AU2004239246A1 - Processing of titanium-aluminum-vanadium alloys and products made thereby - Google Patents

Description

WO 2004/101838 PCT/US2004/013947 TITLE 5 PROCESSING OF TITANIUM-ALUMINUM-VANADIUM ALLOYS AND PRODUCTS MADE THEREBY 10 INVENTOR John J.Hebda, 1480 N.W. Patrick Lane, Albany, Oregon 97321; Randall W. Hickman, P.O. Box 1005, Jefferson, Oregon 97352; and Ronald A. Graham, 3765 7 th Court South, Salem, Oregon 97302. 15 BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to novel methods of processing certain titanium alloys comprising aluminum, vanadium, iron, and oxygen, to articles made 20 using such processing methods, and to novel articles including such alloys. DESCRIPTION OF THE INVENTION BACKGROUND Beginning at least as early as the 1950's, titanium was recognized to have properties making it attractive for use as structural armor against small arms 25 projectiles. Investigation of titanium alloys for the same purpose followed. One titanium alloy known for use as ballistic armor is the Ti-6AI-4V alloy, which nominally comprises titanium, 6 weight percent aluminum, 4 weight percent vanadium and, typically, less than 0.20 weight percent oxygen. Another titanium alloy used in ballistic armor applications includes 6.0 weight percent aluminum, 2.0 weight percent 30 iron, a relatively low oxygen content of 0.18 weight percent, less than 0.1 weight percent vanadium, and possibly other trace elements. Yet another titanium alloy that has been shown suitable for ballistic armor applications is the alpha-beta (a-P3)

