heat treatment. Beta alloys normally are resistance, b annealing is used. Exceeding the
55 C/h (100 F/h) from the annealing tempera- solution treated above the b transus, while a b-transus temperature permanently reduces duc-
ture to 540 C (1000 F). This is attributed to pre- and a/ b alloys normally are done below the tility and fatigue performance. Subsequent ther-
cipitation of the ordered a2 phase within the a. transus. mal treatments cannot fully restore them.
Table 8 Recommended solution treating and aging (stabilizing) treatments for titanium Table 9 Effect of solution treating
alloys temperature on aged mechanical properties
Solution treating temperature and time Aging temperature and time
of Ti-6Al-4V
Cooling
Mechanical properties (room temperature)
Alloy C F Hours media C F Hours
Solution
treatment Tensile Yield
a or near-a alloys
temperature strength(a) strength(b)
Ti-8Al-1Mo-1V 980–1010(a) 1800–1850(a) 1 Oil or 565–595 1050–1100 ...
C F MPa ksi MPa ksi Elongation(c), %
water
Ti-2.5Cu (IMI 230) 795–815 1465–1495 0.5–1 Air or 390–410 735–770
8–24 845 1550 1025 149 980 142 18
water (step 1) 870 1600 1060 154 985 143 17
465-485 870-905 8 (step 2) 900 1650 1095 159 995 144 16
Ti-6Al-2Sn-4Zr-2Mo 955–980 1750–1800 1 Air 595 1100 8 925 1700 1110 161 1000 145 16
Ti-6Al-5Zr-0.5Mo-0.2Si (IMI 685) 1040–1060 1905–1940 0.5–1 Oil 540–560 1005–1040 24 940 1725 1140 165 1055 153 16
Ti-5.5Al-3.5Sn-3Zr-1Nb-0.3Mo- 1040–1060 1905–1940 0.5–1 Air or oil 615–635 1140–1175 2 (a) 13 mm (½ in.) diam bar after solution treating, quenching, and
0.3Si (IMI 829) aging. (b) 0.2% offset. (c) Gage length = 4D (4 diam). Source:
Ti-5.8Al-4Sn-3.5Zr-0.7Nb-0.5Mo- 1020(b) 1870(b) 2 Oil 625 1155 2 Ref 2, 3
0.3Si (IMI 834)
a-b alloys
Temperature, °F
Ti-6Al-4V 955–970(c)(d) 1750- 1 Water 480–595 900–1100 4–8 1800 1835 1870 1905 1940
100
1775(c)(d) 705–760 1300–1400 2–4
Ti-6Al-6V-2Sn (Cu + Fe) 885–910 1625–1675 1 Water 480–595 900–1100 4–8
Ti-6Al-2Sn-4Zr-6Mo 845–890 1550–1650 1 Air or 580–605 1075–1125 4–8 98
water(e) Ti-6AI-4V IMI 829 IMI 834
Ti-4Al-4Mo-2Sn-0.5Si (IMI 550) 890–910 1635–1670 0.5–1 Air 490–510 915–950 24 (a/b alloy) (Near-a alloy) (Near-a alloy)
96
Ti-4Al-4Mo-4Sn-0.5Si (IMI 551) 890–910 1635–1670 0.5–1 Air 490–510 915–950 24
Ti-5Al-2Sn-2Zr-4Mo-4Cr 845–870 1550–1600 1 Air 580–605 1075–1125 4–8
Ti-6Al-2Sn-2Zr-2Mo-2Cr-0.25Si 870–925 1600–1700 1 Water 480–595 900–1100 4–8 94
b or near-b alloys
80
Near-Alpha Alloys. As with a/b alloys, solu- affects subsequent age-hardened strength and 980 1000 1020 1040 1060
tion treatment above the b-transus temperature hardness. Extremely slow cooling is detrimental, Temperature, °C
provides optimum creep resistance with reduced due to diffused a phase affecting the amount of
ductility and fatigue strength. To obtain the best available b phase for decomposition into a Fig. 2 b-transus approach curves of IMI 834, IMI 829,
and Ti-6Al-4V showing b phase volume vs.
combination of creep and fatigue strength, a phase, because the precipitated a will be quite temperature. Source: Ref 5
slightly lower solution treating temperature below coarse, which limits the hardenability.
the b-transus temperature ensures that only 10 to Slow cooling is possible for a alloys, alloys
15% of primary untransformed a phase remains. with relatively high b-stabilizer content, and The age hardening effect can be negated by
A more gradual b-transus approach curve small section sizes that naturally cool faster. Beta slower cooling of large sections. Because
and a wider heat treatment window will com- alloys generally are air quenched from the solu- strength and hardness can be reduced to previous
pensate for temperature fluctuations. This can tion treating temperature. Air or fan cooling is lower levels after solution treatment, quench
be accomplished by alloy modifications. Alloy adequate. Slow cooling minimizes distortion, practice is critical. Up to a 7 s delay is tolerable
IMI 834 (Ti-5.5Al-4.5Sn-4.0Zr-0.5Mo-0.7Nb- provided that the final aged mechanical proper- for some a/b alloys. More highly b-stabilized
0.04Si-0.06C) is an example of how a 0.06% ties meet engineering specifications. This is not alloys can accept longer delay times of up to
C addition widens the deferential between the a problem with b alloys because the aging tem- 20 s, depending on section size (Ref 2).
a and b-transus temperatures and flattens the perature is sufficiently high to remove residual Sensitivity to Quench Delay for Alloy and
approach curve (Fig. 2, Ref 5). stress. Section Size. Quench delay affects mechanical
Alloy IMI 834, heat treated high in the region, If a/b alloys can tolerate some distortion, properties (Fig. 3) (Ref 2, 8).
produces approximately 7.5 to 15 volume per- water, 5% brine, and caustic soda solutions Alloys less sensitive to quench delay are:
cent of primary a in a fine-grained (~0.1 mm, or are preferred quenching media. These quench-
0.004 in.) matrix of transformed b. The combina- ants have faster cooling rates, preventing pre- Ti-6Al-2Sn-4Zr-6Mo
tion of equiaxed a and transformed b creates a mature b-phase decomposition for maximum Ti-4Al-4Mo-2Sn-0.5Si
good combination of strength, creep, and fatigue aging response (Ref 2). Ti-5Al-2Sn-2Zr-4Mo-4Cr
strength (Ref 5). Quench delay is the time required to move
the part from the furnace to the quench tank fol- Up to 100 mm (4 in.) sections of these alloys
lowing solution anneal. Rapid quenching is can develop good strength just by forced-air
Quenching necessary to prevent b-phase decomposition cooling (Fig. 3).
for maximum aging response. Water and 5% In summary, section size strongly influences
Cooling-Rate Effect. The rate of cooling brine solutions are used to speed the cooling quench effectiveness for best aging response.
from the solution treating temperature to ambient rates (Ref 2). The amount and type of b stabilizer determines
Elongation, %
section size, and Fig. 4 shows the effect of
1100 160
quenched section size on Ti-6Al-4V tensile 10
properties (Ref 2).
