pter 3 nderstanding the Metallurgy of Titanium I Structure and Alloy Types TALS generally have simple atomic ar- fs compared to ceramics and plastics. atoms, which can be pictured as hard for convenience, are stranged on crys- AA sain is formed by the ageregate of similar crystals of a given metal p. The orientation of lattice aggregates differs over distance and so a metal J3s Gtanium is composed of many grains Seliberately grown as a single crystal each stain the orientation ofthe lattice is the same with distance but across a Boundary the next grain will have a dif- spatial orientation ‘idtion to the existence of grains and nt grain boundaries, titanium is an al- clement; that i, it exists in more than ‘eqptallographic form. At room tempera- Stanium has a hexagonal close-packed festa structure, which is refered to as e phase. This stracture transforms to a tered cubic (bee) crystal. stecture, “peta” phase, at 888 °C (1621 °F), Beta and alpha phase hard-sphere models are in Fig. 13. is common to separate the alloys into four -beta(alpha-plus-beta) imes a category of near-beta is also con- ‘These categories denote the general type of nucture after processing. _(Micro- refers to the phases and grain struc jpesent in a metallic component.) The cate listed describe the origin of the racture in terms of the basic crystal favored by an alloy composition an alloy with only alpha phase present becomes an alpha alloy. Crystal strucure and grain structure (ie., microstucture) are not Synonymous terms. Both must be specified to completely identify the alloy and is expected ‘mechanical, physical, and corrosion behavior. ‘The important fact to keep in mind is that, \hile grain shape and size affect behavior, the crystal structure changes (from alpha to beta and back again) that occur during processing play a major role in defining titanium proper- lies. Chapter 12 covers this subject in deal. |Lrem | Lreatontr-e | mae brew | Ti8A12582r2Mo TieAnMoTV Uresai2ss ‘Stabilizer Concentration Phase Diagrams—Road Maps for Alloy Relationships. The phase relationships in alloy systems can be represented by phase diagrams When more than two elements are present, its slfficult t0 show the quantitative relationships, Pseudobinary phase diagrams, however, ute useful way fo show behavior, especially on a comparative basis, Figure 3.1 shows the compositions of some US. alloys marked on such @ toad map, a Pseudobinary phase diagram where the compo- ¢ | [Conse [ erasueszca THI Se 824 0 Ti0v.2rezar Fig. 3.1 somes siloycompostonsrelativetoapseudobiniytanium phase diagram14 / Titanium: A Technical Guide sition axis represents the amount of beta phase stabilizing clement, The diagram clearly shows. that alloys such as Ti-5AL-2Sn-4Zr-2Mo ate ‘ner-alpha” alloys because they ate barely into the alpha-plus-beta region of the phase dis ‘gram. Alloys such as Ti-13V-11CE-3AL, how. fever, are clea in the high end of the alpha~ plus-beta Tegion and, owing to slow transfor. Imation kinetics, will remain beta on cooling from higher temperatures. The Mi and M, lines introduced into’ the diagram refer 0” non- ‘equilibrium martenstie phases introduced dur 2 Typical mlcrstucure of alpha, apa pls haan ain alos a quand @ sloyed Ter hat 699° 1250 1) Equoxed 2B) acca In T-GALAN (Equa Bin Tanencesal ing “rapid” cooling, a8 in steel. Martensitic phases are discussed shortly. ‘Crystal Structure Behavior. An alpha al- oy (60 described because its chemistry favors alpha phase) does not normally form beta phase fon heating. A near-alpha (sometimes called “Superalpha") alloy forms only limited beta phase on heating, and so it may appear micro- Structurally similar to an alpha alloy when viewed at ower temperatures. An alpha-beta alloy is one for which the composition permits Complete transformation to beta on heating but transforms back to alpha plus retained and/or transformed beta at lower temperatures. A near-beta or bela alloy composition is one that tends to retain, indefinitely at lower tempera tures, the beta phase formed at high tempera: tures) However, the beta that forms on intial cooling to room temperature is metastable, De~ pendent on chemistry, it may precipitate sec- fondary phases daring heat treatment. ‘Microstructures show variations in the mor- phological development ofthe alpha phase and Temperature, °F N strostctres ofan annealed ner alps allay (TEAM) ter cooling tom diferent areas of he pase PAIS Retaraighe bl Equedalpha and iterganularbea (Fine sipho-bets structure Fig. 3.3, the beta phase, which are dependent on alloy chemistry, prior Work, temperature from whici fooled, and rate of cooling. Coarse and fine fcicular structures can be produced, but equiaxed structures also are possible. (This topie is discussed later in this chapter) Typical titanium microstructures are shown in Fig. 3.2 ‘The microstructures shown are intended 0 be representative but definitely not all-inclusive because the actual microstructure depends on chemistry and processing. Figures 3.3 and 3.4 give some addtional ilustrations of the effect fof prior temperature (and cooling rate) on microstructure of a near-alpha and an alphs- beta titanium alloy Effects of Alloying Elements Alloying elements generally can be classi- fied as alpha stabilizers of beta stabilizers. Al~ pha stabilizes, such as aluminum, oxygen, and -- =~ 6 Transusfeu phase dgram plus miciostecures of an anne alpha alloy (T-6A-A) ate cooling 34 Composton niet Acer spe esorned bt rh pos bea pan Boonen Nie a es. rans primary alpha igh in ara ftraneonmed bets cokning tap tl Ele piney a gen, inerease the temperature at which the phase is stable. On the other hand, beta izes, such as vanadium and molybdenum, it in stability of the beta phase at lower peratures. The transformation