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US20080011391A1 - Method for Producing Wear-Resistant and Fatigue-Resistant Edge Layers in Titanium Alloys, and Components Produced Therewith - Google Patents

Method for Producing Wear-Resistant and Fatigue-Resistant Edge Layers in Titanium Alloys, and Components Produced Therewith Download PDF

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Publication number
US20080011391A1
US20080011391A1 US11/571,818 US57181805A US2008011391A1 US 20080011391 A1 US20080011391 A1 US 20080011391A1 US 57181805 A US57181805 A US 57181805A US 2008011391 A1 US2008011391 A1 US 2008011391A1
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Prior art keywords
resistant
wear
gas
fatigue
titanium
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Berndt Brenner
Steffen Bonss
Frank Tietz
Joerg Kaspar
David Walter
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Siemens Corp
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Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Siemens Corp
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Assigned to FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V. reassignment FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BONSS, STEFFEN, BRENNER, PROFESSOR BERNDT, KASPAR DR., JOERG, TIETZ, FRANK, WALTER, DAVID
Publication of US20080011391A1 publication Critical patent/US20080011391A1/en
Assigned to FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V., SIEMENS AG reassignment FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V.
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/20—Carburising
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/20—Bonding
    • B23K26/32—Bonding taking account of the properties of the material involved
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/34—Laser welding for purposes other than joining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K31/00—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups
    • B23K31/02—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups relating to soldering or welding
    • B23K31/025—Connecting cutting edges or the like to tools; Attaching reinforcements to workpieces, e.g. wear-resisting zones to tableware
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
    • B23K35/325—Ti as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/001—Turbines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/08—Non-ferrous metals or alloys
    • B23K2103/14—Titanium or alloys thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

  • the invention relates to the edge layer finishing of functional components, and in particular to a method for producing wear-resistant and fatigue-resistant edge layers in titanium alloys, and components produced therewith.
  • Articles for which the use thereof is possible and practical are components made of titanium alloys which undergo severe stress from erosion, cavitation, droplet impingement, or sliding abrasion, which in addition to their tribological load are also subjected to high cyclic load.
  • the invention may be used in a particularly advantageous manner for protecting turbine blades in the low-pressure region of steam turbines.
  • components which may thus be finished in a very advantageous manner are those from the aviation and aerospace sectors, such as, e.g., landing flap guides, drive shafts, hydraulic system components, bolts, or similar connecting elements; parts used in chemical equipment construction (e.g., sonotrode tips, sonochemical facilities), medical technology (e.g., instruments, implants), and high-performance engine construction (e.g., injection systems, valve seats, valve stems, or the like).
  • chemical equipment construction e.g., sonotrode tips, sonochemical facilities
  • medical technology e.g., instruments, implants
  • high-performance engine construction e.g., injection systems, valve seats, valve stems, or the like.
  • Titanium is a superior construction material whose high specific strength, exceptional fatigue resistance, good stress-crack corrosion resistance, chemical resistance, and biocompatibility make it ideal for various special applications.
  • the low resistance of titanium to various types of wear is often an obstacle to its more widespread use.
  • the demand for effective wear protection methods has intensified due to the fact that many thermal and chemicothermal edge layer finishing methods used for steel materials, for example, cannot be employed for titanium alloys.
  • the edge layer Due to the high affinity of the titanium for reactive gases such as nitrogen, for example, the gas is immediately dissolved by the melt, and in the case of nitrogen forms titanium nitride, which precipitates from the melt in the form of dendrites.
  • the edge layer is composed of a metallic titanium matrix having an altered ⁇ / ⁇ proportion compared to the initial state, and finely divided titanium nitride dendrites.
  • the hardness of the edge layer is typically 600-1200 HV. Edge layers produced in this manner have very good resistance to stress from sliding abrasion, abrasive wear, or oscillatory sliding abrasion.
  • the aim is to identify the disadvantages of edge layers produced in this manner for the case of application of increasing the resistance of steam turbine blades to wear from droplet impingement.
  • rotor blades of low-pressure stages in steam turbines are subjected to extremely high quasistatic (centrifugal force, blade twisting), cyclic (periodic steam pressure impingement, blade vibrations), mechanical-chemical (vibratory corrosion and stress-crack corrosion), and tribological (droplet impingement) loads.