1000 Yield strength
140
0
0 20 40 60 Air cooled
Scaling and Oxidization 900
Time delay, s
(b)
120
800
Effect of Oxygen on Scaling (Oxidization) 0 20 40 60 80 Air cooled
Time delay, s
Rate. Titanium and its alloys easily oxidize (a)
when heated in air, with the oxidation rate
being alloy dependent. It also is affected by sur- Fig. 3 Effects of quench delay on tensile properties of Ti-6Al-4V, 13 mm (½ in.) diam bar solution treated at 955 C
face cleanliness during heating. Heating CP (1750 F) for 1 h, water quenched, aged 6 h at 480 C (900 F), and air cooled. Source: Ref 2, 3
titanium in air from 650 to 980 C (1200 to
1800 F) for 30 min produces surface oxides
ranging from <0.005 to 0.35 mm (<0.0002 to
0.010 in.) thick, depending on temperature Table 10 Tensile strength of solution-treated and aged titanium alloys by section size
(Table 11). The rate increases with temperature
but varies with alloy. Figure 5 shows scaling or Tensile strength of square bar by section size
oxidization rates of selected titanium alloys 13 mm (1/ 2 in.) 25 mm (1 in.) 50 mm (2 in.) 75 mm (3 in.) 100 mm (4 in.) 150 mm (6 in.)
after heating 48 h from 650 to 980 C (1200 Alloy MPa ksi MPa ksi MPa ksi MPa ksi MPa ksi MPa ksi
to 1800 F) (Ref 2, 3). Ti-6Al-4V 1105 160 1070 155 1000 145 930 135 ... ... ... ...
Additional discussion on the effects of tita- Ti-6Al-6V-2Sn (Cu + Fe) 1205 175 1205 175 1070 155 1035 150 ... ... ... ...
Ti-6Al-2Sn-4Zr-6Mo 1170 170 1170 170 1170 170 1140 165 1105 160 ... ...
nium/oxygen reactions is found in the section
Ti-5Al-2Sn-2Zr-4Mo-4Cr (Ti-17) 1170 170 1170 170 1170 170 1105 160 1105 160 1105 160
“Alpha Case” in this article. Ti-10V-2Fe-3Al 1240 180 1240 180 1240 180 1240 180 ... ... ... ...
Ti-13V-11Cr-3Al 1310 190 1310 190 1310 190 1310 190 1310 190 1310 190
Ti-11.5Mo-6Zr-4.5Sn (Beta III) 1310 190 1310 190 1310 190 1310 190 1310 190 ... ...
Age Hardening Ti-3 Al-8V-6Cr-4Zr-4Mo (Beta C) 1310 190 1310 190 1240 180 1240 180 1170 170 1170 170
Source: Ref 2, 3
General Procedure. Age hardening is usu-
ally the final heat treatment for attaining high
strength in a/b and b heat treatable alloys. It
basically is a heat treating process that produces
As-quenched section size, in. As-quenched section size, in.
decomposition of unstable retained supersaturated 0 1.0 2.0 3.0 4.0 5.0 0 1.0 2.0 3.0 4.0 5.0
1300
b phase or martensite formed on quenching, con- 60
and usually is between 425 and 650 C (800 and 40 Reduction in area
1200 F). Typical aging times and temperatures 1100 160
Omega-Phase Prevention. Beta can trans- somewhat lower strength. For Ti-6Al-4V and hydrogen from water vapor decomposition.
form into omega (o) phase during aging of Ti-6Al-4V-ELI alloys: Oxygen, reacting with titanium at temperatures
highly b-stabilized a/b alloys. The o phase, a Advantages: Improved fracture toughness greater than 500 C (930 F), readily diffuses
metastable transition phase, can cause unac- into titanium and titanium alloys, forming a
and fatigue crack growth characteristics
ceptable brittleness when reverting back to a Disadvantages: Reduced strength levels hard, brittle surface layer called a case that
phase with fine a particle sizes. Method: Heat 925 to 955 C (1700 to 1750 F) degrades mechanical properties (Fig. 6, Ref 9).
A stabilization procedure will correct this Alpha case causes surface cracking during
for 4 h minimum, furnace cool to 760 C
problem by severe quenching followed by rapid sheet forming and reduced ductility during ser-
(1400 F) at maximum cooling rate of 56 C/
reheating to aging temperatures above 425 C vice. It affects machinability by being highly abra-
h (100 F/h), cool to 480 C (900 F) at mini-
(800 F). Rapid heating is not required above sive to standard tungsten carbide and high-speed
mum cooling rate of 370 C/h (670 F/h), air
the o solvus temperature. At sufficiently high steel machine tools such as drills and cutters.
cool to room temperature (classic recrystallize
temperature, a phase grows sufficiently large Microstructure and Depth. Alpha case dif-
anneal treatment)
to prevent brittleness. fers optically from the a/b phase by being ligh-
Metastable b Alloys. These are a class of Beta anneal for Ti-6Al-4V, Ti-6Al-4V-ELI, ter (whiter), smoother, and more homogeneous
alloys not requiring solution treatment. Final and Ti-6Al-2Sn-4Zr-2Mo alloys: (Fig. 7). To prevent mechanical property degra-
hot working followed by air cooling produces dation, it must be either removed or prevented
a condition comparable to solution treatment if Advantages: Improved fracture toughness, from initially forming.
sufficiently stabilized. Beta alloys with a lower high-cycle fatigue strength, crack growth resis- Vacuum heat treating reduces a-case forma-
b-stabilizer content, such as Ti-10V-2Fe-3Al, tance, and stress-corrosion-cracking resistance tion but does not completely eliminate it. For
will normally require a water quench. Disadvantages: Reduced tensile ductility example, a 79% depth reduction in a-case
Chromium-Containing Alloys and Aging Method: Heat 5 min to 1 h at 1010 to thickness from 57 to 12 mm was obtained after
Time Restriction. Alloys containing chromium 1040 C (1850 to 1900 F), air cool to vacuum heat treating at 954 C (1750 F) for
should not be aged longer than 60 h due to 650 C (1200 F) at minimum rate of 6 h, but some still remained (Ref 10) (Table 12).
chromium-titanium intermetallic compound for- 85 C/min (150 F/min), reheat at 730 to (The vacuum pressure during heat treatment
mation that decreases both ductility and fracture 790 C (1350 to 1450 F) for 2 h (stabiliza- was not indicated.). Figure 8 is an example of
toughness. Shorter aging times often are used on tion anneal), air cool to room temperature a 10 mm (0.0004 in.) a-case layer after vacuum
cold-worked materials to increase strength over heat treatment at 700 C (1300 F) for 30 min
that obtained without the cold work. Cold work- For Ti-6Al-2Sn-4Zr-2Mo alloy: at 104torr (Ref 11).
ing creates generation of dislocations, which Advantages: Improved elevated-temperature Due to production difficulties for some pro-
serve as a-nucleation sites. It is not recom- cessing methods such as casting and forging,
mended that b alloys be held at service tempera- creep strength and fracture toughness vacuum and inert gas atmospheres cannot be
Disadvantages: Lower ductility and fatigue
tures above 315 C (600 F) for prolonged used, so a-case formation occurs and it must
periods, due to possible ductility loss. properties be mechanically or chemically removed.
Method: Heat at 1020 C (1870 F), air cool,
Summary of Typical Thermal Treatments. Approximate a-case thickness must be known
Special thermal treatments previously discussed reheat to 595 C (1100 F) for 8 h, air cool because the oxidation rate and subsequent a-case
enhance mechanical and physical properties. Solution treatment for high-a/b or near-a thickness varies by alloy, temperature, time at
A summary of selected alloys, advantages, dis- alloys for IMI 834 (Ti-5.8Al-4Sn-3.5Zr-0.7Nb- temperature, and cleanliness of the surface.
advantages, and heat treatment method includes: 0.5Mo-0.3Si) alloy: A metallographic examination of a cross section
Solution treat and overage for Ti-6Al-4V including the contaminated surface is the best
alloy: Advantages: Excellent creep, fatigue, and
way to determine the depth.