temperature lpha-plus-beta or from alpha to all beta is wa as the beta transus temperature. The ‘ransus is defined as the lowest equilib- temperature a which the material is 100% ‘The beta transus is ertial in deformation sing and in heat treatment, 2s described wv. Note that che bets transus for T-6AL-4V shown in Fig. 3.4 Below the beta transus temperature teniuim ‘2 mixture of alpha-plus-beta if the material tains some beta stabilizers; otherwise itis alpha if it contains limited or no beta stabi- ‘The beta transus is important because ssing and heat treatment often are caried with reference to same incremental tempet- above or below the beta transus. Alloying ents that favor the alpha crystal structure stabilize it by raising the botatransus tem- Understanding the Metallurgy of perature include aluminum, gallium, germe ‘nium, carbon, oxygen, and nitrogen ‘Two groups of elements stabilize the beta crystal structure by lowering the transforma tion temperature. The beta isomorphous group consists of elements that are miscible in the beta phase, inchuding molybdenum, vanadium, tantalum, and columbium. ‘The other group forms eutectoid systems with titanium, having ceulectoid temperatures as much as 333 °C (600 °F) below the transformation temperature of unalloyed titanium. The eutectoid group in- cludes manganese, icon, chromium, cobalt, nickel, copper, and silicon. ‘Two other elements that often are alloyed in titanium are tin and zirconium. These elements have extensive solid solubilities in alpha and beta phases. Although they do not strongly pro ‘mote phase stability, they retard the rates of transformation and are useful as strengthening agents. The effects and anges of some alloying elements used in titanium are indicated in Table 3 Water quenched from diferent areas ofthe phase fel) Diagram with 6A ie] mat wth eta ar a ror Beta a marco spa pment ‘The transformation temperature (beta trans for completion of transformation to beta on heating) is strongly influenced by ‘© The interstitial elements oxygen, nitrogen, and carbon (alpha stabilizers) which ra the transformation temperature ‘© Hydrogen (beta stabilizer), which lowers the transformation temperature Table 3.1. Ranges and effects of some alloying elements used in titanium ‘Aueioum | ‘Alp sablzer tn Apt baer Gemien Sat elie Coe emilee tian Alpharnete16 / Titanium: A Technical Guide © Metallic impurity or alloying clements, Which can either raise or lower the transfor- ‘ation temperature ‘The role ofthe interstitial elements oxygen, nitrogen, and carbon was already mentioned, ‘The substitutional alloying elements, such as tantalum and vanadium, also play an important role in controlling the microstructure and prop ctics of titanium alloys. Tantalum, vanadium, and columbium are beta isomorphous (ie. have similar phase relations) with bee titanium. Titanium does not form intermetallic com pounds with the beta isomorphous elements Eutectoid systems aro formed with chro- ‘ium, iron, copper, nickel, palladium, cobalt, manganese, and certain other (ansition metal. ‘These elements have low solubility in alpha t ‘anium and decrease the transformation temper ature. They usually ae added to alloys in com: bination with one or more of the bela isomorphous elements to stabilize the beta 5 Mc wl manent Fig.3. phase and prevent or minimize formation of Inermetallic compounds that can occur during service at elevated temperature Zigeonium and bafoium are unigue in that they are isomorphous with both the alpha and beta phases of titanium. Tin and aluminum hhave significant solubility in both alpha and beta phases. Aluminum increases the transfor- mation temperature significantly whereas tin Towers it slightly. Aluminum, tin, and zirco- nium commonly are used together in alpha and ha alloys, In alpha-beta alloys, these el- ements are distributed approximately equally between the alpha and beta phases. Almost ail commercial titanium. alloys contain one or ‘more of these three elements because they are soluble in both alpha and beta phases, and pat ticularly because they improve creep strength inthe alpha phase, ‘Many more elements ate soluble in beta ti nium than in alpha. Beta isomorphous alloying elements are preferred as additions because they do not form intermetallic compounds. However, iron, chromium, manganese, and ‘other compound formers sometimes are used in beta-rich alpha-beta alloys or in beta alloys be- eause they ate strong beta stabilizes and im- prove hardenability and response to heat treat- ment, Nickel, molybdenum, and palladium improve the corrosion resistance of unalloyed titanium in certain media. Transformations and Secondary Phase Formation Intermetallic Compounds and Other Secondary Phases. Intermetallic compounds and transient secondary phases are formed ia titanium alloy systems along with micro- scvtural variants of the traditional eta and al- pha phases, The more important secondary Dhases, historically, have been omega and ale ig. 3.6 Micosrucre oan alphabets ttn alloy T-6A-1 ate slow cong fn above the bet ans. The ths eo sve pts ae and th dak gens een then re. Thiel Wms see, Ope pha-2, chemically written as TiAl. Omega Phase hss not proven tobe a factor in commer- systems using present-day processing practice. Alpha-2 has heen considered to be a ‘concern in some cases of sress-corrosionerack= ing. (Most presen interest in alpha-2 centers on its use as & matrix for a high-temperature tits nium alloy where stress-corrosion may not be & factor.) ‘When phase transformations occur, they ean be fusion controlled and modersely fast of they ‘an be dlifusionless (no composition change) and very rapid. Diffusionless transformations usually ead to nonequilibrium phases, (Martensits in steel are phases formed