EP0421705A1 - Exhaust valve alloy - Google Patents

Exhaust valve alloy Download PDF

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Publication number
EP0421705A1
EP0421705A1 EP90310724A EP90310724A EP0421705A1 EP 0421705 A1 EP0421705 A1 EP 0421705A1 EP 90310724 A EP90310724 A EP 90310724A EP 90310724 A EP90310724 A EP 90310724A EP 0421705 A1 EP0421705 A1 EP 0421705A1
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EP
European Patent Office
Prior art keywords
alloy
alloys
exhaust valve
marine
exhaust
Prior art date
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Application number
EP90310724A
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German (de)
French (fr)
Inventor
Carol Henry White
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Inco Alloys Ltd
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Inco Alloys Ltd
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Publication date
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Publication of EP0421705A1 publication Critical patent/EP0421705A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention is concerned with components of diesel exhaust systems particularly of diesel exhaust systems in large marine diesel engines.
  • the exhaust system of a marine diesel engine should comprise components which are resistant to the products of combustion in a marine atmosphere of a representative grade of fuel likely to be encountered.
  • the prior art has not solved the problem of providing such components in a satisfactory manner.
  • marine atmosphere means atmospheric air which contains aerosol size or larger particles of sea salt generally produced by the action of wind on the crests of ocean waves. Wind tears at the crest of ocean waves dislodging particles of water containing sea salt. Some of these particles fall back into the ocean as spray while others tend to remain in suspension in the air either as liquid or as solid particles of dried out (or semi-dried out) solid.
  • marine atmospheres contain not only high amounts of water vapor, but also significant amounts of sodium, potassium and other metals principally in the form of chlorides. For all practical purposes, a marine diesel engine is continuously burning fuel with air which contains these metals.
  • the present invention contemplates components of the exhaust systems of marine diesel engines particularly exhaust valves having at least exhaust contacting surfaces made of an alloy comprising 0.02-0.07% carbon, 24-32% chromium, 0.7-3.0% titanium, 0.7-1.5% aluminum, 0.7-1.5% niobium, 0 to 0.1% zirconium, 0-0.006% boron, 0-1% iron, balance essentially nickel, together with conventional amounts of incidental and impurity elements. More specifically, entire exhaust components of marine diesel engines are made of the alloy of the present invention which can be in cast/­wrought form or can be made by powder metallurgical or other methods.
  • the alloy can be heat treated by age-hardening in the range of about 675°C to about 725°C for about 2 to about 48 hours preferably after solution treatment at a temperature in excess of about 1000°C.
  • age-hardening can be accomplished by slow cooling through the age-hardening temperature range or by use of two or more steps where the alloy is held at each step for a particular temperature and a particular length of time.
  • iron should not exceed that amount which may be introduced inadvertently by use of scrap in preparing a melting charge or otherwise.