I

WO 2004/101838 PCT/US2004/013947 titanium alloy of United States Patent No. 5,980,655, issued November 9, 1999 to Kosaka. In addition to titanium, the alloy claimed in the '655 patent, which is referred to herein as the "Kosaka alloy", includes, in weight percentages, about 2.9 to about 5.0 aluminum, about 2.0 to about 3.0 vanadium, about 0.4 to about 2.0 iron, greater 5 than 0.2 to about 0.3 oxygen, about 0.005 to about 0.03 carbon, about 0.001 to about 0.02 nitrogen, and less than about 0.5 of other elements. Armor plates formed from the above titanium alloys have been shown to satisfy certain V 50 standards established by the military to denote ballistic 10 performance. These standards include those in, for example, MIL-DTL-96077F, "Detail Specification, Armor Plate, Titanium Alloy, Weldable". The V 50 is the average velocity of a specified projectile type that is required to penetrate an alloy plate having specified dimensions and positioned relative to the projectile firing point in a specified manner. 15 The above titanium alloys have been used to produce ballistic armor because when evaluated against many projectile types the titanium alloys provide better ballistic performance using less mass than steel or aluminum. Despite the fact that certain titanium alloys are more "mass efficient" than steel and aluminum against certain ballistic threats, there is a significant advantage to further improving the 20 ballistic performance of known titanium alloys. Moreover, the process for producing ballistic armor plate from the above titanium alloys can be involved and expensive. For example, the '655 patent describes a method wherein a Kosaka alloy that has been thermomechanically processed by multiple forging steps to a mixed a+3 microstructure is hot rolled and annealed to produce ballistic armor plate of a desired 25 gauge. The surface of the hot rolled plate develops scale and oxides at the high processing temperatures, and must be conditioned by one or more surface treatment steps such as grinding, machining, shotblasting, pickling, etc. This complicates the fabrication process, results in yield losses, and increases the cost of the finished ballistic plate. 30 2 WO 2004/101838 PCT/US2004/013947 Given the advantageous strength-to-weight properties of certain titanium alloys used in ballistic armor applications, it would be desirable to fabricate articles other than ballistic plate from these alloys. However, it is generally believed that it is not possible to readily apply fabrication techniques other than simple hot 5 rolling to many of these high-strength titanium alloys. For example, Ti-6AI-4V in plate form is considered too high in strength for cold rolling. Thus, the alloy is typically produced in sheet form via a complicated "pack rolling" process wherein two or more plates of Ti-6AI-4V having an intermediate thickness are stacked and enclosed in a steel can. The can and its contents are hot rolled, and the individual 10 plates are then removed and ground, pickled and trimmed. The process is expensive and may have a low yield given the necessity to grind and pickle the surfaces of the individual sheets. Similarly, it is conventionally believed that the Kosaka alloy has relatively high resistance to flow at temperatures below the a-3 rolling temperature range. Thus, it is not known to form articles other than ballistic 15 plate from the Kosaka alloy, and it is only known to form such plate using the hot rolling technique generally described in the '655 patent. Hot rolling is suited to production of only relatively rudimentary product forms, and also requires relatively high energy input. Considering the foregoing description of conventional methods of 20 processing certain titanium alloys known for use in ballistic armor applications, there is a need for a method of processing such alloys to desired forms, including forms other than plate, without the expense, complexity, yield loss and energy input requirements of the known high temperature working processes. 25 SUMMARY In order to address the above-described needs, the present disclosure provides novel methods for processing the a-P titanium-aluminum-vanadium-alloy described and claimed in the '655 patent, and also describes novel articles including the a-P3 titanium alloy. 30 3 WO 2004/101838 PCT/US2004/013947 One aspect of the present disclosure is directed to a method of forming an article from an a-P titanium alloy comprising, in weight percentages, from about 2.9 to about 5.0 aluminum, from about 2.0 to about 3.0 vanadium, from about 0.4 to about 2.0 iron, from about 0.2 to about 0.3 oxygen, from about 0.005 to about 0.3 5 carbon, from about 0.001 to about 0.02 nitrogen, and less than about 0.5 of other elements. The method comprises cold working the a-P titanium alloy. In certain embodiments, the cold working may be conducted with the alloy at a temperature in the range of ambient temperature up to less than about 1250oF (about 677 0 C). In certain other embodiments, the a-13 alloy is cold worked while at a temperature 10 ranging from ambient temperature up to about 1000F (about 538 0 C). Prior to cold working, the a-P titanium alloy may optionally be worked at a temperature greater than about 16001F (about 8710C) to provide the alloy with a microstructure that is conducive to cold deformation during the cold working. The present disclosure also is directed to articles made by the novel f5 methods described herein. In certain embodiments, an article formed by an embodiment of such methods has a thickness up to 4 inches and exhibits room temperature properties including tensile strength of at least 120 KSI and ultimate tensile strength of at least 130 KSI. Also, in certain embodiments an article formed by an embodiment of such methods exhibits elongation of at least 10%. 20 The inventors have determined that any suitable cold working technique may adapted for use with the Kosaka alloy. In certain non-limiting embodiments, one or more cold rolling steps are used to reduce a thickness of the alloy. Examples of articles that may be made by such embodiments include a sheet, a strip, a foil and a plate. In the case where at least two cold rolling steps are used, 25 the method also may include annealing the alloy intermediate to successive cold rolling steps so as to reduce stresses within the alloy. In certain of these embodiments, at least one stress-relief anneal intermediate successive cold rolling steps may be conducted on a continuous anneal furnace line. 4 WO 2004/101838 PCT/US2004/013947 Also disclosed herein is a novel method for making armor plate from an a-0 titanium alloy including, in weight percentages, from about 2.9 to about 5.0 aluminum, from about 2.0 to about 3.0 vanadium, from about 0.4 to about 2.0 iron, from about 0.2 to about 0.3 oxygen, from about 0.005 to about 0.3 carbon, from 5 about 0.001 to about 0.02 nitrogen, and less than about 0.5 of other elements. The method comprises rolling the alloy at temperatures significantly less than temperatures conventionally used to hot roll the alloy to produce armor plate. In one embodiment of the method, the alloy is rolled at a temperature that is no greater than 400°F (about 222 0 C) below the Tp of the alloy. 10 An additional aspect of the present invention is directed to a cold worked article of an a-13 titanium alloy, wherein the alloy includes, in weight percentages, from about 2.9 to about 5.0 aluminum, from about 2.0 to about 3.0 vanadium, from about 0.4 to about 2.0 iron, from about 0.2 to about 0.3 oxygen, from about 0.005 to about 0.3 carbon, from about 0.001 to about 0.02 nitrogen, and less 15 than about 0.5 of other elements. Non-limiting examples of the cold worked article include an article selected from a sheet, a strip, a foil, a plate, a bar, a rod, a wire, a tubular hollow, a pipe, a tube, a cloth, a mesh, a structural member, a cone, a cylinder, a duct, a pipe, a nozzle, a honeycomb structure, a fastener, a rivet and a washer. Certain of the cold worked articles may have thickness in excess of one 20 inch in cross-section and room temperature properties including tensile strength of at least 120 KSI and ultimate tensile strength of at least 130 KSI. Certain of the cold worked articles may have elongation of at least 10%. Certain methods described in the present disclosure incorporate the use of cold working techniques, which were not heretofore believed suitable for 25 processing the Kosaka alloy. In particular, it was conventionally believed that the Kosaka alloy's resistance to flow at temperatures significantly below the a-3 hot rolling temperature range was too great to allow the alloy to be worked successfully at such temperatures. With the present inventors' unexpected discovery that the Kosaka alloy may be worked by conventional cold working techniques at 30 temperatures less than about 1250 0 F (about 6770C), it becomes possible to produce myriad product forms that are not possible through hot rolling and/or are significantly 5 WO 2004/101838 PCT/US2004/013947 more expensive to produce using hot working techniques. Certain methods described herein are significantly less involved than, for example, the conventional pack rolling technique described above for producing sheet from Ti-6AI-4V. Also, certain methods described herein do not involve the extent of yield losses and the 5 high energy input requirements inherent in processes involving high temperature working to finished gauge and/or shape. Yet an additional advantage is that certain of the mechanical properties of embodiments of the Kosaka alloy approximate or exceed those of Ti-6Al-4V, which allows for the production of articles not previously available from Ti-6Al-4V, yet which have similar properties. 