by a diffusions transfor mation.) Martensic nonequilibrium phases exist in some ttasum alloys. Martensites and Transformed Beta (Acicular Alpha). The decomposition of beta phase in titanium alloys can take place by ‘martensitic transformations, and this frequently hhappens in the alpha-beta alloys. Nonequili ‘ujum martensite phases are produced in al- pha-beta alloys a8 function of alloy chemistry and. processing. There are several of these martensite types formed in tanium, The beti- to-marensite transition is responsible for an scicular (plate-like) structure in quenched andlor ‘quenched and aged titanium alloys (Fg. 33). Other acicular or lenticular plate-like struc tures can appear in titanium alloys without the formation of martensite. Figure 3.6 shows al- pha platelets formed by slow cooling from the beta region. Since plate-like stractures can be alpha or martensite, it i necessary to fully characterize the behavior of any given alloy. Figure 37 shows the rang of structure that ean exist in a superalpha alloy (a description of superalphaalloysis presented later inthis chap ter), The alpha that forms from beta is inva ably acicular but with different degrees of fine- ress of structure. For Ti-6AL-2Sn-1Zs-2Mo-0.28i, itean be seen that a very fine alpha (Fig. 3.78) ‘can result ftom transformation of beta, of & te: atively coarse alpha platelet structure (Fig. 3.6 and 3.7b) can be formed. It may be diffcule for the casual observer to recognize the difference between martensitic transformed beta and plate-like alpha formed from beta, Prior know edge, including alloy chemistry and processing condition, is necessary 10 properly identity the phase present Although s number of martensites were re ported over the years, the two principal ‘martensite turned out to be alpha prime and pha double prime. Alpha prime, appearing as tn acicular phase, is hexagonal in crystal lattice structure but similar in microstructural appear- nce to acicular alpha. (Acicular alpha is dis- cussed inthe section “Microstructural Develop- ment in Titanium Alloys" in this chapter. Alpha double prime is a supersaturated ortho: rhombic phase. Alphs-prime and alpha-double- prime martensites are brought out by cooling, and they decompose, on subsequent aging, to alpha and beta phases. Cooling rate plays an important role in the creation ofthe martensite phases.‘Microstructural Ranges in Titanium Al- Heys. A graphic illustration of the range of Serosiructural transformation variations that Fig 3.8 (earsormed Bator Brain boundares pa phase present at the time of cooling (primary alpha) can remain relatively globular (equiaxed), but the transformed beta (martensites or alpha) canbe very acicular of elongated, The amount of ‘equiaxed alpha and the coarseness or fineness of the transformed beta products affect the alloy properties of titanium. SEMIS NS SPAN 7 pac pa (Wits ofan aipha-bt aia alloy T-6A -4V) in epresenative metre! conn (a quand ard asl aunt of inerrant Bb Exulned ar seu @ anda sal runt ie |gevela (6 Equiared a ina aciularetrantonmed 8 mat Salat of tana onan ater rane ‘Rees ft: Pate ail transformed Bator grain bounds loky and plat Me sear 3.7 Optical micrograph of ttaniam lly 61-250 4%-20-0.281 aera 2/1024 11876 Fico and) 2968°C(1774"F¥sr col Metastable beta can show more variety in de- ‘composition than does the supersaturated alpha ‘or marensiic alpha structure, The omega ‘Phase ean form from beta, as ean alpha phase and a low-solute-content beta phase, Other intermetallic compounds also can form, and, under certain circumstances, ordering Of the beta phase can occur. (Ordering removes the randomness in atom location that normally ex- ists and puts atoms in specific locations.) Hardenability isa term much used in stel technology fo describe the ability to create & level of harness where it is desired by achiev ing a specific amount of martensite, The same concept is sometimes used in titanium technol- ogy. Hardenability of a titanium alloy is a Phrase that refers to its bility to permit full transformation of the alloy to tansformed beta (martenstes, alpha) or to retain beta to room temperature. Titanium Groupings General Background. Although the four categories or clasts of titanium have been de~ scribed, a slightly different classification or grouping is sometimes used in commercial practice. For example, its common to group ti- ‘anium materials as © Unalloyed (CP) © Alpha and neae-alpha © Alpha-beta| © Metastable beta Table 22 lists the room-temperature tensile property levels and the chemistries for some commercial and semicommercial titanium agrades (ie, kinds) and alloys currently avail- able, A more comprehensive listing of compo- sitions for many CP grades is given in Table 3.2. A similar comparison listing for commer- cial alpha, near-alpha, alpha-beta, and beta al- Joysis given in Table 3.3,18 / Titanium: A Technical Guide The different titanium families or groupings have different characteristics, as would be ex pected, Figure 39 shows schematically the Iain characteristics of the titanium alloy fam: ily groupings (excloding commercial purity ti- tanium) with a few alloy compositions indi- cated for reference Unalloyed titanium, generally known as ‘commercial purity (CP) titanium is the weakest ‘but most corrosion-resistant version of the metal, The interstitial elements oxygen and ni trogen greatly strengthen “pure” titanium, CP titanium takes advantage of the interstitial hardening of oxygen and the effects of small additions of olher elements (eg, iron and pal: Jadium) t© provide for various grades of the metal to fit a variety of applications. The pr ‘ary difference between CP grades is oxygen and iron content, and oxygen content is the principal regulator of tensile properties. (Refer