  • the corrosion rate of alloys similar to those of the invention but containing in excess of 1% iron is significantly increased compared to that of alloys of the invention when tested at temperatures in excess of about 700°C in contact with synthetic ash containing vanadium in oxide form.
  • Residual fuel ash deposits resulting from combustion of diesel fuel as described in Table II generally have compositions as set forth in weight percent in Table IV.
  • Example 1 Five casts of Example 1 and four casts of Example 2 were made having average compositions in percent by weight as set forth in Table V. TABLE V Element Example 1 Example 2 C 0.03 0.03 Al 1.32 0.77 Cr 24.9 29.9 Nb 1.33 0.72 Ti 2.67 1.60 Zr 0.08 0.07 B 0.004 0.004 Ni Bal. Bal.
  • the casts of the alloys of Example 1 and Example 2 were forged to bar stock and made into marine diesel exhaust valves. The alloys were heat treated for 2 hours at 1080°C followed by air cooling and, subsequently were aged for 16 hours at 700°C followed by air cooling.
  • valves were tested in actual marine engine usage using residual fuel SSF7 with a sulfur content of 3.6% max., a vanadium content of 380 ppm max., an aluminum content of 3 ppm max. and a maximum ash of 0.1% (all by weight) and found to be very satisfactory. The tests of these valves gave full indication of practical utility in marine diesel engine service.
  • Table VII shows that the tensile properties of the alloys of Examples 1 and 2 (especially Example 1) are more than adequate for use as marine diesel engine exhaust valves as compared to the tensile properties of prior art Alloy A.
  • the tensile properties of the laboratory heats of Examples 1 and 2 reasonably matched the tensile properties of the comparable heats used to make exhaust valves when tested at room temperature and 550°C.
  • the dynamic Young's moduli of 19 mm, forged bar samples of alloys of Examples 1 and 2 heat treated as specified hereinbefore were in units of N/mm2 x 103, about 217.7 at room temperature and decreased to about 182.7 at 600°C. These values are significantly higher than the dynamic Young's moduli of Alloy A at these temperatures. Mean coefficients of thermal expansion from 20°C to temperatures as high as 600°C for alloys of Examples 1 and 2 were marginally lower than such coefficients of thermal expansion for Alloy A.
  • Table VIII sets forth data concerning relative corrosion of samples of Alloy A and the alloys of Examples 1 and 2 under laboratory conditions in contact with air and synthetic ash (as defined hereinbefore) when tested at 650°C for 500 hours with the air containing 0.2% sulfur oxide as the dioxide or trioxide.
  • the alloys of the invention must contain less than about 1% iron in order to exhibit the excellent corrosion resistance as indicated in Table VIII at temperatures in excess of 700°C.
  • alloys of the present invention are particularly useful as exhaust valves and parts, e.g. facings, coatings, external portion of composite exhaust valves and other exhaust contacting items for marine diesel engines and other diesel engines employing non-distillate diesel fuel, particularly such fuel contaminated with vanadium. It is to be noted that while alloys of the invention are contemplated to contain from 24 to 32% chromium, best results are obtained with alloys containing 24-28% chromium as is evident by the relatively better tensile characteristics disclosed in Table VII for the alloy of Example 1 compared to the alloy of Example 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Exhaust Silencers (AREA)