10 These and other advantages will be apparent upon consideration of the following description of embodiments of the invention. DESCRIPTION OF EMBODIMENTS OF THE INVENTION As noted above, United States Patent No. 5,980,655, issued to Kosaka, describes an alpha-beta (a-p) titanium alloy and the use of that alloy as 15 ballistic armor plate. The '655 patent is hereby incorporated herein in its entirety by reference. In addition to titanium, the alloy described and claimed in the '655 patent comprises the alloying elements in Table 1 below. For ease of reference, the titanium alloy including the alloying element additions in Table 1 is referred to herein as the "Kosaka alloy". 20 6 WO 2004/101838 PCT/US2004/013947 Table 1 Alumin um from about 2.9 to about 5.0 Vanadium from about 2.0 to about 3.0 Vanadium from about 2.0 to about 3.0 Iron from about 0.4 to about 2.0 Oxygen greater than 0.2 to about 0.3 Carbon from about 0.005 to about 0.03 Nitrogen from about 0.001 to about 0.02 Other elements less than about 0.5 As described in the '655 patent, the Kosaka alloy optionally may include elements other than those specifically listed in Table 1. Such other elements, and their percentages by weight, may include, but are not necessarily 5 limited to, one or more of the following: (a) chromium, 0.1% maximum, generally from about 0.0001% to about 0.05%, and preferably up to about 0.03%; (b) nickel, 0.1% maximum, generally from about 0.001% to about 0.05%, and preferably up to about 0.02%; (c) carbon, 0.1% maximum, generally from about 0.005% to about 0.03%, and preferably up to about 0.01%; and (d) nitrogen, 0.1% maximum, 10 generally from about 0.001% to about 0.02%, and preferably up to about 0.01%. One particular commercial embodiment of the Kosaka alloy is available from Wah Chang, an Allegheny Technologies Incorporated company, having the nominal composition, 4 weight percent aluminum, 2.5 weight percent vanadium, 1.5 weight percent iron, and 0.25 weight percent oxygen. Such nominal composition is 15 referred to herein as "Ti-4AI-2.5V-1.5Fe-.250 2 ". 7 WO 2004/101838 PCT/US2004/013947 The '655 patent explains that the Kosaka alloy is processed in a manner consistent with conventional thermomechanical processing ("TMP") used with certain other a-13 titanium alloys. In particular, the '655 patent notes that the Kosaka alloy is subjected to wrought deformation at elevated temperatures above 5 the beta transus temperature (Tp) (which is approximately 1800OF (about 9820C) for Ti-4Al-2.5V-1.5Fe-.250 2 ), and is subsequently subjected to additional wrought thermomechanical processing below Tp. This processing allows for the possibility of beta (i.e., temperature > Tp) recrystallization intermediate the a-3 thermomechanical processing cycle. 10 The '655 patent is particularly directed to producing ballistic armor plate from the Kosaka alloy in a way to provide a product including a mixed a+13 microstructure. The a+3 processing steps described in the patent are generally as follows: (1) P forge the ingot above Tp to form an intermediate slab; (2) a-13 forge the intermediate slab at a temperature below Tp; (3) a-P roll the slab to form a plate; and 15 (4) anneal the plate. The '655 patent teaches that the step of heating the ingot to a temperature greater than Tp may include, for example, heating the ingot to a temperature of from about 1900OF to about 2300°F (about 10380C to about 12600C). The subsequent step of a-P forging the intermediate gauge slab at a temperature below Tp may include, for example, forging the slab at a temperature in the a+3 20 temperature range. The patent more particularly describes a-13 forging the slab at a temperature in the range of from about 501F to about 200'F (about 280C to about 1110 C) below Tp, such as from about 1550aF to about 1775oF (about 843 0 C to about 9680C). The slab is then hot rolled in a similar a-13 temperature range, such as from about 1550'F to about 1775 0 F (about 8430C to about 9680C), to form a plate of a 25 desired thickness and having favorable ballistic properties. The '655 patent describes the subsequent annealing step following the a-3 rolling step as occurring at about 1300 0 F to about 1500OF (about 7040C to about 8160C). In the examples specifically described in the '655 patent, plates of the Kosaka alloy were formed by subjecting the alloy to 13 and a-13 forging, a-13 hot rolling at 1600oF (about 8710C) or 30 1700OF (about 9270C), and then "mill" annealing at about 14501F (about 7880C). Accordingly, the '655 patent teaches producing ballistic plate from the Kosaka alloy 8 WO 2004/101838 PCT/US2004/013947 by a process including hot rolling the alloy within the a-j3 temperature range to the desired thickness. In the course of producing ballistic armor plate from the Kosaka alloy according to the processing method described in the '655 patent, the present 5 inventors unexpectedly and surprisingly discovered that forging and rolling conducted at temperatures below Tp resulted in significantly less cracking, and that mill loads experienced during rolling at such temperatures were substantially less than for equivalently sized slabs of Ti-6AI-4V alloy. In other words, the present inventors unexpectedly observed that the Kosaka alloy exhibited a decreased 10 resistance to flow at elevated temperatures. Without intending to be limited to any particular theory of operation, it is believed that this effect, at least in part, is attributable to a reduction in strengthening of the material at elevated temperatures due to the iron and oxygen content in the Kosaka alloy. This effect is illustrated in the following Table 2, which provides mechanical properties measured for a sample 15 of the Ti-4AI-2.5V-1.5Fe-.250 2 alloy at various elevated temperatures. Table 2 800 63.9 85.4 22 1000 46.8 67.0 32 1200 17.6 34.4 62 1400 6.2 16.1 130 1500 3.1 10.0 140 9 WO 2004/101838 PCT/US2004/013947 Although the Kosaka alloy was observed to have reduced flow resistance at elevated temperatures during the course of producing ballistic plate from the material, the final mechanical properties of the annealed plate were 5 observed to be in the general range of similar plate product produced from Ti-6AI-4V. For example, the following Table 3 provides mechanical properties of 26 hot rolled ballistic armor plates prepared from two 8,000 lb. ingots of Ti-4AI-2.5V-1.5Fe-.250 2 alloy. The results of Table 3 and other observations by the inventors indicate that products less than, for example, about 2.5 inches in cross-sectional thickness 10 formed from Kosaka alloy by the processes disclosed herein may have 120 KSI minimum yield strength, minimum 130 KSI ultimate tensile strength, and minimum 12% elongation. However, it is possible that articles with these mechanical properties and much larger cross-section, such as less than 4 inches, might be produced through cold working on certain large-scale bar mills. These properties 15 compare favorably with those of Ti-6AI-4V. For example, Materials Properties Handbook, Titanium Alloys (ASM International, 2d printing, January 1998) page 526, reports room temperature tensile properties of 127 KSI yield strength, 138 KSI ultimate tensile strength, and 12.7% elongation for Ti-6AI-4V cross-rolled at 9550C (about 1777oF) and mill annealed. The same text, at page 524, lists typical Ti-6AI 20 4V tensile properties of 134 KSI yield strength, 144 KSI ultimate tensile strength, and 14% elongation. Although tensile properties are influenced by product form, cross section, measurement direction, and heat treatment, the foregoing reported properties for Ti-6AI-4V provide a basis for generally evaluating the relative tensile properties of the Kosaka alloy. 