  • selected titanium alloys such as, e.g., Ti6AI4V withstand the quasistatic, cyclic, and mechanical-chemical loads very well, their resistance to droplet impingement wear is not adequate to effectively protect highly stressed steam turbine blades from wear erosion as the result of the continuous impact of water droplets in the vicinity of the leading edge.
  • Gerdes claims the application of laser gas alloying for increasing the wear resistance of low-pressure steam turbine blades (see EP 0491075 B1).
  • a boride-, carbide-, or nitride-forming gas is thereby added to the melt bath in a concentration that results in precipitation of borides, carbides, or nitrides in the melt.
  • nitrogen as reaction gas
  • extremely hard titanium nitride is formed when volumetric proportions of nitrogen of typically 20 to 60% with respect to inert gas are used.
  • a hardness of 500 to 900 HV, preferably 500 to 700 HV is obtained in the edge layer of the Ti6AI4V alloy. Information was not provided concerning the wear resistance and fatigue resistance achieved.
  • the thickness of the protective layer is limited to 0.4 to 1.0 mm.
  • a mechanical or thermal aftertreatment of the layers thus produced is not mentioned, but should not be provided, since particular reference is made to the fact that protection from droplet erosion is obtained with a single method step, namely, the laser gas alloying.
  • the shortcoming of the method is that an edge layer-finished turbine blade of this type has a cyclic load capacity that is far too low. Therefore, the method cannot be used for turbine blades subjected to high cyclic load.
  • a further shortcoming results from the very limited depth of the protective layer of 0.4 to 1.0 mm.
  • erosive types of wear such as, e.g., the droplet impingement wear on turbine blades, this results in limited service life.
  • the shortcoming results from the fact that microfissures form when the nitrogen content in the gas mixture exceeds 20%.
  • the tendency for microfissure formation increases with the thickness of the protective layer.
  • the heterogeneous structure which is formed from a relatively brittle ⁇ -titanium matrix with very hard embedded TiN particles, in principle is not suitable for achieving high fatigue resistance.
  • the protective layer having a thickness between 0.4 mm and 1.0 mm, essentially contains titanium nitrides embedded in an ⁇ -titanium matrix. The morphology and distribution of the titanium nitrides depends on the process parameters during laser gas alloying, and the nitrogen concentration in the gas atmosphere. Depending on the nitrogen concentration, the titanium nitrides are to be embodied in a plate-like or dendritic manner.
  • the proportions are to be between 1:4 and 1:2; i.e., the nitrogen content is to be between 20% and 33%.
  • the protective layer formed may then have a Vickers hardness of 600 to 800 HV, depending on the conditions during the laser gas alloying.
  • the roughening reduces the near-surface internal pressure stress of the shot blast treatment. Furthermore, the negative effect of the microfissures, which are still present but the effects of which have been removed by the shot blasting, may reoccur.
  • the shortcoming results from the fact that the purpose of the claimed heat treatment is to form a high-vanadium phase having a ⁇ -titanium lattice structure.
  • the present invention provides a method for producing wear-resistant and fatigue-resistant edge layers in titanium alloys by high-intensity energy gas alloying, including: carrying out high-intensity energy gas alloying in a treatment zone using a reaction gas that contains or releases interstitially soluble elements in the titanium alloy used, and wherein the partial pressure of the reaction gas is selected such that the partial pressure remains below the threshold value above which nitride, carbide, or boride titanium phases are produced.
  • nitrogen is used as the reaction gas which is interstitially soluble in the titanium alloy, and the nitrogen together with an inert gas is fed to the laser treatment zone.
  • the volumetric proportion V N of the nitrogen in the working gas mixture is 1% ⁇ V N ⁇ 15%.
  • the volumetric proportion V N of the nitrogen is selected in the range of 1% ⁇ V N ⁇ 11% for components subjected to particularly high fatigue stress.
  • the volumetric proportion V N of the nitrogen in the working gas is altered during the processing and is adapted to the localized load conditions and to the ratio of wear to cyclic load.
  • the gas-alloyed edge layer is subjected to an accelerated cooling.