Abstract

An alloy for a marine diesel exhaust valve comprising 0.02-0.07% C, 24-32% (preferably 24-28%) Cr, 0.7-3% Ti, 0.7-1.5% Al, 0.7-1.5% Hb, 0-1% Zr, 0-0.006% B, 0-1% Fe, balance essentially nickel, and exhaust valves made from this alloy.

Description

  • The present invention is concerned with components of diesel exhaust systems particularly of diesel exhaust systems in large marine diesel engines.
    • BACKGROUND OF THE INVENTION
  • In the past twenty years or so, a number of suggestions have been made concerning alloys suitable for diesel engine exhaust valves and other components of diesel engine exhaust systems. The documents set forth in Table I contain many of these suggestions. TABLE I
    Patent No. Inventor Date
    U.S. 3,573,901 Economy 1971
    U.S. 3,972,713 Muzyka et al 1976
    U.S. 4,379,120 Whitney et al 1983
    U.S. 4,631,169 Isobe et al 1986
    U.S. 4,714,501 Yamanaka et al 1987
    U.S. 4,715,909 Minami et al 1987
    Japanese Appln. 85/101,589 -- 1985
    Alloy Digest Pyromet 31, Dec. 1977
    As valid and as useful as these suggestions may be, they have not solved satisfactorily a continuing problem of severe hot erosion and corrosion which exists when diesel exhaust components are exposed to hot (e.g. greater than 650°C) diesel exhaust streams resulting from internal combustion in marine atmospheres of poor grades of marine diesel fuels.
  • Specifications for marine fuels have been established by the International Organization for Standardization, Petroleum Products-Fuels (Class F), Specifications of Marine Fuels, ISO8217:1987(E) (1987) and the International Council on Combustion Engines (CIMAC). Specifications for the poorest grades of marine diesel fuel as specified by these organizations is set forth in Table II. TABLE II
    ISO 8217 RMH/RML 55 CIMAC 12/13
    Density at 15°C kg/l 0.991 0.991/1.010
    Kinematic viscosity at 80°C 130
    (centi-stokes) at 100°C 55 55
    Flash point °C 60 60
    Pour point °C Winter quality 30 30
    Summer quality 30 30
    Conradson carbon res. w% 22 22
    Ash (max) w% 0.2 0.2
    Water content (max) v% 1.0 1.0
    Sulfur content (max) w% 5.0 5.0
    Vanadium content (max) wppm 600 600
    Aluminum content (max) wppm -- 30
    The grades of marine diesel fuels as set forth in Table II are distinguished from diesel fuels employed in most automotive, truck and land-based vehicle and machinery usages in not being distillate fuels. Thus, contaminants, particularly sulfur and vanadium which are to a great extent not present in distillate fuels, are generally characteristic of localities at which a diesel powered ship may be bunkered. In short, depending upon where a ship picks up fuel, the diesel fuel taken on may grade from reasonable to very poor especially with respect to vanadium content. Accordingly, the exhaust system of a marine diesel engine should comprise components which are resistant to the products of combustion in a marine atmosphere of a representative grade of fuel likely to be encountered. As far as is known, the prior art has not solved the problem of providing such components in a satisfactory manner.
  • For purposes of this specification and claims, the term "marine atmosphere" means atmospheric air which contains aerosol size or larger particles of sea salt generally produced by the action of wind on the crests of ocean waves. Wind tears at the crest of ocean waves dislodging particles of water containing sea salt. Some of these particles fall back into the ocean as spray while others tend to remain in suspension in the air either as liquid or as solid particles of dried out (or semi-dried out) solid. Thus, marine atmospheres contain not only high amounts of water vapor, but also significant amounts of sodium, potassium and other metals principally in the form of chlorides. For all practical purposes, a marine diesel engine is continuously burning fuel with air which contains these metals.
    • STATEMENT OF THE INVENTION
  • The present invention contemplates components of the exhaust systems of marine diesel engines particularly exhaust valves having at least exhaust contacting surfaces made of an alloy comprising 0.02-0.07% carbon, 24-32% chromium, 0.7-3.0% titanium, 0.7-1.5% aluminum, 0.7-1.5% niobium, 0 to 0.1% zirconium, 0-0.006% boron, 0-1% iron, balance essentially nickel, together with conventional amounts of incidental and impurity elements. More specifically, entire exhaust components of marine diesel engines are made of the alloy of the present invention which can be in cast/­wrought form or can be made by powder metallurgical or other methods. Once the alloy is made and formed into the exhaust syo tem component desired, it can be heat treated by age-hardening in the range of about 675°C to about 725°C for about 2 to about 48 hours preferably after solution treatment at a temperature in excess of about 1000°C. Those skilled in the art will appreciate that other aging treatments can be employed. For example, age-hardening can be accomplished by slow cooling through the age-hardening temperature range or by use of two or more steps where the alloy is held at each step for a particular temperature and a particular length of time.
