(19)
(11) EP 1 654 393 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
14.11.2007 Bulletin 2007/46

(21) Application number: 04780090.9

(22) Date of filing: 04.08.2004
(51) International Patent Classification (IPC): 
C22F 1/18(2006.01)
C22C 14/00(2006.01)
(86) International application number:
PCT/US2004/025192
(87) International publication number:
WO 2005/017225 (24.02.2005 Gazette 2005/08)

(54)

PROCESS FOR MANUFACTURE OF parts FROM TITANIUM OR A TITANIUM ALLOY

VERFAHREN ZUR HERSTELLUNG VON Teilen AUS TITAN ODER EINER TITANLEGIERUNG

PROCEDE DE FABRICATION D'elements A PARTIR DE TITANE OU D'ALLIAGE DE TITANE


(84) Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

(30) Priority: 05.08.2003 US 492526 P

(43) Date of publication of application:
10.05.2006 Bulletin 2006/19

(73) Proprietor: Dynamet Holdings Inc.
Wilmington, DE 19810 (US)

(72) Inventor:
  • RIFFEE, Buford, R., Jr.
    New Port Richey, FL 34654 (US)

(74) Representative: Gill, Stephen Charles et al
Mewburn Ellis LLP York House 23 Kingsway
London WC2B 6HP
London WC2B 6HP (GB)


(56) References cited: : 
EP-A- 0 425 461
US-A- 5 032 189
US-A- 2 804 409
US-A- 5 173 134
   
       
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Field of the Invention



    [0001] This invention relates to processes for making fasteners and other parts from titanium or a titanium alloy, and in particular to a process in which a titanium or titanium alloy part is solution heat treated before being thermomechanically formed.

    Background of the Invention



    [0002] The titanium alloy Ti-6Al-4V has been used to make high strength fasteners, such as bolts and screws. The alloy is supplied in bar, rod, or wire form depending on the type and size of fastener to be made. Hitherto, the bar, rod, or wire has been supplied to the consumer in the annealed condition. The consumer forms the fasteners by such techniques as forging, heading, or extrusion, or a combination of those techniques. The fastener blanks are usually formed at an elevated temperature starting from about 649°C, but usually not below about 427°C. The fastener blanks are then cleaned by immersion in a molten salt bath, which is followed with acid etching.

    [0003] The fastener blanks are next heat treated to achieve a desired strength level. The known heat treatment is a two-stage treatment. In the first stage, the parts are solution treated, typically in an inert atmosphere, at about 899 to 968°C for about 1 hour and then water quenched. In the second stage of the heat treatment, the parts are precipitation hardened by an aging treatment at about 427 to 566°C for 2 to 8 hours and then cooled in an inert gas or in a vacuum. Hitherto, the aging step has been performed directly after the solution-treating step.

    [0004] The solution treatment is the most problematic step in the heat treatment cycle because during solution treatment contamination of the fasteners must be prevented. Titanium and its alloys are very reactive, especially at elevated temperatures such as those typically used for solution treatment. Any foreign material which comes into contact with the titanium or titanium alloy during solution heat treatment will result in contamination of the material. Common sources of foreign material in the solution treating process are contaminants in the furnace atmosphere or residual processing materials such as lubricants on the surfaces of the titanium blanks. In order to avoid the problems associated with the presence of such contaminants, special furnace atmospheres must be maintained and the fasteners must be thoroughly cleaned before they are placed in the heat treating furnace. Cleaning of the fasteners presents another problem because it involves the use of aggressive chemicals which pose environmental hazards and disposal concerns. Additionally, the cleaning operation can change the chemistry of the fasteners, such as by adding hydrogen, and can alter the dimensions of the fastener by dissolving metal from the blank. These problems make the cleaning step unreliable, time consuming, and costly.

    [0005] The known solution treating operations are also troublesome because the process often results in the final parts being unacceptable. In some cases the parts become contaminated with impurities because of less than desirable furnace atmospheres or residual lubricants on the parts. In other cases the parts have poor mechanical properties because of inadequate quenching. Moreover, parts can become distorted or they may stick together during solution treatment, or they may become bent or develop flat spots. It is also a fact that solution heat treating equipment is expensive and costly to operate for parts manufacturers. Elimination of the need to solution treat the headed fastener blanks, along with the associated relaxation of cleaning requirements, would permit significant improvements in the efficiency of the manufacturing process and greater uniformity of product quality.