Figure 9 shows the relationship between time
Advantages: Improved notch strength, frac- tensile properties and temperature on a-case depth for IMI 834
Disadvantages: None indicated
ture toughness, and creep strength relative
Method: Use the b-transus value supplied by
(Ti-6Al-4Sn-4Zr) alloy from 600 to 900 C
to solution treat and aging (1112 to 1652 F) (Ref 10, 12).
Disadvantages: Lower strength. Strength the vendor. See the section “Appendix A: Case Removal by Chemical Milling.
levels are similar to annealing. Methods for Determination of the b-Transus Table 13 is a guide for approximating the minimum
Method: Heat 1 h at 955 C (1750 F), water Temperature” in this article for discussion of
quench, hold 2 h at 705 C (1300 F), air b-transus-determination methods.
cool to room temperature
Alpha Case
Recrystallization annealing is an alternate to
a/b annealing for improved fracture resistance Alpha-Case Formation. Titanium reacts
of critical air frame components without sacrifi- with oxygen, water, and carbon dioxide in oxi-
cing ductility or fatigue, but it will have dizing heat treating atmospheres, and with
amount of surface metal removal to remove a case candidates (Ref 14, 15). Of the four, aluminum Titanium aluminide intermetallic com-
after heat treatment in oxidizing atmospheres at oxide, Al2O3, was the preferred material. It pounds (TiAl, a2-Ti3Al, and TiAl3) and
various times and temperatures (Ref 2, 3). thermodynamically did not favor TiO2 a-case TiO2/TiAl3 (TiAl3 is another form of tita-
The following chemical methods will chemi- formation, was low cost, had good molding nium aluminide.)
cally remove a case (Ref 13): material structural strength, and had high per- Presynthesized TiO2
meability for easy gas and moisture release.
Hydrofluoric acid/nitric acid mixtures However, in spite of a case not being ther- The Ti/Al2O3 reaction products, TiAl3 (tita-
a. Temperature must be controlled between modynamically possible, castings from Al2O3 nium aluminide), and others, when added to
45 and 60 C (110 and 140 F) due to molds had greater a-case affinity than the the Al2O3 mold material, produced an a-case-
strong exothermic reactivity others. Castings from the Al2O3 molds had dee- controlled mold that prevented a-case forma-
b. Highly hazardous: requires safety proce- per and higher microhardness readings tion during casting. This was indicated by both
dures and caution in handling (Fig. 10). At 200 mm deep, it had double the uniform hardness versus depth profiles and a
c. Requires agitation for uniformly finished hardness of the others. The microhardness did bright surface appearance after casting
parts not stabilize at minimum levels until 600 mm (Ref 14, 15).
d. Can produce hydrogen embrittlement deep, while the others stabilized at 300 mm No evidence was found that this mixture was
e. Hydrogen pickup could be accelerated if (Ref 14, 15). The higher hardness and increased being used as a-case preventative coating dur-
temperature exceeds 45 to 60 C (110 to hardness depth suggested that a-case formation ing titanium alloy heat treatment. However,
140 F) involved secondary reactions by a mold compo- other aluminide coatings, such as titanium alu-
nent (Ref 10, 14, 15). minide, platinum aluminide, and Al/SiO2, are
Elemental surface mapping, transmission used for this purpose.
5% fluoroboric acid
electron microscopy, and convergent beam ele- Coatings for Prevention of a-Case Forma-
a. Effective alternative to hydrofluoric acid mental diffraction studies determined that Ti3Al tion during Heat Treatment. Plain titanium
b. Temperature: 65 C (150 F) (titanium aluminide) as well as TiO2 (titanium
c. No hydrogen embrittlement oxide) were formed. Titanium aluminide was
d. 0.5 M sodium fluoride/0.5 M ammonium considered to be the main a-case source, pro- Table 12 Alpha-case depth in Ti-6Al-4V
persulfate solution ducing greater amounts of it in Al2O3 molds after air and vacuum heat treatment
e. Temperature: 75 and 100 C (170 and than by the titanium/O2 reaction alone
212 F) (Ref 10, 14–16). Sample Time,
Temperature
a-case depth,
f. 10% copper sulfate/50% sodium hydrox- condition Grade h C F mm
Sung et al. solved the Al2O3 a-case casting
ide/40% H2O problem by preparing Al2O3 molds containing Atmospheric Ti-6-4 6 955 1750 57
g. Temperature: 105 C (220 F) previous titanium surface-reaction products as
Vacuum Ti-6-4 6 955 1750 12
h. Wyman-Gordon method ingredients: Source: Ref 10
i. 10% HNO3/8% HF/82% H2O
j. Temperature: 45 to 60 C (110 to 140 F)
Table 13 Minimum metal removal for titanium alloys after thermal exposure in oxidizing atmosphere
480–593 900–1100 12 0.005 0.0002 1–2 0.051 0.0020 0.5–1 0.091 0.0036
594–648 1101–1200 4 0.008 0.0003 816–871 1501–1600 0.5 0.058 0.0023 1–2 0.107 0.0042
4–12 0.015 0.0006 0.5–1 0.066 0.0026 927–954 1701–1750 0.5 0.097 0.0038
649–704 1201–1300 1 0.013 0.0005 1–2 0.076 0.0030 0.5–1 0.107 0.0042
1–8 0.020 0.0008 872–898 1601–1650 0.5 0.066 0.0026 1–2 0.122 0.0048
8–12 0.025 0.0010 0.5–1 0.081 0.0032 955–982 1751–1800 0.5 0.114 0.0045
705–760 1301–1400 1 0.025 0.0010 1–2 0.089 0.0035 0.5–1 0.137 0.0054
1–4 0.036 0.0014 899–926 1651–1700 0.5 0.086 0.0034 1–2 0.160 0.0063
4–8 0.038 0.0015 0.5–1 0.091 0.0036 983–1010 1801–1850 0.5 0.145 0.0057
8–12 0.043 0.0017 1–2 0.107 0.0042 0.5–1 0.178 0.0070
761–787 1401–1450 1 0.030 0.0012 927–954 1701–1750 0.5 0.097 0.0038 1–2 0.216 0.0085
1–2 0.038 0.0015 0.5–1 0.107 0.0042 1011–1038 1851–1900 0.5 0.178 0.0070
2–4 0.046 0.0018 1–2 0.122 0.0048 0.5–1 0.229 0.0090
4–8 0.051 0.0020 872–898 1601–1650 0.5 0.066 0.0026 1–2 0.292 0.0115
8–12 0.056 0.0022 0.5–1 0.081 0.0032 1039–1066 1901–1950 0.5 0.229 0.0090
788–815 1451–1500 0.5 0.036 0.0014 1–2 0.089 0.0035 0.5–1 0.305 0.0120
0.5–1 0.041 0.0016 899–926 1651–1700 0.5 0.076 0.0030 1–2 0.406 0.0160
Note: Measure a-case depth metallographically after heat treatment. (a) Values shown are typical; actual values may vary with alloy type. Source: Ref 2, 3
400 3.5
AI2O3 Table 14 Actual and percent weight gain
3 Bare IMI 834
ZrSiO4 Aluminizing and reduction by coating with time for IMI
2
Weight gain, mg/cm
Elongation, %
With coating
strength, MPa
With coating 200 29 600 Without coating 900 °C
200 29
150 33 500 With coating
150 22
400
100 18 100 18 300
50 9 50 9 200
100
0 0 0 0
–1 –2 –3 0
10–1 10–2 10–3 10 10 10 10
–1
10
–2 –3
10
Strain rate, m/s Strain rate, m/s Strain rate, m/s
Elongation, %
600
90 13 450
900 °C Without coating 900 °C
Ultimate tensile strength, ksi
80 Without coating 12 400
Elongation, %
100 14
Fig. 12 Variation of mechanical properties as a function of coating, strain rate, and temperature. (a) Ultimate tensile strength. (b) Yield strength. (c) Elongation. Adapted from
Ref 10, 18
Tensile elongation, %
b. Sputter coating a silicon dioxide (SiO2)
topcoat over the aluminum sublayer 5 5
Ammonium bifluoride macroetch method: shows the embrittling effect of hydrogen on hydrogen phase diagram Fig. 17. Dissolved
a. Surface not machined: Etch the heat trea- tensile properties. As the hydrogen level hydrogen at 5% atomic concentration (0.125%
ted part in 18 g/L (2.4 oz/gal) aqueous increases greater than 600 ppm, tensile strength by weight, or 1250 ppm) lowers the a/b transi-
ammonium bifluoride solution. Light rapidly increases, with a corresponding reduc- tion temperature by 580 C (1044 F), from
gray indicates a case is present, while tion in strain to failure (Ref 20). In CP titanium, 880 C (1616 F) to the eutectoid temperature
dark gray indicates it is not. embrittlement has been observed at hydrogen of 300 C (572 F) (Ref 23).