  • the accelerated cooling is achieved by a self-quenching as the result of an external cooling of the untreated portions of the component during the gas alloying.
  • the accelerated cooling is achieved by a localized gas cooling subsequent to the treatment zone.
  • the component is mechanically fixed before the high-intensity energy gas alloying and is maintained in the fixed state during the high-intensity energy gas alloying.
  • the fixing and cooling are implemented by the same device.
  • the gas-alloyed edge layer is mechanically smoothed by vibratory finishing, grinding, and/or polishing.
  • an aging heat treatment of the entire component is performed at a temperature T A of 350° ⁇ T A ⁇ 700° C. for an aging period t A of 2 h ⁇ t A ⁇ 24 h.
  • a stress-free annealing is subsequently carried out at a temperature T SR of 300° ⁇ T SR ⁇ 620° C. and a period t SR of 1 h ⁇ t SR ⁇ 10 h.
  • the gas-alloyed layer is shot-blasted after the cooling from the last heat treatment.
  • a non-vac electron beam unit is used as a high-intensity energy source.
  • a plasma torch is used as a high-intensity energy source.
  • a laser is used as a high-intensity energy source.
  • the present invention also provides a wear-resistant and fatigue-resistant component made of a titanium alloy, having a gas-alloyed edge layer formed by carrying out high-intensity energy gas alloying in a treatment zone using a reaction gas that contains or releases interstitially soluble elements in the titanium alloy used, and wherein the partial pressure of the reaction gas being selected such that the partial pressure remains below the threshold value above which nitride, carbide, or boride titanium phases are produced, such that the wear-resistant edge layer is composed of a fine-grain mixture of ⁇ -titanium and ⁇ -titanium grains with an interstitially dissolved reaction gas, has a surface hardness H S , measured on the ground surface, of 360 HV0.5 ⁇ H S ⁇ 500 HV0.5, or an edge layer microhardness H R , measured at the polished cross section 0.1 mm below the surface, of 360 HV0.1 ⁇ H R ⁇ 560 HV0.1, extends over a depth t R of 0.1 mm ⁇ t R ⁇ 3.5
  • ü is 0.5 ⁇ ü ⁇ 0.9.
  • the edge layer is composed of a wide individual track which is produced by oscillating a beam of the high-intensity energy source transverse to a feed direction.
  • the component represents a turbine blade subjected to erosion or droplet impingement stress.
  • the wear-resistant edge layer includes a leading edge of the blade in a direction of a concave side of the blade and as well as in a direction of a back side of the blade.
  • the wear-resistant edge layer is composed of overlapping tracks parallel to the leading edge.
  • the sequence of track production is selected in such a way that the tracks are each situated in alternation with the neutral fiber with respect to a bending of the turbine blade in the pliant direction.
  • the wear-resistant edge layer is composed of tracks situated transverse to the longitudinal axis of the turbine blade or to the leading edges thereof, the tracks extend around the leading edge, and the oscillation of the beam from the high-intensity energy source is produced about the longitudinal axis of the blade as a result of an oscillating vibratory motion of the turbine blade.
  • a track field boundary on the blade foot side runs at an angle of 20-65° with respect to the leading edge.
  • the edge layer hardness is correspondingly adapted according to localized load conditions and a ratio of wear to cyclic load.
  • FIG. 1 illustrates the cavitational wear rate ⁇ ⁇ dot over (m) ⁇ as a function of the nitrogen content V N in the working gas.
  • FIGS. 2 ( a )-( b ) illustrate the cross section of a laser-gas-alloyed leading edge.
  • the aim of the present invention is to provide a method for improving the wear resistance of titanium alloys which results in the least possible decrease in cyclic load capacity in the laser gas-alloyed state compared to the initial state, and which also allows an improved retention of the cyclic load capacity during continued wear.
  • a further aim is to provide wear-resistant and fatigue-resistant components which may be advantageously manufactured using this method.
  • the object of the present invention is to provide an edge layer finishing method which allows establishment of a homogeneous and semi-rigid structural state without the presence of brittle titanium nitride, carbide, or boride phases, regardless of the vanadium content of the titanium alloy, achievement of very good resistance to stress from non-abrasive, cavitational, or droplet impingement wear, and realization of layer thicknesses greater than 1 mm without the formation of microfissures.