fo Appendix B for more information on srades.) Grades of higher purity (lower intesti- til content) are lower in strength and hardness, and have a lower transformation temperature, than those higher in interstitial content. ‘Unfortunately, although oxygen and nitrogen are not only strengtheners of titanium, they ean be difficult to keep oat of titanium alloys due to the high solubility of the interstitial elements, Thus, atmospheres containing oxygen oF nitco- gen create problems that are not concers ith ‘most other metals, ‘Oxidation is always of concern in ele. vated-temperature operation. Heating titanium insir at hightemperature results not only in ox ‘dation bat also in solid-solution hardening of the surface a a result of inward diffusion of ox- yygen (and nitrogen). Whea titanium aad its a: loys are heated in an oxygen- oF nitrogen-con taining environment, a surface-hardened zone is formed. This surface-hardened layer is re ferred to as “alpha case” because oxygen and nitrogen stabilize the alpha phase, Alpha case (Qhe “si-contamination laye) is hard and beit- tle and invariably detrimental to service application. Nommally, ths layer is removed by chemical mulling, pickling, or machining or by other mechanical means prior to placing part in service because the presence of alpha case das- tically reduces fatigne strength and ductility. Castomarly, CP titanium is selected for its excellent corrosion resistance, especially in ap- Plications where high strength is not required Yield strengths of commercially pure grades ‘may vary from about 170 MPa (25 ks) to about simply as a result of varia ‘ions in the interstitial and impurity evel, with strength increasing as the oxygenfnitrogen (and inon) contents increase (Table 2.2) ‘Alpha and Near-Alpha (Superalpha) Al- loys. Alpha alloys are alloys with relatively large amounts of alpha stabilizer and low con: centrations of beta stabilizers. Such alloys gen rally are more resistant 1 creep at high tem- perature than alpha-beta of beta alloys, Within the alpha and near-alpha systems, those alpha alloys that contain aluminum, tin, andor zitco- nium are preferred for high-temperature and cryogenic applications. However, ductility and toughness of alpha-rich alloys are compromised at cryogenic temperatures unless interstitial content is reduced, Reduced-interstita-level i> tanium alloys are designated “extra low inter- stitial” (ELD. The higher cost, ELI alpha alloys retain ductility and toughness at cryogenic tem: peratures. TI-SAF-2.5Sn-ELI was one alpha al Toy used extensively in eyogenit applications. ‘Because there is limited phase transforms tion under normal heat treatment conditions (structure stays all alpha oF almost all alpha, alpha alloys usually cannot be strengthened by deat treatment, Near-alpha or superalpha alloys are made by introducing some amount of beta Stabilizing elements to an alpha-alloyed chem- istry. The superalpha alloys are somewhat heat treatable Grain structure changes in alpha and super- alpha alloys are made by inducing recrystal= Table 3.2 Comparison of some commercially pure titanium mill products lization through cold work and annealing. Re- sidual stresses induced by cold working of al pha and superalpha alloys are relieved by Stress-relief annealing or reerystallization an- nealing, Microstructure changes are effected by ‘modifications in the maximum solution-tea ment temperature and the cooling rates from solution heat treatment, Reference should be made to Fig. 3.7, which shows optical micro- graphs of a superalpha titanium alloy (Ti-6AL- 2Sn-4Z1-2Mo-0.1Si) as influenced by changes inthe heating and cooling conditions. Ti-BAI-IMo-1V and Ti-6A-2Nb-ITa-0.8Mo are examples of alpha alloys that contain small additions of beta stabilizers. These alloys have been classed as near-alpha or supereipha alloys. ‘The modest amount of beta-favoring elements provides fora very small amount of beta to be Formed in the microstructure during processing Although the alloys contain some retained beta phase after heating and cooling, they consist Primarily of alpha phase and tend to behave ‘more like conventional alpha alloys than sl pha-beta alloys. Because the alpha phase isthe ‘more creep resistant of the phases in Ganium alloys, superalpha alloys ave outstanding creep Strength. Because aluminum is frequently used to achieve the superalpha structure, suck alloys may have a greater tendeney to produce the alpha-2 phase that has been implicated in hot-salt stress-corrosion cracking of titanium: alloys. In the superalpha alloys, stress-corr- sion resistance is limited and care must be exer cised in the use of such material One benefit of alpha alloys is their intrinsé cally good weldabiity, which stems from the fact that alpha alloys generally are insensitive to heat treatment, However, the alpha alloys usually have poorer forgeability and narrower forging temperature ranges than alpha-beta or beta alloys, particularly at temperatures below the beta tfansus. This poorer forgeability is manifested by # greater tendency for center bursts or surface eracks to occur, Which means Chet cmp Asta 1 ONS RID, © ti sca? ‘ois ASDipsie2 ONSRSOM ‘o Dates bs Asintpade3 ONS RS © fstwgnss{UNS RSID, ° ‘state 10831525 8 AStMtpnde21UNSTOROD ols ‘ines 02s 00 390-540, as ed aio ae BeehENBERE eefat small reduction steps and frequent reheats faust be incorporated in forging schedules. Iso- Ahermal forging processes can reduce ths prob- Jem. (More information can be found in Chap- mer) Alpha-Beta Alloys. When a blend of eta-favoring und alpha-favoring alloy cle- fonts is added to titanium, alloys with struc fers inthe alpha-beta range may form, Alloys fn alpha-beta systems contain one or more a: pha stabilizers (¢., aluminum) or