b. Surface machined: Prior to ammonium contents on the order of 20 to 30 ppm. Hydrogen Adsorption and Crystal Structure.
bifluoride treatment, etch in 5% HF/30% Microstructural Changes. Hydrogen content Hydrogen solubility is affected by both crystal
min HNO3/balance water. significantly affects fractured surface structure. structure and microstructure. Body-centered cubic
Blue etch anodize to SAE specification AMS Large microvoids are present in low-hydrogen (bcc) b phase has higher hydrogen solubility and a
2642 (32 ppm) fractured surfaces (Fig. 15a). As the much higher diffusion rate than hexagonal close-
Metallographic: hydrogen concentration increases to 600 ppm, packed (hcp) a phase, due to more open lattice
a. Grind with 180 to 600 grit previous large microvoids coalesce into smaller spacing. There is solubility in the hcp a phase.
b. Al2O3 polish: 1.0, 0.05, and 0.06 mm ones (Fig. 15b). As hydrogen continues to Hydrogen Adsorption and Microstructure.
c. Colloidal silica: 0.02 mm increase to higher levels (3490 ppm), the small Hydrogen adsorption is dependent on micro-
d. Nital etch: 3 to 5 mL HNO3/100 mL microvoids become brittle facets (Fig. 15c). structure. Duplex a/b microstructures are less
ethanol Hydrides are formed, initiating cracking in a susceptible to adsorption than continuous micro-
Microhardness: The section “Wyman-Gordon phase or at a/b grain boundaries (Fig. 16). structures with nearly single-phase a-phase
Coatings” in this article suggests that microhard- Hydrogen contamination in titanium and its microstructures. Electrochemical hydrogenation
ness depth measurements are more accurate alloys can originate from internal and/or external studies of Ti-6Al-4V alloys with a/b duplex
than metallography and other optical methods sources. Internal contamination is hydrogen microstructure showed greater hydrogen absorp-
to detect a-case depth. This is due to a hidden, present as dissolved hydrogen and/or as hydrides tion than continuous, nearly single-phase a
hard diffusion layer not optically visible but (titanium-hydrogen compounds). External con- microstructure (Fig. 18) (Ref 20).
detected by the microhardness measurements. tamination is hydrogen pickup from the environ- Hydrogen adsorption is dependent on micro-
ment, including heat treating atmospheres and structure. Duplex a/b microstructures are less
electrochemical processes. susceptible than continuous, single-phase a
Hydrogen Embrittlement Internal Hydrogen Contamination. Hydro- microstructures (Fig. 18).
gen, with its high solubility in titanium, is an Titanium hydrides are forms of internal hydro-
Hydrogen embrittlement of titanium alloys a/b phase stabilizer. Depending on concentration, gen contamination that occur in three
causes premature failure by significantly it can significantly lower the a/b transition
degrading mechanical properties. Figure 14 temperature, shown clearly in the titanium- 800 116
3490 ppm
700 102
Table 15 Alpha-case depth of Wyman-Gordon Co. SJ and SJ advanced coatings, Ti-6Al-4V, 600 87
2900 ppm
and Ti-6Al-4V-ELI
500 2790 ppm 73
Stress, MPa
Stress, ksi
a-case depth, heated at 954 C (1750 F) a-case depth change and
for 6 h in air effect of coating and alloy 400 58
Measurement method Comparison method 800 ppm
300 44
Titanium grade(a) Wyman-Gordon coating Optical, mm Microhardness, mm Microhardness(b), % Optical, % Effect 32 ppm
... 200 29
Ti-6Al-4V Uncoated(c) 57 90 0 0
Ti-6Al-4V SJ 67 110 22 18 Increased 100 14
Ti-6Al-4V SJ advanced 42 50 44 26 Decreased
Ti-6Al-4V-ELI Uncoated(c) 43 80 0 0 ... 0
Ti-6Al-4V-ELI SJ 45 100 25 5 Increased 0 5 10 15 20 25 30 35 40
Ti-6Al-4V-ELI SJ advanced 21 30 63 51 Decreased Strain, %
(a) ELI, extra-low interstitial. (b) a-case depth measurement by microhardness was more reliable than optical, due to diffusion. (c) Control specimen.
Source: Ref 10 Fig. 14 Stress-strain curves of hydrogenated grade
2 commercially pure titanium. Source: Ref 20
Fig. 15 Effect of hydrogen concentration on surface fracture of commercially pure grade 2 titanium. (a) As-received, 32 ppm hydrogen, large microvoids. (b) Hydrogenated, 600
ppm hydrogen, large microvoid coalescence into smaller microvoids. (c) Hydrogenated, 3490 ppm hydrogen, small microvoid conversion into brittle facets. Source:
Ref 20
Temperature, °F
maximum hydrogen in accordance with ASTM
(bTi) + G F136, MIL-T-9047, and ASTM F1472. Arcam,
1000 1830
a Swedish titanium powder metal producer,
800 1470 further enhanced the excellent Ti-6Al-4V-ELI
(bTi)
ductility, fracture toughness, and corrosion prop-
600 1110 erties by additional purification. Interstitial
(aTi)
hydrogen was reduced to an extremely low
400 750
g g+G
30 ppm maximum level (Ref 26).
200 390 Table 16 is an elemental and mechanical prop-
erties comparison between Arcam Ti-6Al-4V-
0 30 ELI, standard Ti-6Al-4V-ELI, and Ti-6Al-4V
0 1 2 3 4 5 alloys. The high-cycle fatigue strength of the
Ti Hydrogen, wt%
Arcam high-purity alloy with <30 ppm hydrogen
in the mill-annealed condition was 10 times
greater than standard Ti-6Al-4V (ASTM F136),
Fig. 17 Titanium-hydrogen phase diagram. Source: Ref 21, 22
with slightly higher tensile properties.
External Hydrogen Contamination. As
previously discussed, current materials specifi-
cations limit hydrogen to 125 to 200 ppm. The
exception is alloys such as Ti-6Al-4V-ELI that
were developed for higher ductility, fracture
toughness, and corrosion resistance due to
lower (<30 ppm) hydrogen.