  • This object is attained according to the invention by a method for producing wear-resistant and erosion-resistant edge layers in titanium alloys.
  • Components according to the invention and advantageous embodiments are described herein.
  • the method proceeds from introducing into the melt gaseous elements which are soluble in the melt and which after solidification are interstitially dissolved, up to a concentration in which nitride, carbide, or boride titanium phases are not yet formed.
  • this results in a comparatively homogeneous and fine-grained structure having structure lengths of several micrometers, of ⁇ -titanium grains, individual ⁇ -titanium grains, and an arrangement of a mixture of very fine ⁇ -titanium and ⁇ -titanium grains located between the ⁇ -titanium grains.
  • the nitride, carbide, or boride phases heretofore known for their negative effects on microfissure formation and development of localized stress concentrations may be avoided.
  • nitrogen is used as an element to be introduced interstitially
  • the specific choice thereby depends on the track overlap rate ü and the extent of wear stress relative to the magnitude of the cyclic load. In general, low nitrogen contents are selected for elevated cyclic loads at low wear stress, and vice versa. Likewise, low nitrogen contents are used for higher track overlap rates.
  • Use may be made of a further influencing variable for setting the ratio between strength and ductility by virtue of the selection of the cooling rate.
  • the component is mechanically fixed in an initial position before starting the gas alloying, and this fixed position is maintained during the treatment. This procedure also has the advantage that the target coordinates for the laser beam do not drift during the treatment, and the CNC program therefore does not require follow-up correction.
  • the surface After the laser gas alloying, the surface has a roughness which generally is excessive for components under high cyclic load, for which one embodiment provides mechanical aftertreatment.
  • the mechanical aftertreatment may be performed by grinding, vibratory finishing, and/or polishing.
  • the mechanical properties, in particular the fatigue resistance, may be further improved by the heat treatment.
  • a procedure which the structure formation resulting from phase transitions and hardening, as well as the simultaneous reduction of the internal tension stress remaining after the gas alloying, or in another embodiment, a procedure wherein the internal tension state may be improved without significant alteration of the structure.
  • one embodiment of the present invention provides for shot blasting of the wear-resistant edge layer as a further measure for increasing the fatigue resistance.
  • the gas alloying of titanium is carried out using a laser as an energy source with sufficiently high power density.
  • a non-vac electron beam or a plasma source may also be used as an energy source.
  • the working gas mixture composed of reaction gas and inert gas must be fed in a careful and reproducible manner by use of collimator systems.
  • the wear-resistant edge layer can be composed of a fine-grain mixture of ⁇ -titanium and ⁇ -titanium grains with an interstitially dissolved reaction gas has a surface hardness H S , measured on the ground surface, of 360 HV0.5 ⁇ H S ⁇ 500 HV0.5, or an edge layer microhardness H R , measured at the polished cross section 0.1 mm below the surface, of 360 HV0.1 ⁇ H R ⁇ 560 HV0.1, extends over a depth t R of 0.1 mm ⁇ t R ⁇ 3.5 mm.
  • the required width of the wear protection zone is greater than the track width that is normally possible, overlapping track patterns may be produced, or wider tracks may be realized by a rapid oscillation of the beam from the energy source transverse to the feed direction of the component. If necessary, in individual cases the component may be set in oscillatory motion instead of the beam.
  • the present invention may be applied in a particularly advantageous manner to turbine blades stressed by droplet impingement or erosion.
  • technically expedient and beneficial embodiments of the shape, position, and production of the wear-resistant edge layer can be provided.
  • the sonotrode is composed of the material Ti6AI4V, and in the initial state has a hardness of 340 HV0.5.
  • the aim is to provide better protection of the sonotrode tip and the adjacent regions of the cylindrical surface area from cavitational load while ensuring sufficiently high cyclic load capacity.
  • the sonotrode is placed in a concentric chuck of a CNC rotational axis of a laser processor.
  • the sonotrode has an oversized dimension of 0.2 mm in the region to be treated.