25 30 10 WO 2004/101838 PCT/US2004/013947 Table 3 Lonqitudinal Yield Strength 120.1 - 130.7 KSI Ultimate Tensile Strength 133.7 - 143.1 KSI Elongation 13% - 19% Transverse Yield Strength 122.6 - 144.9 KSI Ultimate Tensile Strength 134.0 - 155.4 KSI Elongation 15% - 20% The present inventors also have observed that cold rolled Ti-4AI-2.5V 1.5Fe-.250 2 generally exhibits somewhat better ductility than Ti-6AI-4V material. For 5 example, in one test sequence, described below, twice cold rolled and annealed Ti 4AI-2.5V-1.5Fe-.250 2 material survived 2.5T bend radius bending in both longitudinal and transverse directions. Thus, the observed reduced resistance to flow at elevated 10 temperatures presents an opportunity to fabricate articles from the Kosaka alloy using working and forming techniques not previously considered suitable for use with either the Kosaka alloy or Ti-6AI-4V, while achieving mechanical properties typically associated with Ti-6AI-4V. For example, the work described below shows that Kosaka alloy can be readily extruded at elevated temperatures generally considered 15 "moderate" in the titanium processing industry, which is a processing technique that is not suggested in the '655 patent. Given the results of the elevated temperature extrusion experiments, other elevated temperature forming methods which it is 11 WO 2004/101838 PCT/US2004/013947 believed may be used to process Kosaka alloy include, but are not limited to, elevated temperature closed die forging, drawing, and spinning. An additional possibility is rolling at moderate temperature or other elevated temperatures to provide relatively light gauge plate or sheet, and thin gauge strip. These processing 5 possibilities extend substantially beyond the hot rolling technique described in the '655 patent to produce hot rolled plate, and make possible product forms which are not readily capable of being produced from Ti-6AI-4V, but which nevertheless would have mechanical properties similar to Ti-6AI-4V. 10 The present inventors also unexpectedly and surprisingly discovered that the Kosaka alloy has a substantial degree of cold formability. For example, trials of cold rolling of coupons of Ti-4Al-2.5V-1.5Fe-.250 2 alloy, described below, yielded thickness reductions of approximately 37% before edge cracking first appeared. The coupons were initially produced by a process similar to the conventional armor plate 15 process and where of a somewhat coarse microstructure. Refining of the rnicrostructure of the coupons through increased a-3 working and selective stress relief annealing allowed for cold reductions of up to 44% before stress-relief annealing was required to permit further cold reduction. During the course of the inventors' work, it also was discovered that the Kosaka alloy could be cold worked to 20 much higher strengths and still retain some degree of ductility. This previously unobserved phenomenon makes possible the production of a cold rolled product in coil lengths from the Kosaka alloy, but with mechanical properties of Ti-6AI-4V. The cold formability of Kosaka alloy, which includes relatively high 25 oxygen levels, is counter-intuitive. For example, Grade 4 CP (Commercially Pure) titanium, which includes a relatively high level of about 0.4 weight percent oxygen, shows a minimum elongation of about 15% and is known for being less formable than other CP grades. With the exception of certain CP titanium grades, the single cold workable a-3 titanium alloy produced in significant commercial volume is Ti-3AI 30 2.5V (nominally, in weight percent, 3 aluminum, 2.5 vanadium, max. 0.25 iron, max. 0.05 carbon, and max. 0.02 nitrogen). The inventors have observed that embodiments of the Kosaka alloy are as cold formable as Ti-3Al-2.5V but also 12 WO 2004/101838 PCT/US2004/013947 exhibit more favorable mechanical properties. The only commercially significant non-a-P3 titanium alloy that is readily cold formable is Ti-15V-3Al-3Cr-3Sn, which was developed as a cold rollable alternative to Ti-6Al-4V sheet. Although Ti-15V-3AI 3Cr-3Sn has been produced as tube, strip, plate and other forms, it has remained a 5 specialty product that does not approach the production volume of Ti-6AI-4V. The Kosaka alloy may be significantly less expensive to melt and fabricate than specialty titanium alloys such as Ti-1 5V-3AI-3Cr-3Sn. Given the cold workability of Kosaka alloy and the inventors' 10 observations when applying cold working techniques to the alloy, some of which are provided below, it is believed that numerous cold working techniques previously believed unsuited for the Kosaka alloy may be used to form articles from the alloy. In general, "cold working" refers to working an alloy at a temperature below that at which the flow stress of the material is significantly diminished. As used herein in 15 connection with the present invention, "cold working", "cold worked", "cold forming" or like terms, or "cold" used in connection with a particular working or forming technique, refer to working or the characteristic of having been worked, as the case may be, at a temperature no greater than about 12501F (about 6770C). Preferably, such working occurs at no greater than about 1000°F (about 538 0 C). Thus, for 20 example, a rolling step conducted on a Kosaka alloy plate at 950oF (5100C) is considered herein to be cold working. Also, the terms "working" and "forming" are generally used interchangeably herein, as are the terms "workability" and "formability" and like terms. 25 Cold working techniques that may be used with the Kosaka alloy include, for example, cold rolling, cold drawing, cold extrusion, cold forging, rocking/pilgering, cold swaging, spinning, and flow-turning. As is known in the art, cold rolling generally consists of passing previously hot rolled articles, such as bars, sheets, plates, or strip, through a set of rolls, often several times, until a desired 30 gauge is obtained. Depending upon the starting structure after hot (a-13) rolling and annealing, it is believed that at least a 35-40% reduction in area (RA) could be achieved by cold rolling a Kosaka alloy before any annealing is required prior to 13 WO 2004/101838 PCT/US2004/013947 further cold rolling. Subsequent cold reductions of at least 30-60% are believed possible, depending upon product width and mill configuration. The ability to produce thin gauge coil and sheet from Kosaka alloy is a 5 substantial improvement. The Kosaka alloy has properties similar to, and in some ways improved relative to, properties of Ti-6AI-4V. In particular, investigations conducted by the inventors indicate that the Kosaka alloy has improved ductility relative to Ti-6AI-4V as evidenced by elongation and bend properties. Ti-6AI-4V has been the main titanium alloy in use for well over 30 years. However, as noted 10 above, sheet is conventionally produced from Ti-6AI-4V, and from many other titanium alloys, by involved and expensive processing. Because the strength of Ti 6AI-4V is too high for cold rolling and the material preferentially texture strengthens, resulting in transverse properties with virtually no ductility, Ti-6AI-4V sheet is commonly produced as single sheets via pack rolling. Single sheets of Ti-6Al-4V 15 would require more mill force than most rolling mills can produce, and the material must still be rolled hot. Single sheets lose heat rapidly and would require reheating after each pass. Thus, the intermediate gauge Ti-6AI-4V sheets/plates are stacked two or more high and enclosed in a steel can, which is rolled in its entirety. However, because the industry mode for canning does not utilize vacuum sealing, 20 after hot rolling each sheet must be belt ground and sanded to remove the brittle oxide layer, which severely inhibits ductile fabrication. The grinding process introduces strike marks from the grit, which act as crack initiation sites for this notch sensitive material. Therefore, the sheets also must be pickled to remove the strike marks. Furthermore, each sheet is trimmed on all sides, with 2-4 inches of trim 25 typically left on one end for gripping while the sheet is ground in a pinch-roll grinder. Typically, at least about 0.003 inch per surface is ground away, and at least about 0.001 inch per surface is pickled away, resulting in a loss that is typically at least about 0.008 inch per sheet. For sheet of 0.025-inch final thickness, for example, the rolled-to-size sheet must be 0.033 inch, for a loss of about 24% through grinding and 30 pickling, irrespective of trim losses. The cost of steel for the can, the cost of grinding belts, and the labor costs associated with handling individual sheets after pack rolling causes sheets having thickness of 0.040 inch or less to be quite expensive. 14 WO 2004/101838 PCT/US2004/013947 Accordingly, it will be understood that the ability to provide a cold rolled a-P titanium alloy in a continuous coil form (Ti-6AI-4V is typically produced in standard sheet sizes of 36x96 inches and 48x120 inches) having mechanical properties similar to or better than Ti-6AI-4V is a substantial improvement. 