Above the 125 to 200 ppm limit, hydrogen is
an embrittling agent. It reduces ductility, fracture
toughness, impact strength, notch tensile
strength, corrosion resistance, and crack poten-
tial. For these reasons, hydrogen pickup by the
alloy from external sources must be avoided.
Sources of External Hydrogen Contamina-
tion. External hydrogen pickup occurs in vari-
ous ways:
Fig. 18 Effect of microstructure on amount of hydrogen adsorption in Ti-6Al-4V (by electrical hydrogenation; During heat treatment from the furnace
current density: 100 mA/cm2). (a) Microstructure: fully laminar with continuous b phase; hydrogen
adsorption: more, 1110 ppm. (b) Microstructure: duplex a/b with equiaxed primary a and packets of lamellar atmosphere
transformed b (secondary a); hydrogen adsorption: less, 240 ppm. Beta phase has a higher tolerance for hydrogen, During a-case removal by chemical cleaning
and diffusion is much more rapid in the open body-centered cubic b phase. Source: Ref 20 or pickling
Table 16 Chemistry and mechanical property comparisons for Ti-6Al-4V-ELI (standard alloy), Ti-6Al-4V-ELI (Arcam high-purtiy alloy),
and Ti-6Al-4V (standard alloy)
Mechanical Properties
Mill annealed
Ultimate
Chemistry tensile Yield
strength strength
H, Fe, O, C, Other, Reduction
Alloy Al, % V, % ppm % % % % Ti MPa ksi MPa ksi Elongation in area, % Fatigue strength
Ti-6Al-4V-ELI 5.5 to 6.5 3.5 to 4.5 130 0.25 0.13 0.08 0.4 bal 896 130 827 120 15 45 Not available
Carpenter Technology(a)
Ti-6Al-4V-ELI Arcam(b) 6.0 4.0 <30 0.10 0.10 0.03 ... bal 970 141 930 135 16 50 Arcam: 10,000,000 cycles
ASTM F136: 1,000,000 cycles
Ti-6Al-4V Carpenter 5.50 to 6.75 3.50 to 4.50 150 0.4 0.02 0.1 0.4 bal 965 140 875 127 16 46 Not available
Technology(a)
(a) Carpenter Technology data sheets. (b) Ref 26
Coating use solution treat temperature, approximately Vacuum Furnaces. Production vacuum fur-
Hydrogen contamination 1100 C (2012 F), should be employed for sur- naces come in various sizes and styles, depend-
Surface contamination face protection to minimize contamination. ing on use. Vacuum furnaces are of two general
Mechanical testing methods These will not eliminate a case but will make types:
Mechanical properties of selected alloys removal easier. See Table 8 for recommended
Metallography maximum temperatures. Protective coatings Cold wall: Electrical resistance or induction
Record keeping were previously discussed in the section “Alpha heating
Heat treating parameters Case” in this article. Hot wall: Gas, oil, or electrical heating
Vacuum Heat Treatment. The best method
Many aspects of MIL-H-81200 are discussed for eliminating or reducing atmospheric con- Cold wall vacuum furnaces are large, sin-
in this article. The original specification should tamination is by vacuum heat treating, previ- gle-chamber heat treating chambers with
be referenced for additional information. ously discussed in the “Alpha Case” section, water-cooled outer surfaces. Water cooling
Furnace Preference. Electrically heated fur- or with an argon inert gas atmosphere if not allows construction of large units by main-
naces are preferred if heat treating is not done cost-prohibitive. Some contamination still may taining the outer walls to near room tempera-
in an inert atmosphere that minimizes hydrogen occur, but it will be minimal. Even if the sur- ture, so chamber strength is not affected by
pickup. Fuel-fired furnaces with slightly oxidiz- face is shiny, it should be examined for a case. high interior temperatures. There is sufficient
ing atmospheres or isolated muffles that protect If any contamination is observed, chemically chamber strength to support fixtures, internal
the metal from combustion products are also remove that amount plus perhaps an extra insulation, electrical heating elements, and
used successfully. Resistance and induction 0.025 mm (0.001 in.). the workload bed. The heat zone is limited
heating reduce heating time and minimize con- Temperature control is critical. Accuracy to the vicinity of the heating elements or
tamination during solution treatment. of better than ±5 C (±10 F) is desired. induction coils. Figures 19 and 20 show illus-
Titanium usually is annealed or stress relieved MIL-H-81200 specifies ±15 or 10 C (±25 or trations of several types of cold wall furnaces
in conventional furnaces constructed for general 15 F), depending on the application. (Ref 27, 28).
heat treating of ferrous and nonferrous materials.
These furnaces must be adapted for titanium use
due to atmospheric contamination issues because
they may be electric, gas fired, or oil fired.
Atmospheres. A slight oxidizing atmosphere
should be maintained during thermal treatment
of titanium to reduce hydrogen contamination.
Care should be taken when placing titanium
parts into a furnace that was previously used
for heat treating other materials, due to possible
contamination.
Exothermic, endothermic, and cracked-ammo-
nia and/or hydrogen atmospheres present hydro-
gen pickup dangers. The furnace should be
thoroughly “burned out” before introducing tita-
nium and its alloys into the furnace. Hydrogen
contamination is discussed in the section “Inter-
nal Hydrogen Contamination” in this article.
If dimensions, shape, or size do not permit
scale removal by subsequent pickling or
machining after heat treatment, antioxidant
coatings stable at higher than the highest Fig. 19 Top-loading cold wall vacuum furnace. Source: Ref 28
Fig. 20 Typical cold wall vacuum furnaces. (a) Three-chamber horizontal cold wall furnace. (b) Bottom-loading cold wall vacuum furnace. Source: Ref 27
In addition to protection from oxygen and Hot wall electric and gas-fired vacuum fur- at 760 C (1400 F) at a vacuum of <10 mm
hydrogen contamination, a vacuum with essen- naces incorporate an atmospherically isolated (1 102 torr).
tially zero thermal conductivity is an excellent metallic or ceramic inner chamber or retort To reduce distortion in long, thin products
thermal insulator. It protects such interior located inside the main unit. Only the retort such as sheet or extrusions, in hollow cylinders,
components as heating elements, heat shields, fix- is evacuated. It is externally heated by electri- and in long forgings during immersion quench-
tures, and the support hearth from heat damage. cal resistance, induction, or gas positioned out- ing, parts often are suspended vertically in an
Cold wall electric vacuum furnaces commonly side the retort. Heat zone dimensions are electrically heated drop-bottom furnace. In
used in titanium heat treating usually are limited by retort size. The maximum tempera- addition, weights usually are attached to the
designed for 980 C (1800 F) maximum temper- ture is limited by the retort material. Figure 22 bottom ends of the sheet to improve flatness
ature, which is adequate for all titanium alloys. illustrates typical hot wall furnace designs during heating and to facilitate lowering of the
The maximum operating temperature is depen- (Ref 29). sheet into the quench tank. Water quenching
dent on furnace construction. Electrical heating Vacuum Pressure. Vacuum pumping systems is not recommended unless absolutely required;
elements are located inside the furnace (Fig. 21). employ mechanical pumps in combination with it is not recommended unless the part is
diffusion pumps. These systems can attain symmetrical.
extremely low vacuums, down to 0.01 mm of Solution treating equipment varies from sim-
mercury (1 105 torr) or less. Pumping is in ple furnaces with accurate temperature controls
two or three stages, depending on the desired to specialized installations with internal quench
pressure and application (Ref 30): capability (Fig. 23).