    [0006] Fasteners are also manufactured by direct machining of solution treated titanium alloy bar. The machined fasteners are then age hardened. However, that process does not involve a forging operation. Therefore, it is not susceptible to the problems discussed above.

    [0007] Beta titanium alloys, such as Ti 3-8-6-4-4 and others, are supplied in the solution treated condition for forming into fasteners. The fasteners are then aged to achieve the desired properties. However, there are significant metallurgical differences between the beta alloys and the other known titanium alloys such as alpha, near-alpha, an alpha-beta alloys.

    [0008] US-A-2 804 409 describes a process for solution heat treating titanium-base alloy products to obtain a low yield strength, in order to facilitate cold working of the material prior to an age-hardening step. EP-A-0 425 461 describes a process for continuously solution heat treating an elongated metal alloy, such as titanium alloy. The final product can be aged after a final cold reduction.

    Summary of the Invention



    [0009] According to claim 1, the present invention provides a process of making parts from titanium and titanium alloy wire, rod, or bar. Here and throughout the remainder of this specification the term titanium means unalloyed titanium as well as alpha, near-alpha, and alpha-beta titanium alloys. The process includes the step of preparing an intermediate form of titanium. The intermediate form is solution treated under conditions of temperature and time that are sufficient to produce a desired level of strength when the alloy is subsequently age hardened. The solution treated material is then formed into a desired part or component, such as a fastener or a preform for a fastener. The forming stop is conducted with the alloy at an elevated temperature and the as-tormed part is rapidly cooled from the finish temperature. Subsequent to the forming step, the part is age hardened to achieve the desired level of strength and hardness.

    Detailed Description



    [0010] In a preferred embodiment of the process according to the present invention, an intermediate form of a titanium alloy, preferably Ti-6Al-4V, is prepared by any known method. Preferred intermediate forms include wire, rod, and bar. The Ti-6Al-4V alloy is a known titanium alloy that contains about 6 weight percent (%) aluminum, about 4 % vanadium, and the balance is titanium and usual impurities. The impurities present in the alloy are restricted such that the alloy contains not more than about 0.10% carbon, not more than about 0.05% nitrogen, not more than about 0.0125% hydrogen, and not more than about 0.20% oxygen. In the preferred titanium alloy used in this process, the oxygen is preferably limited to about 0.14-0.17%. The method by which the intermediate form is made is not critical and any of the known methods for making titanium alloy wire, rod, or bar may be used.

    [0011] The intermediate form of the titanium alloy is then solution treated at about 899-968 °C for a time of at least about 1 minute up to about 2 hours, and then water quenched. Preferably, the intermediate form is heated at the solution temperature for about 1 hour. Prior to forming a desired product from the intermediate form, the intermediate form may be coated with a lubricant. The preferred lubricant is a dry film lubricant, which consists of graphite and molybdenum disulfide. Other lubricants that are known to those skilled in the art for similar purposes may also be suitable.

    [0012] The lubricated wire, rod, or bar is then subjected to thermomechanical working to form the desired part. The preferred forming operation is forging, and heading is particularly preferred for making small parts from wire or rod. For some applications extruding techniques can be used in connection with the preparation of parts by this process. Prior to forming, the intermediate form is cut to a starting size, heated to an elevated starting temperature, and then mechanically worked to the desired size and shape. The elevated starting temperature for the thermomechanical forming is selected to be as close to the solution treating temperature as practicable. A lower forming temperature can be used for applications where adequate lubrication, extended die life, or dimensional control of the part or preform is important. Preferably, the parts are formed from a starting temperature of about 871 °C, but preferably not below about 704°C or 649°C. Lower finishing temperatures may be used under appropriate circumstances. However, it is expected that the finishing temperature would, in any event, not be below about 427°C. The as-formed parts are rapidly cooled from the finishing temperature, preferably by water quenching.

    [0013] The as-formed parts are then age hardened, preferably in a vacuum heat treating furnace. The parts may also be aged in an inert atmosphere such as argon or helium. It is also expected that the parts can be aged in air. When the parts are aged in a vacuum furnace, it may be preferable to clean the parts to prevent their being contaminated in the heat treating furnace. Such cleaning is accomplished by first immersing the parts in a molten salt bath and then acid etching. Aging is conducted at a temperature of about 427 to 566°C for about 2 to 8 hours, followed by cooling in inert gas or in a vacuum.