5 Based on the inventors' observations, cold rolling of bar, rod, and wire on a variety of bar-type mills, including Koch's-type mills, also may be accomplished on the Kosaka alloy. Additional examples of cold working techniques that may be used to form articles from Kosaka alloy include pilgering (rocking) of extruded tubular 10 hollows for the manufacture of seamless pipe, tube and ducting. Based on the observed properties of the Kosaka alloy, it is believed that a larger reduction in area (RA) may be achieved in compressive type forming than with flat rolling. Drawing of rod, wire, bar and tubular hollows also may be accomplished. A particularly attractive application of the Kosaka alloy is drawing or pilgering to tubular hollows for 15 production of seamless tubing, which is particularly difficult to achieve with Ti-6AI-4V alloy. Flow turning (also referred to in the art as shear-spinning) may be accomplished using the Kosaka alloy to produce axially symmetric hollow forms including cones, cylinders, aircraft ducting, nozzles, and other "flow-directing"-type components. A variety of liquid or gas-type compressive, expansive type forming 20 operations such as hydro-forming or bulge forming may be used. Roll forming of continuous-type stock may be accomplished to form structural variations of "angle iron" or "uni-strut" generic structural members. In addition, based on the inventors' findings, operations typically associated with sheet metal processing, such as stamping, fine-blanking, die pressing, deep drawing, coining may be applied to the 25 Kosaka alloy. In addition to the above cold forming techniques, it is believed that other "cold" techniques that may be used to form articles from the Kosaka alloy include, but are not necessarily limited to, forging, extruding, flow-turning, hydro 30 forming, bulge forming, roll forming, swaging, impact extruding, explosive forming, rubber forming, back extrusion, piercing, spinning, stretch forming, press bending, electromagnetic forming, and cold heading. Those having ordinary skill, upon 15 WO 2004/101838 PCT/US2004/013947 considering the inventors' observations and conclusions and other details provided in the present description of the invention, may readily comprehend additional cold working/forming techniques that may be applied to the Kosaka alloy. Also, those having ordinary skill may readily apply such techniques to the alloy without undue 5 experimentation. Accordingly, only certain examples of cold working of the alloy are described herein. The application of such cold working and forming techniques may provide a variety of articles. Such articles include, but are not necessarily limited to the following: a sheet, a strip, a foil, a plate, a bar, a rod, a wire, a tubular hollow, a pipe, a tube, a cloth, a mesh, a structural member, a cone, a cylinder, a duct, a pipe, 10 a nozzle, a honeycomb structure, a fastener, a rivet and a washer. The combination of unexpectedly low flow resistance of Kosaka alloy at elevated working temperatures combined with the unexpected ability to subsequently cold work the alloy should permit a lower cost product form in many cases than using 15 conventional Ti-6AI-4V alloy to produce the same products. For example, it is believed that an embodiment of Kosaka alloy having the nominal composition Ti-4AI 2.5V-1.5Fe-.250 2 can be produced in certain product forms in greater yields than Ti 6AI-4V alloy because less surface and edge checking is experienced with the Kosaka alloy during typical a+3 processing of the two alloys. Thus, it has been the 20 case that Ti-4AI-2.5V-1.5Fe-.250 2 requires less surface grinding and other surface conditioning that can result in loss of material. It is believed that in many cases the yield differential would be demonstrated to an even greater degree when producing finished products from the two alloys. In addition, the unexpectedly low flow resistance of the Kosaka alloy at a-13 hot working temperatures would require less 25 frequent re-heating and create less stress on tooling, both of which should further reduce processing costs. Moreover, when these attributes of the Kosaka alloy are combined with its unexpected degree of cold workability, a substantial cost advantage may be available relative to Ti-4AI-6V given the conventional requirement to hot pack roll and grind Ti-6AI-4V sheet. The combined low resistance to flow at 30 elevated temperature and cold workability should make the Kosaka alloy particularly amenable to being processed into the form of a coil using processing techniques similar to those used in the production of coil from stainless steel. 16 WO 2004/101838 PCT/US2004/013947 The unexpected cold workability of the Kosaka alloy results in finer surface finishes and a reduced need for surface conditioning to remove the heavy surface scale and diffused oxide layer that typically results on the surface of a Ti-6AI 4V pack rolled sheet. Given the level of cold workability the present inventors have 5 observed, it is believed that foil thickness product in coil lengths may be produced from the Kosaka alloy with properties similar to those of Ti-6AI-4V. Examples of the inventors' various methods of processing the Kosaka alloy follow. 10 EXAMPLES Unless otherwise indicated, all numbers expressing quantities of ingredients, composition, time, temperatures, and so forth in the present disclosure are to be understood as being modified in all instances by the term "about." 15 Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light 20 of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth 25 in the specific examples are reported as precisely as possible. Any numerical value, however, may inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Example 1 30 Seamless pipe was prepared by extruding tubular hollows from a heat of the Kosaka alloy having the nominal composition Ti-4AI-2.5V-1.5Fe-.250 2 . The actual measured chemistry of the alloy is shown in Table 4 below: 17 WO 2004/101838 PCT/US2004/013947 Table 4 Aluminum 4.02-4.14 wt.% Vanadium 2.40-2.43 wt.% Iron 1.50-1.55 wt.% Oxygen 2300-2400 ppm Carbon 246-258 ppm Nitrogen 95-110 ppm Silicon 200-210 ppm Chromium 210-240 ppm Molybdenum 120-190 ppm The alloy was forged at 1700aF (about 927oC), and then rotary forged at about 1600OF (about 871 0 C). The calculated Tp of the alloy was approximately 5 17900F (about 977oC). Two billets of the hot forged alloy, each having a 6 inch outer diameter and 2.25 inch inner diameter, were extruded to tubular hollows having 3.1 inch outer diameter and 2.2 inch inner diameter. The first billet (billet #1) was extruded at about 788 0 C (about 1476 0 F) and yielded about 4 feet of material satisfactory for rocking to form seamless pipe. The second billet (billet #2) was 10 extruded at about 843 0 C (about 1575 0 F) and produced a satisfactory extruded tubular hollow along its entire length. In each case, the shape, dimensions and surface finish of the extruded material indicated that the material could be successfully cold worked by pilgering or rocking after annealing and conditioning. 18 WO 2004/101838 PCT/US2004/013947 A study was conducted to determine tensile properties of the extruded material after being subjected to various heat treatments. Results of the study are provided in Table 5 below. The first two rows of Table 5 list properties measured for the extrusions in their "as extruded" form. The remaining rows relate to samples 5 from each extrusion that were subjected to additional heat treatment and, in some cases, a water quench ("WQ") or air cool ("AC").. The last four rows successively list the temperature of each heat treatment step employed. Table 5 As Extruded (billet #1) N/A 131.7 148.6 16 As Extruded (billet #2) N/A 137.2 149.6 18 Anneal 4 hrs. (#1) 1350°F/732oC 126.7 139.2 18 Anneal 4 hrs. (#2) 1350 0 F/732 0 C 124.4 137.9 18 Anneal 4 hrs. (#1) 1400°F/760 0 C 125.4 138.9 19 Anneal 4 hrs. (#2) 1400oF/760 0 C 124.9 139.2 19 Anneal 1 hr. (#1) 1400 0 F/760 0 C 124.4 138.6 18 Anneal 1 hr. (#2) 1400aF/760 0 C 127.0 139.8 18 Anneal 4 hrs. (#1) 1450oF/788 0 C 127.7 140.5 18 Anneal 4 hrs. (#2) 1450oF/788 0 C 125.3 139.0 19 Anneal 1 hr. + WQ 1700aF/927 0 C N/A 187.4 12 (#1) Anneal 1 hr. + WQ - 1700°F/927 0 C 162.2 188.5 15 (#2) Anneal 1 hr. + WQ + 8 1700aF/927 0 C 157.4 175.5 13 hrs. + AC (#1) 1000F/538 0 C Anneal 1 hr. + WQ + 8 1700aF/927 0 C 159.5 177.9 9 hrs. + AC (#2) 1000°F/538 0 C Anneal 1 hr. + WQ + 1 1700cF/927 0 C 133.8 147.5 19 hr. + AC (#1) 1400oF/760 0 C Anneal 1 hr. + WQ + 1 1700aF/927 0 C 132.4 146.1 18 hr. + AC (#2) 1400OF/760 0 C 10 The results in Table 5 show strengths comparable to hot-rolled and annealed plate as well as precursor flat stock which was subsequently cold rolled. All of the results in Table 5 for annealing at 1350aF (about 732 0 C) through 1450aF 19 WO 2004/101838 PCT/US2004/013947 (about 7880C) for the listed times (referred to herein as a "mill anneal") indicate that the extrusions may be readily cold reduced to tube via rocking or pilgering or drawing. For example, those tensile results compare favorably with results obtained by the inventors from cold rolling and annealing Ti-4AI-2.5V-1.5Fe-.250 2 , and also 5 from the inventors' prior work with Ti-3AI-2.5V alloy, which is conventionally extruded to tubing. The results in Table 5 for the water quenched and aged specimens (referred to as "STA" for "solution treated and aged") show that cold rocked/pilgered 10 tube produced from the extrusions could be subsequently heat-treated to obtain much higher strengths, while maintaining some residual ductility. These STA properties are favorable when compared to those for Ti-6AI-4V and sub-grade variants. Example 2 15 Additional billets of the hot-forged Kosaka alloy of Table 5 described above were prepared and successfully extruded to tubular hollows. Two sizes of input billets were utilized to obtain two sizes of extruded tubes. Billets machined to 6.69-inch outer diameter and 2.55-inch inner diameter were extruded to a nominal 3.4-inch outer diameter and 2.488-inch inner diameter. Two billets machined to 20 6.04-inch outer diameter and 2.25-inch inner diameter were extruded to a nominal. 