Thermocouple Placement. Both the tempera-
ture of the hot zone and the workload are
Vacuum pressure
measured and monitored because a vacuum
No. Operation torr mm
functions as a natural thermal insulator. Because
1A Roughing pump 40 4000 heating is by radiation only, imbalances between
1B Heating starts 4 102 40 the heat source and the workload throughout the
2 Booster pump 1 103 0.10
3 Oil diffusion pump 1 105 0.001 heat cycle, particularly during startup, cause
thermal lag. The workload is cooler than the heat
source, producing higher heat demand than nec-
essary, which could damage the heating ele-
For example, removal of 100 ppm of hydro- ments. To protect the elements from overheat
Fig. 21 Cold wall furnace with curved graphite electrical
gen from 13 to 25 mm (0.5 to 1 in.) sections damage and for accurate workload temperature
heating elements located inside the furnace.
Courtesy of VAC AERO International Inc. of Ti-6Al-4V alloy required approximately 2 h control, two temperature-control systems are
Baffles
Sight port
Heating
Push rod elements
Charge
To vacuum
space (c)
Water jacket
To vaccum
Fine vacuum Furnace shell Refractory insulation
(d)
Fig. 22 Typical hot wall vacuum furnaces. (a) Bell-type vacuum furnace. (b) Pit-type furnace. (c) Vertical two-zone furnace. (d) Horizontal, two-zone, hot wall vacuum furnace.
Source: Ref 29
used: one at the hot zone and the other at the For compliance, the rack and part size Check that the furnace passed prior furnace
workload. placed in the furnace must match the adver- reference probe tests. Check all resistance
For heating element protection, the hot zone tised working zone. element connections to be sure they are tight
or heat source temperature is monitored by at Thermocouples must match calibration certi- before starting the TUS.
least two type S (platinum-platinum/rhodium; fications. Correction factors can be either Aging furnaces are of two types: general and
1480 C, or 2700 F) thermocouples placed 0.75% of the reading or 2.2 C (4 F), special.
close to the heating elements. By feeding an whichever is greater. General Types. Electrical-resistance heating is
electrical signal into their respective control- Sensor locations must be correctly logged. preferable for aging titanium and its alloys
lers, they control power and protect from over- High overshoot and approach temperatures because there are no detrimental combustion
heating, protect from element burnout, and should be recorded. products harmful to the alloy, such as hydrogen.
provide data-recording capability. Thermocouples must not make sharp turns Hot-walled furnaces are allowable with oil or
At least three workload thermocouples are that could cause full or partial short circuits gas-fired furnaces. The retort isolates the heat
attached directly to the load to monitor time between the two thermocouple wires, caus- treated alloy from combustion products in the
and temperature throughout the thermal cycle ing read errors. furnace atmosphere.
and to provide data to compensate for thermal When performing a TUS: A protective atmosphere is not required at
lag. The workload thermocouples are either a. Prior to the TUS, use a calibrated thermo- normal aging temperatures between 480 and
type K (chromel-alumel; 1350 C, or 2460 F, couple signal source to simulate readings 595 C (900 and 1100 F).
maximum) or type N (nicrosil-nisil; 1130 C, at common vacuum system temperatures: Aging furnaces normally are equipped with
or 2066 F, maximum). Type S, with its greater 93, 538, 800, and 1205 C (200, 1000, internal fans for air or other atmosphere circula-
stability and oxide resistance than type K, is 1475, and 2200 F). tion through the heat zone. Aging in air pro-
preferred but is more expensive. b. Prior to the TUS, remove all low- duces a superficial scale that can be removed
The workload thermocouples are placed at temperature materials and alloys. easily by mechanical or chemical means.
three locations: c. Compensate for external recorder deviations. Special Furnaces. The aerodynamic heat
d. Match the TUS temperature ramp rate to treating furnace is a unique heating method
Buried deep inside the load center
the production ramp rate. Do not slow developed in approximately 1964 in the former
At a midpoint between the center and out-
the rate for easier recording. Record the Soviet Union. A centrifugal fan with specially
side of the load TUS ramp rate for audit review. contoured blades self-heats a moving gas
At the outermost surface location
e. Measure and record the location of the stream by directly transferring gas flow through
control thermocouple to ensure set point the blades into heat. There is no electrical or
Because heating deep inside the center uniformity from test to test. other external heating. Temperatures up to
requires longer time than at the surface, the f. Protect from stray induced currents. 700 C (1292 F) are possible (Ref 34).
heating rate must be controlled. Overall heating Check for high-resistance shorts, damp This process is a heat treatment method that
of the entire part can be balanced by monitoring insulation, and dirty connections. Plug significantly reduces process time and improves
all three workload thermocouples and adjusting empty jack panel ports to keep out dirt. the material properties compared to electric air
the hot zone temperature accordingly (Ref 31). Replace jack panel feedthrough plates on a furnaces and salt baths. It is used for convection
A typical thermocouple arrangement is shown yearly or regularly scheduled basis to prevent heat treating of aluminum and titanium alloys.
in Fig. 24 (Ref 32). connection problems from dirty contacts and No further information about its commercial
AMS 2750D, “Furnace Pyrometry and Tem- lowered connector spring tension from heat. use was found for heat treating titanium alloys.
perature Uniformity Survey” describes furnace Ensure that calibration of portable TUS
pyrometry, including sensors, instrumentation, recorders is accurate to ±1.5 C (3 F) or
equipment, calibration, accuracy tests, and ±0.05%, whichever is greater. Quenching
temperature-uniformity survey techniques Check the ground resistance of all resistance
(Ref 33). heating elements to ensure uniformity. Quenching Media. Rapid cooling is
In addition to AMS 2750D procedures, the Ensure that thermocouples are new and pref- required after solution treatment for most tita-
following precautionary measures should be erably from the same wire lot. nium alloys. Water, 5% brine, water/glycol
conducted prior to and during a temperature Ensure that the thermocouple correction fac- mixtures, and caustic soda solutions are widely
uniformity survey (TUS) (Ref 16): tors are less than the survey spread allowance. used. If the quenching rate must be controlled,
Use AMS 2750D-certified thermocouples various glycol/water concentrations produce
certified in 120 C (250 F) set point steps. quench rates between those of water and oil.
Do not extrapolate set point steps greater Low-viscosity, high-flash-point oil is an
than this value. effective medium for vertical immersion
quenching of sheet products to reduce distor-
tion. Steel quench oils are satisfactory. They
provide rapid cooling in the 370 to 425 C
(700 to 800 F) critical temperature range.
Oil-based quenchants after solution treatment
should be limited to thin sections. Due to the
slower heat-transfer rate of oil, there could be
a strength reduction after aging when compared
to the faster rate of water-based quenchants
from the same solution treat temperature.
The quench medium should be thoroughly
agitated, recirculated, and maintained below
40 C (100 F). If the part is not symmetrical,
distortion could occur during the quench or
Fig. 23 Gas quench vertical vacuum furnace. Fig. 24 Example of thermocouple placement. Source:
subsequent machining.