    [0014] The heat-treated parts are then ground or machined as necessary to final dimension and shape.


    Claims

    1. A process for making parts from titanium or a titanium alloy comprising the steps of:

    preparing an intermediate form of titanium or of a titanium alloy selected from the group consisting of an alpha alloy, a near-alpha alloy, and an alpha-beta alloy; then

    solution heat treating the intermediate form under conditions of temperature and time that are selected to produce a desired level of strength when the titanium or titanium alloy are subsequently age hardened; then

    reheating the intermediate form to an elevated starting temperature;

    mechanically working the reheated intermediate form from the starting temperature to a finishing temperature to provide a desired part or a preform for a desired part; and then

    age hardening the as-formed part or preform under conditions of temperature and time that are selected to produce the desired level of strength.


     
    2. The process as set forth in Claim 1 wherein the intermediate form is prepared from an alpha-beta titanium alloy.
     
    3. The process as set forth in Claim 1 or 2 wherein the intermediate form is prepared from a titanium alloy comprising about 6% aluminum, about 4% vanadium, and the balance titanium and usual impurities.
     
    4. The process as set forth in Claim 1, 2, or 3 wherein the step of preparing the intermediate form comprises the step of forming the titanium alloy into an elongated form selected from the group consisting of wire, rod, and bar.
     
    5. The process as set forth in any of Claims 1-4 which comprises the step of cutting the intermediate form into pieces having a substantially uniform length, after the solution heat treating step and before the mechanical working step.
     
    6. The process as set forth in any of Claims 1-5 comprising the step of rapidly cooling the part from the finishing temperature after said mechanical working step.
     
    7. The process as set forth in any of Claims 1-6 wherein the step of preparing the intermediate form of titanium or the titanium alloy comprises the step of preparing the titanium or titanium alloy such that it contains not more than about 0.10% carbon, not more than about 0.05% nitrogen, not more than about 0.0125% hydrogen, and not more than about 0.20% oxygen.
     
    8. The process as set forth in Claim 7 wherein the step of preparing the titanium or titanium alloy comprises the step of controlling the melting of the titanium or titanium alloy such that it contains not more than about 0.17% oxygen.
     
    9. The process as set forth in any of Claims 1-8, wherein the step of solution treating the intermediate form comprises the step of heating the intermediate form at a temperature of about 899-968°C for at least about 1 minute up to about 2 hours, and then quenching the intermediate form.
     
    10. The process as set forth in any of Claims 1-9 wherein the step of reheating the solution treated intermediate form comprises the step of heating the intermediate form to a starting temperature of about 871°C.
     
    11. The process as set forth in any of Claims 1-10 wherein the age-hardening step comprises the steps of heating the as-formed part or preform to a temperature of at least about 427°C to not greater than about 566°C , holding the part or preform at said temperature for about 2 to 8 hours, and then cooling the part from said temperature.
     
    12. The process as set forth in any of Claims 1-11 wherein the mechanical working step is performed from a starting temperature of about 871°C to a finishing temperature not below about 427°C .
     
    13. The process as set forth in any of Claims 1-12 wherein the mechanical working step is performed from a starting temperature of about 871°C to a finishing temperature not below about 649°C .
     
    14. The process as set forth in any of Claims 1-13 wherein the mechanical working step is performed from a starting temperature of about 871 °C to a finishing temperature not below about 704°C .
     


    Ansprüche

    1. Verfahren zur Herstellung von Teilen aus Titan oder einer Titanlegierung, umfassend folgende Schritte:

    Herstellung einer Zwischenform aus Titan oder einer Titanlegierung, die aus der aus einer Alpha-Legierung, einer Alpha-nahen Legierung und einer Alpha-Beta-Legierung bestehenden Gruppe ausgewählt ist; dann

    Lösungsglühen der Zwischenform unter Temperatur- und Zeitbedingungen, die so ausgewählt sind, dass ein gewünschtes Maß an Festigkeit erzeugt wird, wenn das Titan oder die Titanverbindung in der Folge ausgehärtet werden; dann

    erneutes Erhitzen der Zwischenform auf eine erhöhte Ausgangstemperatur;

    mechanische Bearbeitung der erneut erhitzten Zwischenform von der Ausgangstemperatur auf eine Endtemperatur zur Bereitstellung eines gewünschten Teils oder einer Vorform des gewünschten Teils; und dann

    Aushärten des so geformten Teils oder der Vorform unter Temperatur- und Zeitbedingungen, die so ausgewählt sind, dass ein gewünschtes Maß an Festigkeit erzeugt wird.