alpha-solu Bic clements plus one or more beta stabilizers eg, Yanadium, molybdenum) in larger amounts Gan in near-alpha alloys. By moving alloy Understanding the Metallurgy of Titanium / 19 chemistry away from the alpha solyus phase boundary, these alloys form significant bets phase when heated. When sufficient beta formers are present, it is relatively easy 10 eX ceed the beta transus by heating, and the alloy will be all beta before subsequent cooling, The alpha-betaslloys can retain significant untrans- formed beta after solution treatment and cooling “The transformation of lowersemperature al- pha to highertemperature beta phase, which fakes place upon heating alpha-beta titanium al- loys, is complete if the heating. temperature {goes above the beta transus, The formation of a Titde beta or a complete structure of beta per- ‘Table 3.3(a) Compositions of various alpha and near-alpha titanium alloys mits alpha-beta alloys tobe strengthened by s0- lution treating (exceeding the beta transus, or at least producing significant beta phase for sub- Sequent transformation) and aging (heating 10 produce further change in the transformed beta—martensites, acicular alpha—and the re tained beta). ‘The specific amount of beta available for transformation from a fixed temperature de- pends on the quantity of beta stabilizers present and on processing concitions. A wide variety of microstructures ean be generated in alpha-beta, alloys by adjusting the thermomechanical pro- ‘ess parameters. It should be noted that beta Meine toying ents “B25Cu (ACMA designation, HPI) Fes (AECMA str oN252 an 251) 00s 00k oar a2 03 staaotae 2020¢e Seco rEN2 andes nos ba diz 0203 daar 2oace SANDS) TESAL2S80(UNS designation RSIS) INIT lny WL3.7115) ons 008 0m aso 4069 20-30 AS 10pm hosp) ous oa om 303 omit) asist5 200-40 “AMS #25 (hrs esa AMS 96 en) Imprints as AMS 410 ‘don-600 20-300 ASTD 25 (pe ters) oo: 010" om Os 02) inca 20n80 arraasig ASIME 3h Garileysal ASTMB3S1 Gaping) O08 0100S OF 0 ‘in0.600 200-300 STA Caen Ons 010 Ons a3 2 nse Sm-600 200300 “TSA2SSn LI (UNS designation R521) 9.909 pa she. sp) ms 00s 00s 02512 O+Fe=022, 200-300 05,005, Ans #72s ou orn) ms 005 o0ns 02s 012 OeFe=aa 47056 200300 ates) wriusse) 00s 010 oots os om O58; gm-509 208-800 BAALIY-1No(UNS REASON ACMA Te py nitrate 5 1 w FASS 115.1916 955 (inn, 855(vn, 4720S O08 DAIS OSD DID OMY) 738-838, O7S-125 075.125 Mansi tine vin) 01s ons 00050290120 735.835 orsias arsiasv SOO UNSRSLEADK) 2352919.1975,976, 0s 00s o0ns 2s as yas, 550.65) 1822 1644 1822 85. axremmem ining) 00F 005 001s 02s OS oNtSOsme $50.60 1822 3644 1822 GALAN. 1TH.A5Mo (UNS RSGEIO) a om ons ons on oo ‘ of omits TES goverment) Om Ons ORS 35 BID Osta sss assim “15250 osist 9 UNSRSET) Type om 008 ome oon 225m 1 ose IAS 174, orig) Ooi Of OOS BOIS Myowiy “2045” MSHS oo aSL2 BIST: Sesh TA IS: TANS TADS nd TA2 ons 020 2023 1nsuis aban OS12 “ONLOssi TOR BeenTAmTAD ovis a0 2025 Insts 40-60 a8:12 SamewTA2T (er neat ays Baas.) 6 2 2 oon PesALSor72Nat) cis Gis ims ois ola $5 3 ks Besaiase see ee ema mass ss 353 tas tego) mass er ‘ace 00 om 007 ee a cal Sep gt in Sons oy Tes = penyGaetedarasaesta was abaya20 / Titanium: A Technical Guide formed at high temperatures and transformed to alpha or martensitic variants when cooled is often referred to as transformed beta, While this is a good generalization of the micro- structural changes occurring, it dacs not do justice to the actual microstructure of alpha- beta systems. Heat Treatment of Alpha-Beta Alloys. Solution treating usually is dose at a tempers ture high in the two-phase alpha-bota fied and is followed by quenching in wate, oil, or n= ‘ther soluble quenchant, As a result of queneh- ing, the beta phase present at the solution-reat- ing’ temperature may be retained or may be parly transformed during cooling by cither ‘martensitic transformation or nucleation and growth (conventional dffusion-contolled phase formation) reactions. The specie response de pends on alloy composition, solution-teating Temperature (bete-phase composition a the S0- lution temperature), cooling rate, and/or section size, Solution treatment is followed by aging, normally at 480 to 650 °C (900-1200 *F), to precipitate alpha phase and produce a fine mix- ture of alpha and beta in the retained or trans- formed beta pase Transformation kinetics, transformation products, and specific response ofa given alloy can be quite complex; a detailed review ofthe stibject is beyond the scope ofthis book. Chap ters 4, 7, and 9 contain addtional discussions ofthe transformations and microstructures in i tanium, as affected by wrought alloy deforma. tion processing and heat treatment. Also refer to the discussion of microstructural develop- ‘ment in titanium alloys, which follows, Response to solution treating and aging de- ppends on section size; alloys relatively Tow in beta stabilizers (eg, Ti-GAI-8V) have. poor hhardenability and must be quenched rapidly to achieve significant strengthening. It has been shown that proper solution treating and aging can increase the strength of alpha-beta alloys by 30 to 50%, or more, over the annealed or Table 3.3(6) Compositions of various alpha-beta titanium alloys fover-aged condition. Adequate cooling rates ate often difficult to achieve unless section sizes are small, For Ti-6A1-4V, the cooling rate of a water quench isnot rapid enough to signifi- ‘cantly harden sections thicker than about 25 ‘mm (1 in), Hardenabilty increases asthe content of beta stabilizers increases. Tr-SAL-2Sn-2Zs-4Mo-4Cr, for example, ean be through-hardened with rel- atively uniform response throughout sections up to 150 mm (6 in) thick, For some alloys with intermediate content of beta stabilizers, the surface of a relatively thick section can be