Courtesy of VAC AERO International Inc. Ref 32
transformations and that the observed micro- Normally, test samples are not aged. How- The equation for the b-transus temperature
structure is the true phase relationship. This ever, the phase-disappearing method incorpo- calculation (in degrees Centigrade) is a constant
may not be completely true when heating is rates aging as part of the procedure (Ref 40): followed by the summation of each critical ele-
near the b-transus temperature, because nonop- ment times a multiplier or correction factor
tically visible phase changes can occur. Never- 1. Solution treat and water quench above the (Ref 41).
theless, it is an excellent tool providing estimated b-transus temperature. The Gou et al. equation is in the form of:
accurate b-transus temperature determinations. 2. Age at a lower temperature below the esti-
Interpretation of the exact microstructural mated b-transus temperature to precipitate b transus ð CÞ ¼ Constant þ ½Sum of each critical
indication for complete transformation is sub- a phase. element times a multiplier
jective and varies between different metallogra- 3. Heat for 15 min in 15 C (25 F) or less
phers and laboratories (Ref 37). There is no intervals starting below to above the esti- (The constant is 882, the b-transus temperature
ASTM International standard for the procedure. mated b-transus temperature. for CP titanium.)
However, British Standards Institute standards 4. Water quench. The equation is:
BS EN 3684:2007 and BS EN 3114-001:2006 5. Polish and etch.
are available (Ref 38, 39). 6. Visually determine the b-transus tempera- b transus ð CÞ ¼ 882 þ ½ð21:1 AlÞ ð9:5 MoÞ
The b-transus temperature is determined ture. It is no more than 15 C (25 F) above þ ð4:2 SnÞ ð6:9 ZrÞ
metallographically by heating and quenching test the lowest temperature where the a phase ð11:8 VÞ ð12:1 CrÞ
specimens in precise, accurate temperature steps was last detected.
ð15:4 FeÞ þ ð23:3 SiÞ
starting below and ending above the approxi-
mated b-transus temperature. The temperature þ ð123:0 OÞ
Calculation Method
where 100% a-to-b transformation occurs, the
Confirmation. The author of this article
b-transus temperature, is optically determined. The calculation method is based on thermo- tested the equation by calculating b-transus
The general procedure is to: dynamic modeling combined with a three-layer temperatures for eleven titanium alloys from
1. Heat 2 h at the selected temperatures in 5 to artificial neural network (ANN) requiring lim- different suppliers and alloy groups. The calcu-
15 C (10 to 25 F) intervals. ited process knowledge. The ANN basically is lated results were compared to known pub-
2. Water quench. a nonlinear statistical analysis technique for lished values:
3. Polish and etch. linking input to output data with minimal infor-
4. Visually determine the lowest temperature mation. It finds the set of nonlinear functions The alloy chemistry specifications are in a
where 100% a-to-b phase transformation and coefficients that target outputs closely to high/low range.
occurs. inputs. The b-transus temperature is affected by
The b-transus temperature equation, devel- chemistry variations within an alloy.
The methods for determining the 100% oped by Gou et al. using linear regression cal- The alloy chemistry where the b-transus
phase-transformation level vary. By plotting culations from ANN data, is a set of
percent transformation versus temperature, it temperature was measured was unknown.
dependent chemical element variables within a The published b-transus temperatures have a
is possible to extrapolate between temperature
steps the temperature where 100% transforma-
compositional range. The ANN has been used minimum accuracy of ±15 C (±25 F).
for determining mechanical properties based For the comparison:
tion occurs. on chemical analysis for many materials,
Figure 26 shows examples of phase changes a. The high end of the chemistry specifica-
including steel and titanium (Ref 40, 41). tion was used to account for residual ele-
occurring in titanium alloys after heating and The b-transus temperature is a function of
water quenching at temperatures starting below ments that could affect results.
and ending above the b transus. The phase
alloy chemistry. In titanium alloys, the critical b. The average published b-transus tempera-
elements affecting it are aluminum, chromium, ture was used for comparisons, due to
change that signals 100% a-to-b conversion is iron, molybdenum, silicon, vanadium, zirconium,
the b-transus temperature. It is between published variations. Some vendor speci-
and oxygen. They are used in the equation. fications specify a high/low range, and
Fig. 26(b) and (c).
others just provide a value.
Table 18 Calculated b-transus temperature of titanium alloys from various vendors based on chemistry high versus published specifications
Ti-6Al-4V Carpenter ASTM R56400 Alpha- Al 21.1 6.75 142.43 Ti-3Al-2.5V (cont.) Mo 9.5 0.10(a) 0.95
Tech grade 5 beta Sn 4.2 0.10(a) 0.42
Mo 9.5 0.10(a) 0.95 Zr 6.9 0.10(a) 0.69
Sn 4.2 0.10(a) 0.42 V 11.8 3.00 35.40
Zr 6.9 0.10(a) 0.69 Cr 12.1 0.10(a) 1.21
V 11.8 4.50 53.10 Fe 15.4 0.25 3.85
Cr 12.1 0.10(a) 1.21 Si 23.3 0.10(a) 2.33
Fe 15.4 0.40 6.16 O 123.0 0.15 18.45
C ... 0.08 ...
Si 23.3 0.10(a) 2.33
H ... 0.0150 ...
O 123.0 0.02 2.46
... ... N ... 0.03 ...
C 0.10
... ... Ni ... ... ...
H 0.0150
... ... ... Other ... (a) ...
N
... ... ... Corrected ... 886
Ni
Other ... (a) ... constant(c)
... Sum of element ... 53
Corrected 886
constant(c) corrections
... Calculated b ... 939
Sum of element 86
corrections transus(d)
... Published b ... 935
Calculated b 972
transus(d) transus(e)
... Comparison ... 4
Published b 996
transus(e) error
... Ti-7Al- Timet ... ... Alpha- Al 21.1 7.30 154.03
Comparison 24
error 4Mo Timetal beta
Ti-6Al-4V RMI ASTM RS6400 Alpha- Al 21.1 6.75 142.43 7-4
grade 5 beta Mo 9.5 4.50 42.75
Mo 9.5 0.10(a) 0.95 Sn 4.2 0.10(b) 0.42
Sn 4.2 0.10(a) 0.42 Zr 6.9 0.10(b) 0.69
Zr 6.9 0.10(a) 0.69 V 11.8 0.10(b) 1.18
V 11.8 4.50 53.10 Cr 12.1 0.30 3.63
Cr 12.1 0.10(a) 1.21 Fe 15.4 0.10(b) 1.54
... Si 23.3 ... 0.00
Fe 15.4 0.00
Si 23.3 (a) 0.00 O 123.0 0.20 24.60
C ... 0.01 ...
O 123.0 0.02 2.46
... ... ... H ... 0.0130 ...
C
... ... N ... 0.05 ...
H 0.0150
... ... ... Ni ... ... ...
N
... ... ... Other ... (b) ...
Ni
... ... Corrected ... 886
Other (a)
Corrected ... 886 constant(c)
Sum of element ... 130
constant(c)
Sum of element ... 90 corrections
Calculated b ... 1016
corrections
Calculated b ... 976 transus(d)
Published b ... 1005
transus(d)
Published b ... 996 transus(e)
Comparison ... 11
transus(e)
Comparison ... 20 error
Ti-6Al- Timet ... ... Near- Al 21.1 6.50 137.15
error
Ti-6Al-4V Timet ASTM R56400 Alpha- Al 21.1 6.75 142.43 2.7Sn- Timetal alpha
Timetal grade 5 beta 4Zr- 1100
6-4 0.40Mo-
Mo 9.5 0.10(a) 0.95 0.45SI
Sn 4.2 0.10(a) 0.42 Mo 9.5 0.40 3.80
Zr 6.9 0.10(a) 0.69 Sn 4.2 3.00 12.60
V 11.8 4.50 53.10 Zr 6.9 4.50 31.05
Cr 12.1 0.10(a) 1.21 V 11.8 0.10(b) 1.18
Fe 15.4 0.40 6.16 Cr 12.1 0.10 1.21
Si 23.3 0.10(a) 2.33 Fe 15.4 0.03(b) 0.46
O 123.0 0.02 2.46 Si 23.3 0.50 11.65
C ... 0.08 ... O 123.0 0.09 11.07
... ... C ... 0.04 ...