     
    2. Verfahren nach Anspruch 1, worin die Zwischenform aus einer Alpha-Beta-Titanlegierung hergestellt wird.
     
    3. Verfahren nach Anspruch 1 oder 2, worin die Zwischenform aus einer Titanlegierung hergestellt wird, die etwa 6 % Aluminium, etwa 4 % Vanadium und als Rest Titan und die üblichen Verunreinigungen umfasst.
     
    4. Verfahren nach Anspruch 1, 2 oder 3, worin der Schritt der Herstellung der Zwischenform einen Schritt umfasst, bei dem die Titanlegierung in eine längliche Form ausgebildet wird, die aus der aus Draht, Stab und Stange bestehenden Gruppe ausgewählt ist.
     
    5. Verfahren nach einem der Ansprüche 1 bis 4, das einen Schritt umfasst, bei dem die Zwischenform nach dem Lösungsglühen und vor der mechanischen Bearbeitung in Stücke mit im Wesentlichen einheitlicher Länge geschnitten wird.
     
    6. Verfahren nach einem der Ansprüche 1 bis 5, umfassend einen Schritt, bei dem der Teil nach dem Schritt der mechanischen Bearbeitung rasch von der Endtemperatur abgekühlt wird.
     
    7. Verfahren nach einem der Ansprüche 1 bis 6, worin der Schritt der Herstellung der Zwischenform aus Titan oder einer Titanlegierung einen Schritt umfasst, bei dem das Titan oder die Titanlegierung so hergestellt wird, dass es/sie nicht mehr als etwa 0,10 % Kohlenstoff, nicht mehr als etwa 0,05 % Stickstoff, nicht mehr als etwa 0,0125 % Wasserstoff und nicht mehr als etwa 0,20 % Sauerstoff enthält.
     
    8. Verfahren nach Anspruch 7, worin der Schritt der Herstellung von Titan oder der Titanlegierung einen Schritt umfasst, bei dem die Schmelze des Titans oder der Titanlegierung so gesteuert wird, dass es/sie nicht mehr als etwa 0,17 % Sauerstoff enthält.
     
    9. Verfahren nach einem der Ansprüche 1 bis 8, worin der Schritt des Lösungsglühens der Zwischenform einen Schritt umfasst, bei dem die Zwischenform zumindest 1 min und bis zu 2 h lang auf eine Temperatur von etwa 899 bis 968 °C erhitzt wird, wonach die Zwischenform abgeschreckt wird.
     
    10. Verfahren nach einem der Ansprüche 1 bis 9, worin der Schritt des erneuten Erhitzens der lösungsgeglühten Zwischenform einen Schritt umfasst, bei dem die Zwischenform auf eine Ausgangstemperatur von etwa 871 °C erhitzt wird.
     
    11. Verfahren nach einem der Ansprüche 1 bis 10, worin der Schritt des Aushärtens einen Schritt umfasst, bei dem der so geformte Teil oder die Vorform auf eine Temperatur von zumindest etwa 427 °C und nicht mehr als etwa 566 °C erhitzt wird, der Teil oder die Vorform etwa 2 bis 8 h lang auf dieser Temperatur gehalten wird und der Teil dann von dieser Temperatur abgekühlt wird.
     
    12. Verfahren nach einem der Ansprüche 1 bis 11, worin der Schritt der mechanischen Bearbeitung von einer Ausgangstemperatur von etwa 871 °C bis zu einer Endtemperatur von nicht weniger als etwa 427 °C erfolgt.
     
    13. Verfahren nach einem der Ansprüche 1 bis 12, worin der Schritt der mechanischen Bearbeitung von einer Ausgangstemperatur von etwa 871 °C bis zu einer Endtemperatur von nicht weniger als etwa 649 °C erfolgt.
     
    14. Verfahren nach einem der Ansprüche 1 bis 13, worin der Schritt der mechanischen Bearbeitung von einer Ausgangstemperatur von etwa 871 °C bis zu einer Endtemperatur von nicht weniger als etwa 704 °C erfolgt.
     