  • a shielding gas bell designed according to EP 0829325 is located above the component, and ensures that the working gas mixture can be reproducibly set with very good exclusion of oxygen, using simple equipment. By use of a gas mixing station a preset nitrogen-argon mixture in a 9%:91% volumetric ratio is blown into the shielding gas bell.
  • the shielding gas bell is attached to the beam-shaping unit of the laser so as to be movable in the z-direction. By means of an air cushion at its lower boundary, the shielding gas bell is also movable in the two other directions x and y with respect to the component.
  • a CO 2 laser with power set at 3.1 kW is used as the laser.
  • a feed rate of 540 mm/min is preselected via the CNC program. After purging for 90 s with the working gas mixture, the process is initiated by starting the CNC program, which travels over the sonotrode tip in a grid-like manner, and by switching on the laser. After the slow cooling, the sonotrode is removed from the apparatus, and the excess dimensions in the laser-treated region are ground off.
  • the surface hardness H S reaches approximately 440 HV0.5. This corresponds approximately to an edge layer hardness H R of approximately 510 HV0.1, measured on the polished cross section at 0.1 below the surface.
  • the fluctuation in hardness transverse to the tracks is approximately 50 HV0.1.
  • the structure is composed of ⁇ -titanium grains and finely dispersed deposits of ⁇ - and ⁇ -titanium at the grain boundaries of the ⁇ -titanium grains.
  • the maximum size of the ⁇ -titanium grains is several micrometers.
  • This treatment allows the wear rate at the sonotrode tip to be reduced by approximately a factor of three.
  • the cyclic load capacity thus achieved is sufficient to eliminate the need for a further measure for increasing the fatigue resistance.
  • FIG. 1 illustrates the wear rate ⁇ ⁇ dot over (m) ⁇ as a function of the volumetric proportion of nitrogen V N in the working gas.
  • the load from cavitational wear was measured in accordance with ASTM G32-85, using a VC501 high-frequency generator from Sonics & Materials Inc.
  • the test parameters are as follows: indirect vibrational cavitational load on the specimens; frequency: 20 kHz, amplitude: ⁇ 20 ⁇ m, water temperature (controlled): 22° C. ⁇ 1K, immersion depth of the specimen surface: 12 . . . 16 mm; distance sonotrode surface to specimen surface: 0.5 mm, load duration: 20 h, measurement of mass erosion every 1.5 h.
  • the wear rate is determined from the increase in slope of the mass loss-time curve after the end of the incubation period.
  • FIG. 1 clearly shows that, as already known, the resistance to cavitational wear may be significantly improved by laser gas alloying with nitrogen. Contrary to the preconceptions among those skilled in the art, however, this does not require the precipitation of titanium nitride. Even with nitrogen contents of 7 to 13%, wear properties are achieved that are comparable to those with nitrogen contents greater than 20%. In contrast, it was found that the formation of precipitates of dendritic titanium nitride has a very negative effect on the one-way mechanical (crack formation stress) and cyclic (fatigue resistance) load capacity.
  • the crack formation stress for example, at the edge layer already begins to decrease at a nitrogen content greater than 13%, i.e., clearly before the precipitation of titanium nitride dendrites.
  • This threshold value is valid for the stated test conditions and shifts to higher nitrogen contents as the overlap rate decreases.
  • a component according to the invention is to be explained using an end stage rotor blade of a large steam turbine.
  • the leading edges of these rotor blades are subjected to an intensive droplet impingement stress, which in their component stress, wear manifestations, and mechanisms of localized material damage share many commonalities with cavitational wear. Methods and material states which result in improved cavitational wear resistance also have improved resistance to droplet impingement wear.
  • the end stage rotor blade is produced from the titanium alloy Ti6AI4V due to the high stress from centrifugal force.
  • the width of the wear zone is 17 mm on the back side of the blade and 6 mm on the concave side of the blade. Because of the high cyclic load on the blade, other passive protection methods such as soldering of stellite plates, electric spark coating, vacuum plasma injection, or laser gas alloying carried out according to the prior art are excluded.
  • the component designed according to the invention has a layer with a depth up to t R ⁇ 2.5 mm, composed of a fine-particle mixture of ⁇ - and ⁇ -titanium grains with interstitially dissolved nitrogen.