H 0.0150
... ... ... H ... ... ...
N
... ... ... N ... 0.03 ...
Ni
... ... Ni ... 0.02 ...
Other (a)
... Other ... (b) ...
Corrected 886
Corrected ... 886
constant(c)
Sum of element ... 86 constant(c)
Sum of element ... 135
corrections
Calculated b ... 972 corrections
Calculated b ... 1021
transus(d)
Published b ... 996 transus(d)
Published b ... 1015
transus(e)
Comparison ... 24 transus(e)
Comparison ... 6
error
Ti-3Al- Timet ASTM R56320 Alpha- Al 21.1 3.50 73.85 error
2.5V Timetal grade 9 beta Ti-6AL- Timet AMS 4981 R56260 Alpha- Al 21.1 6.50 137.15
3-2-5 2Sn-4Zr- Timetal beta
6Mo 6-2-4-6
(continued)
(a) 0.10 each/0.40 total. (b) 0.10 each/0.30 total. (c) Base constant (882) + adjustment (4) = corrected constant (886). (d) b transus = corrected constant + [sum of element corrections], or b transus = corrected constant + [(21.1 Al)
(9.5 Mo) + (4.2 Sn) (6.9 Zr) (11.8 V) (12.1 Cr) (15.4 Fe) + (23.3 Si) + (123.0 O)]. (e) Calculated values are ±24 C of published data with minor correction. Specification accuracy is ±15 C.
Table 18 (Continued)
(a) 0.10 each/0.40 total. (b) 0.10 each/0.30 total. (c) Base constant (882) + adjustment (4) = corrected constant (886). (d) b transus = corrected constant + [sum of element corrections], or b transus = corrected constant + [(21.1 Al)
(9.5 Mo) + (4.2 Sn) (6.9 Zr) (11.8 V) (12.1 Cr) (15.4 Fe) + (23.3 Si) + (123.0 O)]. (e) Calculated values are ±24 C of published data with minor correction. Specification accuracy is ±15 C.
multipliers. Greater b-transus temperature preci- Both the sample and an inert reference mate- used for the phase-change temperature determi-
sion is possible by calibrating and correlating it rial not undergoing a phase change, typically nation. However, for greater reliability and accu-
with metallographic method data—the “gold Al2O3, are thermally cycled together in an inert racy, the cooling (exothermic) direction was
standard.” atmosphere (Fig. 26). When a phase change selected. The b-transus temperatures are marked
Titanium producers often modify the equation occurs in the sample, its temperature briefly as the first dip in the cooling curve from right to
for critical, proprietary applications where tem- rises higher in an exothermic reaction, or drops left (Fig. 28) (Ref 42).
peratures must be precisely under or over the lower in an endothermic reaction, than the ref- There was good correlation between the
b-transus temperature for rigid mechanical prop- erence, depending on the heating or cooling DTA and metallographic methods, as indicated
erty requirements by customers. direction. by a linear relationship between the two meth-
Due to its speed and accuracy, the calcula- The differential temperature, DT, between ods, with data points closely fitting a straight
tion method is the method of choice for tita- the sample and reference materials is plotted line (Fig. 29) (Ref 42). Comparison to pub-
nium producers. Certification of the minimum against temperature. Any exothermic or endo- lished data indicated the DTA readings were
b-transus temperature of each heat is usually thermic temperature changes occurring during +71 C (128 F) high, suggesting an offset
done by this method. a phase transformation are indicated by brief was needed to compensate for instrument error.
changes in the slope of the DT versus tempera- After adding a 71 C (128 F) correction to
ture curve. The temperature where these deflec- the DTA results, there was excellent ±14 C
High-Temperature Differential tions occur indicates the phase-change location. (±25 F) agreement between the DTA and pub-
Thermal Analysis Method Figure 27 is a diagram of a typical DTA/DSC lished data (Table 19), indicating feasibility of
chamber. The DSC systems can be used for the DTA method.
DTA. The DTA method for industrial b-transus
The article “Heat Treating of Titanium and
Figure 28 shows DTA curves for the b-transus temperature determinations has lost favor due
Titanium Alloys” in Heat Treating, Vol 4,
temperature determination for Ti-6Al-4V and to replacement by the calculation method, but
ASM Handbook, 1991 (Ref 2) indicated that
CP titanium. Typically, the heating direction is it still is used for research. There is increased
the differential thermal analysis (DTA) method
was the preferred method by titanium producers
for determining b-transus temperatures. Cur-
rently, mill producers favor the calculation
method as the first choice, followed by the
metallographic method.
Very little information is available about DTA
currently being used commercially, but a brief
discussion about it is included for reference.
High-temperature DTA can determine
b-transus temperatures. The method is based
on the principle that heat is either released or
generated during phase transformations, depending
on the heating or cooling direction. Brief changes
in the rate and direction of relative temperature
differences, DT, between the sample and an inert
reference material determine the b-transus tem-
peratures. This method is similar to the DSC
method. However, DTA differs from DSC by
not quantifying energy measurements for transi-
tions, phase changes, and melting points, while
DSC can do these measurements. Fig. 27 Diagram of differential thermal analysis/differential scanning calorimetry chamber
Temperature, °F Temperature, °F
930 1380 1830 930 1380 1830
DTA temperature, °F
Heat
Exothermic
Exothermic
Metallographic temperature, °F
1000 1830
⌬T
⌬T
Cool
Endothermic
Endothermic
0.2 °C
Cool
0.2 °C 900 1650
1005 °C
1058 °C
Fig. 28 b-transus temperature determination by differential thermal analysis method for Ti-6Al-4V and commercially
pure (CP) titanium. Size: 50 mg (nominal); progress: 10 C/min; mode: cycle; atmosphere: argon. (a) Ti-6Al-4V, Fig. 29 b-transus correlation between differential
b-transus temperature = 1058 C (1940 F). (b) CP titanium, b-transus temperature = 1005 C (1840 F). DT, differential
thermal analysis (DTA) and metallographic
temperature. Adapted from Ref 42 methods. Adapted from Ref 42
Table 19 Differential thermal analysis (DTA) b-transus data comparison to published data
Published b-transus temperature, C
Measured DTA b-transus temperature, C Timet CP grades
Published data summary 35A 50A 65A 75A
Original(a) Normalized 71 C(b) Fe, wt% 0.20 0.30 0.30 0.50
Alloy Error (average published data) Normalized value Range Low Average High Alloy Dynamet(c) Metals Handbook(d) Timet(e) O, wt% 0.18 0.25 0.35 0.40
Ti-6Al-4V 1058 +57 987 14 982 1001 1020 Ti-6Al-4V 982–1010 990–1020 982–1010 ... ... ... ... ...
CP titanium 1005 +85 934 +14 890 920 950 CP Ti 899–927 910–945 890–950 ... 890 915 920 950
(a) Ref 42. (b) Good ±14 C agreement after 71 C normalization. (c) Dynamet (Carpenter Technology) specification. (d) Ref 3. (e) Timet specification. Source: Ref 42
equipment expense involved with it since most ASM Handbook, ASM International, 2004, 23. H. Ricardo et al., Kinetics of Thermal
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