strengthened, but the core may be as much as 10 to 20% lower in hardness and strength. It must be remembered thatthe strength that can be achieved by heat treatment is also a function of the volume fraction of beta phase present at the solution-treating temperature. In view of the cooling rate requirements, alloy composi ‘ion, solution temperature, and aging conditions ‘must be carefully selected and balanced t0 pro- ‘TH4aLav UNSAID) easter ENDS oe ge DIN TSS by WL3.785) AMS 908 la) AMS 06 ep) |AMSA91 pas rt ip) ‘Asa 508 and 96 ASIM45 et ant F468 ts) TAV-EL1 (UNS R864) AMS 907 kano ‘ms 99st ASIMF sit) |ASTBUF 47) F468) Ti6uL6v-28n(UNS REGARD) Tpit ANS to18 036 997,498, AMS-979 np) ter pa betas ‘UNS Seno Gnas 08) UUNSSca0 gm AMS ON) Te42i6(UNS RS) Te? wean Table330) Teen a8n22-20+ 2M ‘T3AL25V GnaMSen4t) asso Tene) Taos) ® 8 ‘ oa edit ss675 bias SS.is w,o008y (ehovasy © ss07s as 30 ba, Sos Ss.878 Ssars tas o dasy ois 035-10 © ois ‘012s hhaias ois oFmovate ost Abies) asasv assy assy 7503.64 O35 cy, Sov 035 cy, Sowdace the desired mechanical properties in the Seal product Precipitation Hardening of Superalpha and Alpha-Beta Alloys. Precipitation harden- Sng (dispersion hardening by phases dispersed fn the matrix, generally on a submicroscopic scale) to increase creep resistance of titanium alloys was a significant goal of early titanium ‘development programs. Although the ability of Aipho-beta alloys to be precipitation hardened Se ways similar to nickel superalloys und alumi ‘eam was studied in laboratory programs from Ae inception of the titanium industry, the re- salts were not favorable. The most significant evelopment of precipitation-hardened tita- Ssum alloys came with the introduction of si ‘eon fo alpha-beta alloys 0 form a silicide pre~ ‘ipitae that seems to promote dispersion Tardening. One of the more important contin- ‘sed applications of creep-resistant alloys has Been the use of Ti6Al-2Sn-471-2Mo-0.25i, ‘About 0.25% or more of silicon can produce ‘sharply enhanced creep resistance, probably by 4 dispersion-hardening reaction that creates [astcle baiers to deformation. Metastable Beta Alloys. Beta alloys are ‘characterized by high hardenabilty, with the Imetastable beta phase eing completely re ‘ined on air cooling of thin sections of water sguenching of thick sections. Alloys of the smcastable beta systems are richer in beta stabi fizers and leaner in alpha stabilizers than al- pphs-beta alloys (Fig. 3.1), A major factor inthe ‘pplication of beta alloys has been the excellent Aoxgeabilty of alloys with cubic titanium lattice structures. In sheet form, beta alloys can be Understanding the Metallurgy of Titanium / 21 cold formed more readily than high-strength al- Dha-beta or alpha alloys Beta alloys are actually metastable alloys cold work at ambient temperature or heating to a slightly elevated temperature can cause par- tial transformation to alpha asthe alloy reverts {o the equilibrium condition, That metastability is exploited to produce exceptional structures from beta alloys. The principal advantages of beta alloys ae that they have high hardenabilty, ‘excellent forgeability, and good cold formality in the solution-treated condition, and can be hardened to fairly high stength levels. Because beta phase is invariably metastable and has a long-term tendency o transform tothe equilibrium sipha-plus-bera. structure, titanium producers use this tendency (to a point) by aging metastable beta alloys after solution treatment tnd fabrication. Temperatures of 450 t0 650 °C (650-1200 °F) are used to partially transform the metastable beta phase to alpha. The alpha forms 8 finely dispersed particles inthe retained beta, land room-temperature strength levels compara ble or sometimes superior to those of aged al- pha-beta alloys ean be stained. In the solution-teated condition (100% re- tained beta), beta alloys have good ductility and toughness, relatively low strength, and exce!- lent formability. Solution-trested beta alloys begin to precipitate alpha phase at slightly ele- vated temperatures and thus are unsuitable for clevated-temperature service without prior st bilization or over-aging treatment Beta alloys do have some disadvantages ‘compared fo alpha-beta alloys. The beta alloys usually have higher density, lower creep ‘Table 3.3(¢) Compositions of various beta titanium alloys strength, and lower tensile ductility in the aged condition. However, although tensile ductility is lower, the fractare toughness of an aged beta alloy generally is higher than that of an aged alphe-beta alloy of comparable yield Strength. Very high yield strengths—about 1172 MPa (170 ksi)—with excellent tough ness (Kg = 40 ksivin} have been claimed for the beta alloy Ti-1OV-2Fe-3A\, In general, the class of beta alloys serves a great need for tita- rium components that can be fabricated for rmoderate-temperature applications. Microstructural Development in Titanium Alloys Background. Titanium microstructure gen- eration has been mentioned frequently in this chapter. Tt should be apparent that once a chemistry has been selected, microstructures in titanium alloys usually are developed by heat treatment or other processing (wrought/east/powder metallurgy), which of ten uses heat and/or is followed by heat treat ‘ment. With the exception of CP titanium and alpha alloys. microstructural changes are in- variably produced through transformation of some or all of the alpha phase to beta phase. The microsinctre that results i a function of the ay in which the subsequent changes in beta or in residual (primary) alpha occur Microstructural change is limited to grain re- finement and, possibly, to grain shape changes in CP titanium and all alpha alloys. Typical a: Seine Seite Ne # o_extrwal_ a Me Ot