  • In order that the art be particularly apprised of the intent of applicant in setting forth the range of alloying elements as stated hereinbefore, specific amounts of each element constituting the alloy of, and employed in, the present invention are set forth in Table III with the understanding that alloy ranges within the scope of the present invention can be constructed from each and every value set forth in Table III. TABLE III
    Element % by Weight
    Carbon 0.02 0.03 0.04 0.05 0.06 0.07
    Chromium 24 25 26 28 30 32
    Titanium 0.7 1.2 1.8 2.0 2.4 3.0
    Aluminum 0.7 0.9 1.1 1.3 1.5 --
    Niobium 0.7 0.9 1.1 1.3 1.5 --
    Zirconium 0 0.02 0.04 0.06 0.08 0.1
    Boron 0 0.001 0.002 0.003 0.004 0.006
    Iron 0 0.2 0.4 0.6 0.8 1.0
    Nickel Balance Essentially
    In formulating alloys and exhaust system components made of the alloys of the present invention, it is vital that the iron content of the alloys be maintained at less than about 1% by weight. In other words, iron should not exceed that amount which may be introduced inadvertently by use of scrap in preparing a melting charge or otherwise. As will be discussed hereinafter, the corrosion rate of alloys similar to those of the invention but containing in excess of 1% iron is significantly increased compared to that of alloys of the invention when tested at temperatures in excess of about 700°C in contact with synthetic ash containing vanadium in oxide form. Residual fuel ash deposits resulting from combustion of diesel fuel as described in Table II generally have compositions as set forth in weight percent in Table IV. TABLE IV
    Component Range Typical
    V₂O₅ 38-75% 42%
    Na₂O 4-11% 11%
    CaO 4- 9% 7%
    Fe₂O₃ 1-10% 7%
    NiO 5-11% 9%
    SO₃ 11-22% 18%
    Ash corrosion test results specified herein were obtained with a synthetic ash containing 40% V₂O₅, 10% NaVO₃, 20% Na₂SO₄, 15% NiSO₄ and 15% CaSO₄ at temperatures of 650°C and 750°C. As will be made evident by data hereinafter, iron is very detrimental to corrosion resistance in this synthetic ash at temperatures above about 700°C.
    • EXAMPLES OF THE INVENTION
  • Five casts of Example 1 and four casts of Example 2 were made having average compositions in percent by weight as set forth in Table V. TABLE V
    Element Example 1 Example 2
    C 0.03 0.03
    Al 1.32 0.77
    Cr 24.9 29.9
    Nb 1.33 0.72
    Ti 2.67 1.60
    Zr 0.08 0.07
    B 0.004 0.004
    Ni Bal. Bal.
    The casts of the alloys of Example 1 and Example 2 were forged to bar stock and made into marine diesel exhaust valves. The alloys were heat treated for 2 hours at 1080°C followed by air cooling and, subsequently were aged for 16 hours at 700°C followed by air cooling. These valves were tested in actual marine engine usage using residual fuel SSF₇ with a sulfur content of 3.6% max., a vanadium content of 380 ppm max., an aluminum content of 3 ppm max. and a maximum ash of 0.1% (all by weight) and found to be very satisfactory. The tests of these valves gave full indication of practical utility in marine diesel engine service.
  • Prior to production of casts of the alloys of Examples 1 and 2 laboratory heats of the current best alloy of choice for marine diesel exhaust valves (Alloy A) and Examples 1 and 2 were cast and forged and heat treated as specified hereinbefore. Actual compositions of these laboratory heats, in percent by weight, are set forth in Table VI. TABLE VI
    Element Alloy A Example 1 Example 2
    C -- -- --
    Si 0.05 0.02 0.01
    Mn 0.01 0.01 0.01
    Al 1.55 1.35 0.77
    Co 0.01 0.02 0.01
    Cr 19.37 24.90 31.24
    Fe 0.04 0.10 0.05
    Mo -- 0.02 0.01
    Nb -- 1.20 0.74
    Ni Bal. (76.36) Bal. (69.81) Bal. (65.52)
    Ta -- 0.01 --
    Ti 2.48 2.55 1.62
    V 0.01 0.01 0.01
    W 0.02 0.01 --
    Zr 0.065 0.001 0.001
    Cu 0.03 0.01 0.01
    P 0.004 0.002 0.002
    Tensile properties of forged and machined samples of the alloys specified in Table VI are set forth in Table VII. TABLE VII
    Alloy Test Temp. (°C) Stress N/mm² Elong. % R of A %
    0.1% PS 0.2% PS TS
    A RT 797 818 1271 25.4 39.1
    500 722 745 1109 23.2 44.5
    550 704 732 1085 23.2 41.0
    600 706 728 1086 20.5 32.1
    650 687 712 1047 17.9 23.5
    700 655 691 967 17.9 21.1