  • This edge layer has a width of 20 mm on the back side of the blade and a width of 10 mm on the concave side of the blade, and therefore covers a region larger than the width of the wear zone.
  • a laser power of 4.2 kW with a feed rate of 650 mm/min are selected.
  • the layer has a surface hardness of H S ⁇ 425 HV0.5.
  • the provision of thermal stresses during the blade processing causes warpage, which generally is intolerably large in the direction of the lowest bending moment. This is counteracted by forming the wear-resistant zone from individual overlapping tracks and selecting the sequence of the track production such that, after a certain number of starting tracks (see FIG. 2 b, two starting tracks 1 , 2 ), the additional tracks are applied in alternation on the concave side and the back side of the blade. To minimize warpage, more tracks may be applied on the concave side of the blade than would be necessary on the concave side of the blade, based on the dimensions of the wear zone. The last track is applied along the leading edge. Depending on the circumstances, the last track is produced with a lower remelting depth and with higher feed rates. In addition to these measures for warpage reduction, the turbine blade is mechanically fixed before the start of treatment and is maintained in the fixed state during the gas alloying.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Laser Beam Processing (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Vapour Deposition (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Laminated Bodies (AREA)
US11/571,818 2004-07-09 2005-07-08 Method for Producing Wear-Resistant and Fatigue-Resistant Edge Layers in Titanium Alloys, and Components Produced Therewith Abandoned US20080011391A1 (en)

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PCT/EP2005/007393 WO2006005527A1 (de) 2004-07-09 2005-07-08 Verfahren zur herstellung von verschleissbeständigen und ermüdungsresistenten randschichten in titan-legierungen und damit hergestellte bauteile

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US20120184184A1 (en) * 2009-08-21 2012-07-19 Snecma Tool for machining a cmc by milling and ultrasonic abrasion
US8322004B2 (en) 2009-04-29 2012-12-04 Caterpilar Inc. Indirect laser induced residual stress in a fuel system component and fuel system using same
US20140263246A1 (en) * 2013-03-12 2014-09-18 U.S.A. As Represented By The Administrator Of The National Aeronautics And Space Administration Gas Phase Alloying for Wire Fed Joining and Deposition Processes
CN112391625A (zh) * 2020-11-05 2021-02-23 浙江工业大学 一种激光合金化复合微弧氧化制备钛合金防高温氧化涂层的方法
CN113529008A (zh) * 2021-07-15 2021-10-22 西北有色金属研究院 一种在钛或钛合金表面制备梯度复合耐磨涂层的方法
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US20080160891A1 (en) * 2006-12-30 2008-07-03 General Electric Company Method for determining initial burnishing parameters
US8079120B2 (en) * 2006-12-30 2011-12-20 General Electric Company Method for determining initial burnishing parameters
US20090202955A1 (en) * 2008-02-07 2009-08-13 General Electric Company Gasification feed injectors and methods of modifying the cast surfaces thereof
US8322004B2 (en) 2009-04-29 2012-12-04 Caterpilar Inc. Indirect laser induced residual stress in a fuel system component and fuel system using same
US20120184184A1 (en) * 2009-08-21 2012-07-19 Snecma Tool for machining a cmc by milling and ultrasonic abrasion
US20140263246A1 (en) * 2013-03-12 2014-09-18 U.S.A. As Represented By The Administrator Of The National Aeronautics And Space Administration Gas Phase Alloying for Wire Fed Joining and Deposition Processes
US10829857B2 (en) * 2013-03-12 2020-11-10 United States Of America As Represented By The Administrator Of Nasa Gas phase alloying for wire fed joining and deposition processes
CN112391625A (zh) * 2020-11-05 2021-02-23 浙江工业大学 一种激光合金化复合微弧氧化制备钛合金防高温氧化涂层的方法
CN113529008A (zh) * 2021-07-15 2021-10-22 西北有色金属研究院 一种在钛或钛合金表面制备梯度复合耐磨涂层的方法
CN115125463A (zh) * 2022-07-04 2022-09-30 贵州大学 一种提高高强韧钛合金扭转疲劳性能的嵌套式梯度组织的制备方法

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