3.1-inch outer diameter and 2.25-inch inner diameter. The extrusion occurred at an aimpoint of 1450'F (about 7880C), with a maximum of 1550 0 F (about 8430C). This temperature range was selected so that the extrusion would take place at a temperature below the calculated Tp (about 17901F) but also sufficient to achieve 25 plastic flow. The extruded tubes exhibited favorable surface quality and surface finish, were free from visible surface trauma, were of a round shape and generally uniform wall thickness, and had uniform dimensions along their length. These 30 observation, taken in combination with the tensile results of Table 5 and the inventors' experience with cold rolling the same material, indicate that the tubular 20 WO 2004/101838 PCT/US2004/013947 extrusions may be further processed by cold working to tubing meeting commercial requirements. Example 3 Several coupons of the a-13 titanium alloy of Table 5 hot forged as 5 described in Example 1 above were rolled to about 0.225-inch thick in the a-13 range at a temperature of 50-150°F (about 280C to about 830C) below the calculated TP. Experimentation with the alloy indicated that rolling in the a-3 range followed by a mill anneal produced the best cold rolling results. However, it is anticipated that depending on the results desired, the rolling temperature might be in the range of 10 temperatures below Tp down to the mill anneal range. Prior to cold rolling, the coupons were mill annealed, and then blasted and pickled so as to be free of a case and oxygen-enriched or stabilized surface. The coupons were cold rolled at ambient temperature, without application of external 15 heat. (The samples warmed through adiabatic working to about 200-300°F (about 930C to about 1490C), which is not considered metallurgically significant.) The cold rolled samples were subsequently annealed. Several of the annealed 0.225-inch thick coupons were cold rolled to about 0.143-inch thickness, a reduction of about 36%, through several roll passes. Two of the 0.143-inch coupons were annealed for 20 1 hour at 1400OF (7600C) and then cold rolled at ambient temperature, without the application of external heat, to about 0.0765 inch, a reduction of about 46%. During cold rolling of heavier thickness samples, reductions of 0.001 0.003 inch per pass were observed. At thinner gauges, as well as near the limits of 25 cold reduction before annealing was required, it was observed that several passes were needed before achieving a reduction of as little as 0.001 inch. As will be evident to one having ordinary skill, the attainable thickness reduction per pass will depend in part on mill type, mill configuration, work roll diameter, as well as other factors. Observations of the cold rolling of the material indicate that ultimate 30 reductions of at least approximately 35-45% could readily be achieved prior to the need for annealing. The samples cold rolled without observable trauma or defects 21 WO 2004/101838 PCT/US2004/013947 except for slight edge cracking that occurred at the limit of the material's practical ductility. These observations indicated the suitability of the a-3 Kosaka alloy for cold rolling. 5 Tensile properties of the intermediate and final gauge coupons are provided below in Table 6. These properties compare favorably with required tensile properties for Ti-6Al-4V material as set forth in standard industry specifications such as: AMS 4911H (Aerospace Material Specification, Titanium Alloy, Sheet, Strip, and Plate 6AI-4V, Annealed); MIL-T-9046J (Table Ill); and DMS 1592C. 10 Table 6 (K S (K 1) 0.143 125.5 141.9 15 153.4 158.3 16 0.143 126.3 142.9 15 152.9 157.6 16 0.143 125.3 141.9 15 152.2 157.4 16 0.0765 125.6 145.9 14 150.3 157.3 14 0.0765 125.9 146.3 14 150.1 156.9 15 Bend properties of the annealed coupons were evaluated according to ASTM E 290. Such testing consisted of laying a flat coupon on two stationary rollers 15 and then pushing the coupon between the rollers with a mandrel of a radius based upon material thickness until a bend angle of 1050 is obtained. The specimen was then examined for cracking. The cold rolled specimens exhibited the capability of being bent into tighter radii (typically an achieved bend radius of 3T, or in some cases 2T, where "T" is specimen thickness) than is typical for Ti-6AI-4V material, 22 WO 2004/101838 PCT/US2004/013947 while also exhibiting strength levels comparable to Ti-6AI-4V. Based on the inventors' observations of this and other bend testing, it is believed that many cold rolled articles formed of the Kosaka alloy may be bent around a radius of 4 times the article's thickness or less without failure of the article. 5 The cold rolling observations and strength and bend property testing in this example indicate that the Kosaka alloy may be processed into cold rolled strip, and also may be further reduced to very thin gauge product, such as foil. This was confirmed in additional testing by the inventors wherein a Kosaka alloy having the 10 chemistry in the present example was successfully cold rolled on a Sendzimir mill to a thickness of 0.011 inch or less. Example 4 A plate of an a-3 processed Kosaka alloy having the chemistry in Table 15 4 above was prepared by cross rolling the plate at about 1735 0 F (about 9461C), which is in the range of 50-150aF (about 280C to about 830C) less than TP. The plate was hot rolled at 1715 0 F (about 935°C) from a nominal 0.980 inch thickness to a nominal 0.220 inch thickness. To investigate which intermediate anneal parameters provide suitable conditions for subsequent cold reduction, the plate was cut into four 20 individual sections (#1 through #4) and the sections were processed as indicated in Table 7. Each section was first annealed for about one hour and then subjected to two cold rolling (CR) steps with an intermediate anneal lasting about one hour. Table 7 #1 anneal@1400 0 F (7600C) / CR / 0.069 anneal@1400 0 F (7600C) / CR #2 anneal@1550aF (about 843 0 C) / CR / 0.066 anneal@1400oF (7600C) / CR #3 anneal@1700 0 F (about 9270C) / CR / 0.078 anneal@1400 0 F (7600C) / CR #4 anneal@1800OF (about 9820C) / CR / N/A anneal@1400oF (7600C) / CR 25 23 WO 2004/101838 PCT/US2004/013947 During cold rolling steps, rolling passes were conducted until the first observable edge checking, which is an early indication that the material is approaching the limit of practical workability. As was seen in other cold rolling trials with the Kosaka alloy by the inventors, the initial cold reduction in the Table 7 trials 5 was on the order of 30-40%, and more typically was 33-37%. Using parameters of one hour at 1400aF (7600C) for both the pre-cold reduction anneal and the intermediate anneal provided suitable results, although the processing applied to the other sections in Table 7 also worked well. 10 The inventors also determined that annealing for four hours at 1400OF (7600C), or at either 1350 0 F (about 732 0 C) or 1450 0 F (about 7870C) for an equivalent time, also imparted substantially the same capability in the material for subsequent cold reduction and advantageous mechanical properties, such as tensile and bending results. It was observed that even higher temperatures, such as in the 15 "solution range" of 50-150'F (about 280C to about 830C) less than Tp, appeared to toughen the material and make subsequent cold reduction more difficult. Annealing in the |3 field, T > Tp, yielded no advantage for subsequent cold reduction. Example 5 20 A Kosaka alloy was prepared having following composition: 4.07 wt% aluminum; 229 ppm carbon; 1.69 wt% iron; 86 ppm hydrogen; 99 ppm nitrogen; 2100 ppm oxygen; and 2.60 wt% vanadium. The alloy was processed by initially forging a 30-inch diameter VAR ingot of the alloy at 2100°F (about 11490C) to a nominal 20-inch thick by 29-inch wide cross-section, which in turn was forged at 25 1950aF (about 10660C) to a nominal 10-inch thick by 29-inch wide cross-section. After grinding/conditioning, the material was forged at 1835 0 F (about 1002 0 C) (still above the Tp of about 1790)F (about 9770C)) to a nominal 4.5-inch thick slab, which was subsequently conditioned by grinding and pickling. A section of the slab was rolled at 1725 0 F (about 941°C), about 65 0 F (about 360C) below Tp, to about 2.1-inch 30 thickness and annealed. A 12X15 inch piece of the 2.1-inch plate was then hot rolled to a hot band of nominal 0.2-inch thickness. After annealing at 14000F 24 WO 2004/101838 PCT/US2004/013947 (7600C) for one hour, the piece was blasted and pickled, cold rolled to about 0.143 inch thick, air annealed at 1400OF (7600C) for one hour, and conditioned. As is known in the art, conditioning may include one or more surface treatments, such as blasting, pickling and grinding, to remove surface scale, oxide and defects. The 5 band was cold rolled again, this time to about 0.078-inch thick, and similarly annealed and conditioned, and re-rolled to about 0.045-inch thick. On rolling to 0.078-inch thick, the resulting sheet was cut into two pieces for ease of handling. However, so as to perform further testing on equipment 10 requiring a coil, the two pieces were welded together and tails were attached to the strip. The chemistry of the weld metal was substantially the same as the base metal. The alloy was capable of being welded using traditional means for titanium alloys, providing a ductile weld deposit. The strip was then cold rolled (the weld was not rolled) to provide a nominal 0.045-inch thick strip, and annealed in a continuous 15 anneal furnace at 1425 0 F (about 7741C) at a feed rate of 1 foot/minute. As is known, a continuous anneal is accomplished by moving the strip through a hot zone within a semi-protective atmosphere including argon, helium, nitrogen, or some other gas having limited reactivity at the annealing temperature. The semi-protective atmosphere is intended to preclude the necessity to blast and then heavily pickle the 20 annealed strip to remove deep oxide. A continuous anneal furnace is conventionally used in commercial scale processing and, therefore, the testing was carried out to simulate producing coiled strip from Kosaka alloy in a commercial production environment. 