    750 612 632 829 17.9 23.0
    Ex. 1 RT 860 875 1274 25.9 38.6
    500 780 799 1135 21.4 31.1
    550 794 813 1163 17.9 30.3
    600 751 779 1135 13.4 17.3
    650 757 780 1098 9.8 14.3
    700 733 760 1008 7.1 9.7
    750 614 651 872 6.3 10.2
    Ex. 2 RT 580 592 1083 31.3 45.6
    500 576 588 932 25.9 44.2
    550 554 570 912 23.2 36.4
    600 570 581 908 18.8 26.1
    650 556 579 862 11.6 14.5
    700 535 549 784 10.7 13.6
    750 460 471 670 12.5 14.0
    Table VII shows that the tensile properties of the alloys of Examples 1 and 2 (especially Example 1) are more than adequate for use as marine diesel engine exhaust valves as compared to the tensile properties of prior art Alloy A. The tensile properties of the laboratory heats of Examples 1 and 2 reasonably matched the tensile properties of the comparable heats used to make exhaust valves when tested at room temperature and 550°C.
  • The dynamic Young's moduli of 19 mm, forged bar samples of alloys of Examples 1 and 2 heat treated as specified hereinbefore were in units of N/mm² x 10³, about 217.7 at room temperature and decreased to about 182.7 at 600°C. These values are significantly higher than the dynamic Young's moduli of Alloy A at these temperatures. Mean coefficients of thermal expansion from 20°C to temperatures as high as 600°C for alloys of Examples 1 and 2 were marginally lower than such coefficients of thermal expansion for Alloy A. All physical and mechanical tests of Alloy A and the alloys of Examples 1 and 2 indicated that from strength, thermal expansion, thermal conductivity and abrasion and fatigue resistance standpoints Alloy A and the alloys of Examples 1 and 2 were equally well adapted for marine diesel exhaust valve usage.
  • The significant difference between Alloy A and the alloys of Examples 1 and 2 is corrosion resistance in the environment in which a marine engine diesel exhaust valve is operating. Calculated levels of strain, even allowing for excess strain, in marine diesel engine exhaust valves indicate that such valves made of Alloy A are not likely to fail. However, experience has proven that this prediction is faulty because corrosion promotes crack initiation under low cycle and high cycle fatigue conditions. Once a crack or cracks is initiated, failure of an exhaust valve quickly follows.
  • Table VIII sets forth data concerning relative corrosion of samples of Alloy A and the alloys of Examples 1 and 2 under laboratory conditions in contact with air and synthetic ash (as defined hereinbefore) when tested at 650°C for 500 hours with the air containing 0.2% sulfur oxide as the dioxide or trioxide. TABLE VIII
    Alloy Corrosion Loss Per Side (µm)*
    Alloy A 136 ± 50
    Example 1 74 ± 15
    Example 2 57 ± 21
    *Mean plus or minus two standard deviations
    It is vital to note, in contrast to many teachings of the prior art such as set forth in Table I that the alloys of the invention must contain less than about 1% iron in order to exhibit the excellent corrosion resistance as indicated in Table VIII at temperatures in excess of 700°C. Under corrosion testing conditions similar to those used in obtaining the data set forth in Table VIII, gn alloy of the invention containing 25% Or, 2.5% Ti, 1.25% Al, 1.25% Nb, balance essentially nickel, and two alloys outside the invention containing respectively 10% and 20% iron in replacement of nickel provided data as set forth in Table IX. TABLE IX
    % Fe Descaled Weight Loss* (mg/cm²) Surface Loss* (mm) Maximum Penetration* (mm)
    0 49.0 0.06 0.085
    48.5 0.00 0.085
    10 58.9 0.07 0.095
    61.5 0.07 0.095
    20 82.8 0.10 0.125
    89.0 0.11 0.135
    *These data are for a 50 hour exposure
    When exposure times to synthetic ash and air are extended beyond 50 hours at 750°C, e.g. for 300 hours, the descaled weight loss of the alloys containing iron are even greater in proportion to the descaled weight loss of the iron-free alloy of the invention than disclosed in Table IX. The same phenomenon is evident when the criterion of corrosion is total depth of attack.
  • As disclosed, the alloys of the present invention are particularly useful as exhaust valves and parts, e.g. facings, coatings, external portion of composite exhaust valves and other exhaust contacting items for marine diesel engines and other diesel engines employing non-distillate diesel fuel, particularly such fuel contaminated with vanadium. It is to be noted that while alloys of the invention are contemplated to contain from 24 to 32% chromium, best results are obtained with alloys containing 24-28% chromium as is evident by the relatively better tensile characteristics disclosed in Table VII for the alloy of Example 1 compared to the alloy of Example 2.