    Revendications

    1. Procédé de fabrication de pièces à partir de titane ou d'un alliage de titane comprenant les étapes de:

    préparer une forme intermédiaire en titane ou un alliage de titane sélectionné dans le groupe consistant en un alliage alpha, un alliage presque alpha, et un alliage alpha-béta;

    traiter thermiquement en solution la forme intermédiaire dans des conditions de température et de temps qui sont sélectionnées pour produire un niveau souhaité de résistance mécanique quand le titane ou l'alliage de titane sont subséquemment durcis par vieillissement; puis

    réchauffer la forme intermédiaire à une température élevée de départ;

    travailler mécaniquement la forme intermédiaire réchauffée à partir de la température de départ jusqu'à une température de finissage pour donner une pièce souhaitée ou une préforme pour une pièce souhaitée; puis

    durcir par vieillissement la pièce telle que formée ou préforme dans des conditions de température et de temps qui sont sélectionnées pour produire le niveau souhaité de résistance mécanique.


     
    2. Procédé selon la revendication 1 où la forme intermédiaire est préparée à partir d'un alliage de titane alpha-béta.
     
    3. Procédé selon la revendication 1 ou 2 où la forme intermédiaire est préparée à partir d'un alliage de titane comprenant environ 6% d'aluminium, environ 4% de vanadium, et le reste étant du titane et des impuretés usuelles.
     
    4. Procédé selon la revendication 1, 2 ou 3 où l'étape de préparer la forme intermédiaire comprend l'étape de former l'alliage de titane en une forme allongée sélectionnée dans le groupe consistant en un fil, une tige, et une barre.
     
    5. Procédé selon l'une quelconque des revendications 1-4 qui comprend l'étape de couper la forme intermédiaire en morceaux ayant une longueur sensiblement uniforme après l'étape de traitement thermique en solution et avant l'étape d'élaboration mécanique.
     
    6. Procédé selon l'une quelconque des revendications 1-5 comprenant l'étape de refroidir rapidement la pièce à partir de la température de finissage après ladite étape de travail mécanique.
     
    7. Procédé selon l'une quelconque des revendications 1-6 où l'étape de préparer la forme intermédiaire de titane ou d'alliage de titane comprend l'étape de préparer le titane ou l'alliage de titane de façon qu'il ne contienne pas plus d'environ 0,10% de carbone, pas plus d'environ 0,05% d'azote, pas plus d'environ 0,0125% d'hydrogène, et pas plus d'environ 0,20% d'oxygène.
     
    8. Procédé selon la revendication 7 où l'étape de préparer le titane ou l'alliage de titane comprend l'étape de contrôler la fusion du titane ou de l'alliage de titane de façon qu'il ne contienne pas plus d'environ 0,17% d'oxygène.
     
    9. Procédé selon l'une quelconque des revendications 1-8, où l'étape de traiter en solution la forme intermédiaire comprend l'étape de chauffer la forme intermédiaire à une température d'environ 899-968°C pendant au moins environ 1 minute jusqu'à environ 2 heures, et puis de tremper la forme intermédiaire.
     
    10. Procédé selon l'une quelconque des revendications 1-9 où l'étape de réchauffer la forme intermédiaire traitée en solution comprend l'étape de chauffer la forme intermédiaire à une température de départ d'environ 871°C.
     
    11. Procédé selon l'une quelconque des revendications 1-10 où l'étape de durcissement par vieillissement comprend les étapes de chauffer la pièce telle que formée ou préforme à une température d'au moins environ 427°C à pas plus d'environ 566°C, de maintenir la pièce ou préforme à ladite température pendant environ 2 à 8 heures, et puis de refroidir la pièce à partir de ladite température.
     
    12. Procédé selon l'une quelconque des revendications 1-11 où l'étape de travail mécanique est accomplie à partir d'une température de départ d'environ 871°C jusqu'à une température de finissage qui n'est pas en dessous d'environ 427°C.
     
    13. Procédé selon l'une quelconque des revendications 1-12 où l'étape de travail mécanique est accomplie à partir d'une température de départ d'environ 871°C jusqu'à une température de finissage qui n'est pas en dessous d'environ 649°C.
     
    14. Procédé selon l'une quelconque des revendications 1-13 où l'étape de travail mécanique est accomplie à partir d'une température de départ d'environ 871°C jusqu'à une température de finissage qui n'est pas en dessous d'environ 704°C.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description