25 Samples of one of the annealed joined sections of the strip were collected for evaluation of tensile properties, and the strip was then cold rolled. One of the joined sections was cold rolled from a thickness of about 0.041 inch to about 0.022 inch, a 46% reduction. The remaining section was cold rolled from a thickness of about 0.042 inch to about 0.024 inch, a 43% reduction. Rolling was discontinued 30 when a sudden edge crack appeared in each joined section. 25 WO 2004/101838 PCT/US2004/013947 After cold rolling, the strip was re-divided at the weld line into two individual strips. The first section of the strip was then annealed on the continuous anneal line at 1425 0 F (about 7740C) at a feed rate of 1 foot/minute. Tensile properties of the annealed first section of the strip are provided below in Table 8, 5 with each test having been run in duplicate. The tensile properties in Table 8 were substantially the same as those of the samples collected from the first section of the strip after the initial continuous anneal and prior to the first cold reduction. That all samples had similar favorable tensile properties indicates that the alloy may be effectively continuous annealed. 10 Table 8 (K I Strnt ( I Strnt #1 131.1 149.7 14 153.0 160.8 10 #2 131.4 150.4 / 12 152.6 160.0 12 The cold rolling results achieved in this example were very favorable. Continuous annealing suitably softened the material for additional cold reduction to 15 thin gauge. The use of a Sendzimir mill, which applies pressure more uniformly across the width of the workpiece, may increase the possible cold rolling prior to the necessity to anneal. Example 6 A section of a billet of Kosaka alloy having the chemistry shown in 20 Table 4 was provided and processed as follows toward the end of producing wire. The billet was forged on a forging press at about 1725 0 F (about 9410C) to a round bar about 2.75 inches in diameter, and then forged on a rotary forge to round it up. 26 WO 2004/101838 PCT/US2004/013947 The bar was then forged/swaged on a small rotary swage in two steps, each at 1625 0 F (8850C), first to 1.25-inch diameter and then 0.75-inch diameter. After blasting and pickling, the rod was halved and one half was swaged to about 0.5 inch at a temperature below red heat. The 0.5-inch rod was annealed for 1 hour at 5 1400-F (7600C). The material flowed very well during swaging, without surface trauma. Microstructural examination revealed sound structure, with no voids, porosity, or other defects. A first sample of the annealed material was tested for tensile 10 properties and exhibited 126.4 KSI yield strength, 147.4 KSI ultimate tensile strength, and 18% total elongation. A second annealed bar sample exhibited 125.5 KSI yield strength, 146.8 KSI, ultimate tensile strength, and 18% total elongation. Thus, the samples exhibited yield and ultimate tensile strengths similar to Ti-6AI-4V, but with improved ductility. The increased workability exhibited by the Kosaka alloy 15 compared to other titanium alloys of similar strength, alloys which also require an increased number of intermediate heating and working steps and additional grinding to remove surface defects from thermo-mechanical processing trauma, represents a significant advantage. Example 7 20 As discussed above, the Kosaka alloy was originally developed for use as ballistic armor plate. With the unexpected observation that the alloy may be readily cold worked and exhibits significant ductility in the cold-worked condition at higher strength levels, the inventors determined to investigate whether cold working affects ballistic performance. 25 A 2.1-inch (about 50 mm) thick plate of an a-3 processed Kosaka alloy having the chemistry shown in Table 4 was prepared as described in Example 5. The plate was hot rolled at 1715 0 F (9350C) to a thickness of approximately 1.090 inches. The rolling direction was normal to the prior rolling direction. The plate was 30 annealed in air at approximately 1400OF (76000) for about one hour and then blasted and pickled. The sample was then rolled at approximately 1000F (about 5380C) to 27 WO 2004/101838 PCT/US2004/013947 0.840 inch thick and cut into halves. One section was retained in the as-rolled condition. The remaining section was annealed at 1690°F (about 921OC) for approximately one hour and air cooled. (The calculated Tp of the material was 1790°F (about 9770C).) Both sections were blasted and pickled and sent for ballistic 5 testing. A "remnant" of equivalent thickness material of the same ingot also was sent for ballistic testing. The remnant had been processed in a manner conventionally used for production of ballistic armor plate, by a hot rolling, solution anneal, and a mill anneal at approximately 1400aF (7600C) for at least one hour. The solution anneal typically is performed at 50-150°F (about 280C to about 83 0 C) below Tp. 10 The testing laboratory evaluated the samples against a 20 mm Fragment Simulating Projectile (FSP) and a 14.5 mm API B32 round, per MIL-DTL 96077F. There was no discernable difference noted in the effects of the 14.5 mm rounds on each of the samples, and all test pieces were completely penetrated by 15 the 14.5 mm rounds at velocities of 2990 to 3018 feet per second (fps). Results with the 20 mm FSP rounds are shown in Table 10 (MIL-DTL-96077F required Vo 50 is 2529 fps). Table 10 1000°F (about 0.829 2843 4 5380C) Roll + Anneal 1 000F (about 0.830 N/A 3 5380C) Roll, No Anneal Hot Roll + 0.852 2782 4 Anneal (conventional) 28 WO 2004/101838 PCT/US2004/013947 As shown in Table 10, the material rolled at 1000aF (about 5380C) followed by a "solution range" anneal (nominal 1 hour at 1690 0 F (about 9210C) and air cooled) performed significantly better against the FSP rounds than the material rolled at 1000°F (about 5380C) that was not subsequently annealed, and against the 5 material that was hot rolled and annealed in a manner conventional for ballistic armor formed from Kosaka alloy. Thus, the results in Table 10 indicate that utilizing rolling temperatures significantly lower than conventional rolling temperatures during production of ballistic armor plate from Kosaka alloy can lead to improved FSP ballistic performance. 10 Accordingly, it was determined that the V 50 ballistic performance of a Kosaka alloy plate having the nominal composition Ti-4AI-2.5V-1.5Fe-.250 2 with 20 mm FSP rounds was improved on the order of 50-100 fps by applying novel thermo mechanical processing. In one form, the novel thermo-mechanical processing 15 involved first employing relatively normal hot rolling below Tp at conventional a-3 hot working temperatures (typically, 50-150,F (about 280C to about 830C) below TP) in such a manner as to achieve nearly equal strain in the longitudinal and long transverse orientations of the plate. An intermediate mill anneal at about 1400OF (7600C) for approximately one hour was then applied. The plate was then rolled at a 20 temperature significantly lower than is conventionally used to hot roll armor plate from Kosaka alloy. For example, it is believed that the plate may be rolled at 400 700°F (2220C to about 3890C) below Tp, or at a lower temperature, temperatures much lower than previously believed possible for use with Kosaka alloy. The rolling may be used to achieve, for example, 15-30% reduction in plate thickness. 25 Subsequent to such rolling, the plate may be annealed in the solution temperature range, typically 50-100°F (about 280C to about 830C) below To, for a suitable time period, which may be, for example, in the range of 50-240 minutes. The resultant annealed plate may then be finished through combinations of typical metal plate finishing operations to remove the case of alpha (a) material. Such finishing 30 operations may include, but are not limited to, blasting, acid pickling, grinding, 29 WO 2004/101838 PCT/US2004/013947 machining, polishing, and sanding, whereby a smooth surface finish is produced to optimize ballistic performance. It is to be understood that the present description illustrates those 5 aspects of the invention relevant to a clear understanding of the invention. Certain aspects of the invention that would be apparent to those of ordinary skill in the art and that, therefore, would not facilitate a better understanding of the invention have not been presented in order to simplify the present description. Although embodiments of the present invention have been described, one of ordinary skill in 10 the art will, upon considering the foregoing description, recognize that many modifications and variations of the invention may be employed. All such variations and modifications of the invention are intended to be covered by the foregoing description and the following claims. 15 30