Claims (6)

1. An alloy particularly adapted to be employed at high temperatures under corrosive conditions comprising, in percent by weight, 0.02-0.07% carbon, 24-32% chromium, 0.7-3.0% titanium, 0.7-1.5% aluminum, 0.7-1.5% niobium, 0-1% zirconium, 0-0.006% boron, 0-1% iron, balance essentially nickel, together with conventional amounts of incidental and impurity elements.
2. An alloy as in claim 1 containing about 24-28% chromium.
3. An alloy as in claim 1 containing about 25% chromium.
4. A component of a marine diesel exhaust system comprising, at least in part of, the alloy of any one of claims 1 to 3.
5. A component as in claim 4 comprising an exhaust valve.
6. An exhaust valve as in claim 5 made substantially entirely of the alloy of any of claims 1, 2 or 3.
EP90310724A 1989-10-02 1990-10-01 Exhaust valve alloy Withdrawn EP0421705A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8922161 1989-10-02
GB898922161A GB8922161D0 (en) 1989-10-02 1989-10-02 Exhaust valve alloy

Publications (1)

Publication Number Publication Date
EP0421705A1 true EP0421705A1 (en) 1991-04-10

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EP90310724A Withdrawn EP0421705A1 (en) 1989-10-02 1990-10-01 Exhaust valve alloy

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JP (1) JPH03120328A (en)
CA (1) CA2026551A1 (en)
GB (1) GB8922161D0 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0857793A1 (en) * 1997-02-07 1998-08-12 Daido Tokushuko Kabushiki Kaisha High corrosion resisting alloy for diesel engine valve and method for producing the valve
WO2002092865A1 (en) * 2001-05-15 2002-11-21 Thyssenkrupp Vdm Gmbh Austenitic thermally-stable nickel-based alloy
DE102007062417A1 (en) * 2007-12-20 2009-06-25 Thyssenkrupp Vdm Gmbh Austenitic heat-resistant nickel-based alloy

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2570194A (en) * 1946-04-09 1951-10-09 Int Nickel Co Production of high-temperature alloys and articles
FR1584027A (en) * 1967-07-17 1969-12-12
EP0109350A2 (en) * 1982-11-10 1984-05-23 Mitsubishi Jukogyo Kabushiki Kaisha Nickel-chromium alloy
DE3511860A1 (en) * 1984-04-03 1985-10-10 Daido Tokushuko K.K., Nagoya, Aichi ALLOYS FOR EXHAUST VALVES

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Publication number Priority date Publication date Assignee Title
JPS5035023A (en) * 1973-07-14 1975-04-03
JPS5544144B2 (en) * 1973-09-10 1980-11-11
JPS604895B2 (en) * 1980-05-30 1985-02-07 株式会社日立製作所 Structure with excellent stress corrosion cracking resistance and its manufacturing method
JPS6070155A (en) * 1983-09-28 1985-04-20 Hitachi Metals Ltd Ni alloy for exhaust valve
JPS6184347A (en) * 1984-09-25 1986-04-28 Honda Motor Co Ltd Hollow valve for internal-combustion engine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2570194A (en) * 1946-04-09 1951-10-09 Int Nickel Co Production of high-temperature alloys and articles
FR1584027A (en) * 1967-07-17 1969-12-12
EP0109350A2 (en) * 1982-11-10 1984-05-23 Mitsubishi Jukogyo Kabushiki Kaisha Nickel-chromium alloy
DE3511860A1 (en) * 1984-04-03 1985-10-10 Daido Tokushuko K.K., Nagoya, Aichi ALLOYS FOR EXHAUST VALVES

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 1, no. 200 (C-298)[1923], 16th August 1985; & JP-A-60 70 155 (HITACHI KINZOKU K.K.) 20-04-1985 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0857793A1 (en) * 1997-02-07 1998-08-12 Daido Tokushuko Kabushiki Kaisha High corrosion resisting alloy for diesel engine valve and method for producing the valve
WO2002092865A1 (en) * 2001-05-15 2002-11-21 Thyssenkrupp Vdm Gmbh Austenitic thermally-stable nickel-based alloy
DE102007062417A1 (en) * 2007-12-20 2009-06-25 Thyssenkrupp Vdm Gmbh Austenitic heat-resistant nickel-based alloy
WO2009079972A1 (en) * 2007-12-20 2009-07-02 Thyssenkrupp Vdm Gmbh Austenitic heat-resistant nickel-base alloy
DE102007062417B4 (en) * 2007-12-20 2011-07-14 ThyssenKrupp VDM GmbH, 58791 Austenitic heat-resistant nickel-based alloy

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JPH03120328A (en) 1991-05-22
CA2026551A1 (en) 1991-04-03
GB8922161D0 (en) 1989-11-15

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