Bava as=17 a a a) Iss TESaS¥, NSS, 00-128 Auswssoiwie) 00S osm 0357 amnsy ass nsiasy 0-120 ML 5086 es ams ons ats03s 017ml 28.38 nas, MLR ISH Toe ML 0050s os ost ns. NLP io-120ce Migviougiesemde 01S 00s 0008 Olmm, 6 asas nesta a 10-120 “Bo 6V2Fe2AI MILT, se Oe et tea ae oie 7S85 1585 (UNSRGN) MALT 97 aa Mra beac T5048, Cagle ieee Ons oe) eae ace S545 3545 75.85 UNSRSs6u) SMT 9D7 ant MILERIe2 Bet aMs7.4090, ons oD 08S tt 378525 4595 W010 ‘ASTM 38825, Bian Tovrea Roping oss 00s, apis teas ons asas 925-1025 ms Seay fers os oo oe an 2533 ass Ley, Bsc mn Erunecompeseraloy 008 0S aps 02s omeaas 4555 Le2e i624 asus adie Tamers Highs, ons om ams amas) 3332 ka SSE naostaow ‘lon pea Faves ghawegaoy 005g ants Swe) 128 55.85 nesov rane 129 2 1 sv Postagcatest nent) 0005 at ¥andO0A mas22 / Titanium: A Technical Guide pha-beta and beta alloy microstructural devel- ‘opment i covered fortwo selected alloys inthe following sections. i-GAL4V Microstructure. TI-6Al-4V is ‘one of the most widely used titanium alloys. It is an alpha-bets type containing 6 wi% Al and 4 yw V, Typical uses inelude aerospace appli= cations, pressure vessels, aircraft gas turbine disks, cases and compressor blades, and surgi cal implants. Ti-6Al-4V has an excellent com- bination of strength and toughness along with excellent corrosion resistance, ‘The properties ofthis alloy are developed by relying on the refinement of the grains upon cooling from the beta region, othe alpa-plus beta region, and subsequent low-temperature aging to decompose martensite formed upon quenching. When this alloy is slowly cooled from the beta region, alpha begins to form be- low the beta tansus, which is about 980 °C (1.796 °F). The alpha forms in plates, with a exystallographic relationship to the beta in which it forms. The alpha plates form with their basal (close-packed) plane parallel to a special plane in the beta phase. Upon slow cooling, 2 nucleus of alpha forms, and because of the close atomic matching along this com: ‘mon plane, the alpha phase thickens relatively slowly perpendicular to this plane but grows faster along the plane. Thus, plates are devel coped. Because thore aro six sets of nonparallel growth planes ina given beta grain, a steeture Of alpha plates is formed consisting of six noparallel sets. The Widmanstatten. micro structure developed is illustrated in Fig. 3.6 The formation process is shown schemati- cally in Fig, 3.10. I uses a constant-composi- tion phase dingram section at 69% Al to illas- trate the formation of alpha upon cooling. The darker regions ae the beta phase left between the alpha plates that have formed. The micro- structute consists of parallel plates of alpha de- Tineated by the beta phase between them, ‘Where alpha plates formed parallel to one spe= ciffe plane of beta moet alpha plates formed on another plane, a high-angle grain boundary ex- ists between the alpha crystals and etches tore veal a Tine separating them, This microstructural ‘morphology, consisting of these sets of parallel plates that have formed with a crystallographic relationship © the phase from which they formed, is called « Widmansttten structure Upon cooling rapidly, beta may decompose by a martensite reaction, similar to that for pare titanium, and form a Widmanstitten pattern ‘The structure present after quenching to 25 °C (77 °F) depends on the annealing temperature Different types of martensite can form, depend ing on the alloy chemistry and the quenching temperature. These are designated alpha prime and alpha double prime. Upon quenching from above the beta transus (about 980 °C, oF 1796 °F), the structure i all martensitic alpha prime fr alpha double prime with a small amount of beta (although in some alloys the beta has not been observed) ‘The presence of some heta in the structure after quenching from above the beta transus is {due to the fact thatthe temperature for the end of the martensite transformation, Mj, is below oom temperature (25 °C, of 77 °F) for this a Joy. That is because vanadium is a beta stabi- lizer, and the addition of 48% V to 8 Ti-6%Al alloy is sufficient to place the My below 25 °C Formingcapacty hot nd o 2 4 6 8 Vinadum cates, Fal mostcture consi ope 2 (wi) Fig. 3.10 scterticolhedeelpmentots Wisma peratures by sony cooing rom above to Bane oparaodby te fps 8") ster stature an alphabet lay 60-4)(77°F). Thus, pon quenching wo 25 °C (77 *P fot all ofthe beta is converted to alpha prime fr alpha double prime. For the commercial Ti-6AL-4V alloy, there fa some commonly used heat treatments For each of thoso, the following descriptions far typical of the temperatures and times fesed, The actual practice varies with alloy Broducer and user. Figure 3.11 shows some ficrostructares formed from Ti-6AL-4V al- Joy as a function of solution temperature and cooling rate Wister quenched 1005 -¢ (1950) 95510 #750") ed 00° (0680 "F) asso) Understanding the Metallurgy of Titanium / 23 To place the alloy in a soft, relatively ma- chinable condition, the alloy is heated to about 730 °C (1346 “F) in the lower range ofthe a: ppha-plus-heta region, held for 4 hours, then fumace cooled to 25°C (77 °F}. This treatment, called mill annealing, produces a micro: structure of globular crystals of beta i an alpha ‘matrix. A typical microstructure is shown in Fig. 3.12. ‘Another annealing treatment is duplex anneal ing. Several variants ofthis tweatmeat ae used, ‘Typiealy, the alloy is heated to 955 °C (1751 Aireooles Furnece cooted SU B11 fet of cooling rate on he mcrructr f an sphta alloy (T:6A-4V lo = pir beta gin F) for 10 minutes, then air cooled. It then is Deated to 675 °C (1247 "F) for 4 hours and air cooled 0 25°C 77 *F) With the aging treatment called solution treat- ing and aging, typically the alloy is heated