Claims (27)

1. A method of forming an article from an a-13 titanium alloy comprising, in 5 weight percentages, from about 2.9 to about 5.0 aluminum, from about 2.0 to about

3.0 vanadium, from about 0.4 to about 2.0 iron, from about 0.2 to about 0.3 oxygen, from about 0.005 to about 0.3 carbon, from about 0.001 to about 0.02 nitrogen, and less than about 0.5 of other elements, the method comprising: cold working the a-P titanium alloy. 10 2. The method of claim 1, wherein prior to cold working the a-P titanium alloy, the a-P3 titanium alloy is worked at a temperature greater than 1600OF to provide the alloy with a microstructure conducive to subsequent cold deformation. 15 3. The method of claim 1, wherein cold working the a-P titanium alloy is conducted at a temperature in the range of ambient temperature up to less than 1250°F.

4. The method of claim 1, wherein cold working the a-P3 titanium alloy is 20 conducted at a temperature in the range of ambient temperature up to 10001F.

5. The method of claim 1, wherein cold working the a-3 titanium alloy comprises working the a-13 titanium alloy at less than 1250OF by at least one technique selected from the group consisting of rolling, forging, extruding pilgering, 25 rocking, drawing, flow-turning, liquid compressive forming, gas compressive forming, hydro-forming, bulge forming, roll forming, stamping, fine-blanking, die pressing, deep drawing, coining, spinning, swaging, impact extruding, explosive forming, rubber forming, back extrusion, piercing, spinning, stretch forming, press bending, swaging, electromagnetic forming, and cold heading. 30 31 WO 2004/101838 PCT/US2004/013947

6. The method of claim 1, wherein the article is selected from the group consisting of a coil, a sheet, a strip, a foil, a plate, a bar, a rod, a wire, a tubular hollow, a pipe, a tube, a cloth, a mesh, a structural member, a cone, a cylinder, a duct, a pipe, a nozzle, a honeycomb structure, a fastener, a rivet and a washer. 5

7. The method of claim 1, where the a-P titanium alloy has lower flow stress than Ti-6AI-4V alloy.

8. The method of claim 1, wherein cold working the a-0 titanium alloy 10 comprises cold rolling the a-P titanium alloy, and wherein the article is a generally flat-rolled article selected from the group consisting of a sheet, a strip, a foil and a plate.

9. The method of claim 8, wherein cold rolling the a-3 titanium alloy 15 reduces a thickness of the a-3 titanium alloy by about 30% to about 60% prior to annealing the a-P titanium alloy.

10. The method of claim 8, wherein cold working the a-3 titanium alloy comprises reducing a thickness of the a-13 titanium alloy by at least two cold rolling 20 steps, and wherein the method further comprises: annealing the a-P titanium alloy intermediate successive cold rolling steps, wherein annealing the a-3 titanium alloy reduces stresses within the a P3 titanium alloy. 25 11. The method of claim 10, wherein at least one anneal intermediate successive cold rolling steps is conducted on a continuous anneal furnace line.

12. The method of claim 10, wherein in at least one of the cold rolling steps, a thickness of the a-P titanium alloy is reduced by 30% to 60%. 30 32 WO 2004/101838 PCT/US2004/013947

13. The method of claim 1, wherein cold working the a-P titanium alloy comprises rolling the a-j3 titanium alloy, and wherein the article is selected from the group consisting of a bar, a rod, and a wire. 5 14. The method of claim 1, wherein cold working the a-P titanium alloy comprises at least one of pilgering and rocking the a-P3 titanium alloy, and wherein the article is one of a tube and a pipe.

15. The method of claim 1, wherein cold working the a-P titanium alloy 10 comprises drawing the a-P titanium alloy, and wherein the article is selected from the group consisting of a rod, a wire, a bar and a tubular hollow.

16. The method of claim 1, wherein cold working the a-13 titanium alloy comprises at least one of flow-turning, shear spinning and spinning the a-P titanium 15 alloy, and wherein the article has axial symmetry.

17. The method of claim 1, wherein the article has a thickness up to 4 inches, and wherein room temperature properties of the article include tensile strength of at least 120 KSI, ultimate tensile strength of at least 130 KSI and 20 elongation of at least 10%.

18. The method of claim 17, wherein the article has elongation of at least 10%. 25 19. The method of claim 1, wherein yield strength, ultimate tensile strength and elongation properties of the article are each at least as great as for Ti-6AI-4V.

20. The method of claim 1, wherein the article can be bent around a radius of 4 times its thickness without failure of the article. 30 33 WO 2004/101838 PCT/US2004/013947

21. A method of making an article, the method comprising: providing an a-P3 titanium alloy comprising, in weight percentages, from about 2.9 to about 5.0 aluminum, from about 2.0 to about 3.0 vanadium, from about 0.4 to about 2.0 iron, from about 0.2 to about 0.3 oxygen, from about 5 0.005 to about 0.3 carbon, from about 0.001 to about 0.02 nitrogen, and less than about 0.5 of other elements; and working the alloy at a temperature less than 1250 0 F.

22. A method of forming an article from an a-3 titanium alloy comprising, in 10 weight percentages, from about 2.9 to about 5.0 aluminum, from about 2.0 to about 3.0 vanadium, from about 0.4 to about 2.0 iron, from about 0.2 to about 0.3 oxygen, from about 0.005 to about 0.3 carbon, from about 0.001 to about 0.02 nitrogen, and less than about 0.5 of other elements, the method comprising: reducing a thickness of the a-P titanium alloy by at least two cold rolling 15 steps, wherein in at least one cold rolling step a thickness of the a-P titanium alloy is reduced by 30% to 60%; and annealing the a-p titanium alloy intermediate successive cold rolling steps and thereby reducing stresses within the a-p titanium alloy. 20 23. The method of claim 22, wherein the article is selected from the group consisting of a sheet, a strip, a foil and a plate.

24. The method of claim 22, wherein at least one anneal intermediate successive cold rolling step is conducted on a continuous anneal furnace line. 25

25. A cold worked article of an a-p titanium alloy comprising, in weight percentages, from about 2.9 to about 5.0 aluminum, from about 2.0 to about 3.0 vanadium, from about 0.4 to about 2.0 iron, from about 0.2 to about 0.3 oxygen, from about 0.005 to about 0.3 carbon, from about 0.001 to about 0.02 nitrogen, and less 30 than about 0.5 of other elements. 34 WO 2004/101838 PCT/US2004/013947

26. The cold worked article of claim 25, wherein the article is selected from the group consisting of a coil, a sheet, a strip, a foil, a plate, a bar, a rod, a wire, a tubular hollow, a pipe, a tube, a cloth, a mesh, a structural member, a cone, a cylinder, a duct, a pipe, a nozzle, a honeycomb structure, a fastener, a rivet and a 5 washer.

27. The method of claim 25, wherein the article has a thickness up to 4 inches, and wherein room temperature properties of the article include tensile strength of at least 120 KSI and ultimate tensile strength of at least 130 KSI. 10

28. The method of claim 25, wherein the article has elongation of at least 10%.

29. The method of claim 25 wherein the article can be bent around a radius 15 of 4 times its thickness without failure of the article.

30. The article of claim 25, wherein the article is selected from the group consisting of a cold rolled article, a cold forged article, a cold pilgered article, a cold extruded article, a cold drawn article, a flow-turned article, a compressively formed 20 article, a hydro-formed article, a cold roll formed article, a cold stamped article, a fine-blanked article, a cold die pressed article, a cold deep drawn article, a coined article, a cold spun article, a cold swaged article, an impact extruded article, and explosive formed article, a rubber formed article, a back extruded article, a pierced article, a stretch formed article, a press bent article, an electromagnetically formed 25 article, and cold headed article.

31. A method of making an armor plate from an a-P titanium alloy comprising, in weight percentages, from about 2.9 to about 5.0 aluminum, from about 2.0 to about 3.0 vanadium, from about 0.4 to about 2.0 iron, from about 0.2 to 30 about 0.3 oxygen, from about 0.005 to about 0.3 carbon, from about 0.001 to about 0.02 nitrogen, and less than about 0.5 of other elements, the method comprising: 35 WO 2004/101838 PCT/US2004/013947 rolling the alloy at a temperature no greater than 400 0 F below the Tp of the alloy.

32. The method of claim 31, wherein rolling the alloy at a temperature less 5 than 1250°F comprises rolling the alloy at a temperature that is in the range of 400OF to 700°F below the Tp of the alloy. 36