at 955 °C (1751 °F) for 10 minutes, water quenched, then aged for 4 hours ata tempera fe between S40 and 675 °C (1004 and 1247 °F), followed by air cooling to 25 °C (77 °F). ‘Typical tensile mechanical properties for the three treatments are compared in Table 3.4, ‘The strongest alloy isthe one that has been so- lution treated and aged. The mill-annealed con dition is stronger than the duples-annealed con dition, but the difference is slight. Ti13V-11Cr-3Al Microstructure. The sec: ond alloy to be considered is a beta alloy, T-13V-IICr-3AL, This alloy is historically im portant as the first eta alloy to see significant ‘sein an aircraft Body-centered cubic alloy elements (vana ium and chromium have bee crystal struc tures) used to stabilize the beta phase in tita- nium raise the possibility of the development of 4 eutectoid alloy reaction, Figure 3.13 shows the two basie types of phase diagrams for bi nary beta-stabilized titanium alloys. The hor zontal line above the alpha-plus-gamma phase field in Fig, 3.13(b) is the eutectoid tempera ture, and the possible transformation of the beta phase directly to alpha-plus-gamma on cooling ‘escribes the eutectoid reaction Tt might be supposed that in a system with a eutectoid reaction, rapid cooling from the beta region can lead t0 a martensite structure ia the samme way that steel martensites are formed However, the martensite formed in quenching or rapid cooling of tho beta structure is alpha prime, whichis not particularly strong. Conse ‘quently, as determined for alpha-beta alloys, quenching may be necessary to achiove ade- quate property levels in thicker material sec dons, but strengths and hardness levels com- rmensurate with the martensites of steels will not be achieved, a te aire eee ours Prana cand cl Piary anda” Pay and metastable i Acer bet grain boundaries. (1 Primary and acicular =.) Primary and aciulara th Primary and, Paci +B; price grain bourdais. i) Equiased wand strane Bi) Equsned se! itrransa FEesseed cand interranlarB. ena 10H 'SFINO, €5Hz0. 2508 a Sucre of millannale alpha alloy Fig. 312 Nth Scar pr pert Binamaixofac Optialmcostph “S00.24 / Titanium: A Technical Guide Table3.4 Ti-6AL-4V tensile mechanical properties(a) Table 3.5 Effect of alloying elements in several titanium binary alloys on eutectoid temperature and composition, and content needed to retain beta seve era Milsensisd 9457 salad ‘iar Tarun Aoys Preble —— @) simsie Pi eecaa Teanetoraton Transtomaton (Grsomernaus) (Grower L L Sate See r calm ACCS 8 a fe Sn, ‘Solute Content —e gg 3.13. Phos gram schematics for beta-tablzed FiG3.13 croys tal beta mmphous. and 1 bela eed Beta alloys tend 10 be used because of the relative formability of the boe beta structure ‘compared tothe hep alpha structure, Suficient alloy content allows retention of a metastable beta strcture after quenching from the beta re= gion 10 25 °C (77 *F) as indicated previously. In this condition the alloy can be fabricated by plastic deformation. Then the component can be reheated below the eutectoid temperature to Secompose the retained beta to 8 multiphase structure of beta and other phases that depend fn the exact alloy chemistry, providing consid stable strengthening over that of the retained beta. This approach is the basis of @ few com: mercial alloys, and in tis discussion, the phys cal_metallargy of one of these, Ti-13V- TICr-3A\L, is examined, — a Da Toss Temperature, °C Brattice, 10 Time, hours Fig, 3.14 Tinetemperauretarfomaton daa fs bet alo TH 3¥-11C-t, Aly was inl soon sreedinte region ‘The addition of chromium should maintain the desirable corrosion- and oxidation-esis- tance characteristic of titanium alloys. Table 3.5 shows the effect of several clements on the eulectoid temperature and composition and the alloy content required to lower the Me (0 25 °C (77 °F), Note that chromium i relatively effec tive in retaining beta. ata for titanium-vanadium and titanium ‘chromium alloys show that beta can be re- tained upon quenching from the beta region In the titanium-vanadium alloys, hardening ‘occurs upon aging due tothe formation of ale ‘pha in the beta and the appearance ofthe inter- mediate omega phase. In the titanium-cheo- ‘mium alloys, hardening is associated with the formation of alpha in the beta and also, the phase TiCr, is subsequently formed. Thus, in the alloy of Ti-Cr-V, it could be expected that beta ean be retained upon quenching from the bpta region to 28 °C (77 °F}, and that upon ag ing, hardening associated withthe formation of alpha and TiCry, and perhaps the intermediate fomega phase, occurs, These two latter phases are metastable and disappear upon prolonged aging at 760°C 1400 hens cooked 25°C 77 “hen age ‘The recommended commercial heat teat- iment for Ti-13V-L1Cr-4AL is to solution heat treatin the beta region from about 760 to 815, °C (1400-1499 °F) for 0.2 to I hour, then ait cool or quench (depending on the size of the part) to retain the beta strcture. Subsequent aging to precipitate alpha phase is accom plished around 480 °C (896 °F) fora ime usu ally between 2 and 100 hours, depending on the properties desired. The use of aging tempera- tures around 480 °C (896 *F) is based on data that show that this is the optimum range to use for maximum strength for aging times up 10 100 hours. Below this temperature, the rate of {formation of alpha is too low to give apprecia ble hardening. This is seen in the time-tempera ‘ure transformation (TTT) diagram of Fig. 3.14, Which describes the transformation products of beta breaking down isothermally to alpha and other phases ‘At aging (Isothermal holding) temperatures above 480 °C (896 °F), the bets phase trans forms 100 rapidly and the resultant structure is too coarse (0 attain maximum strengthen- ing.