EP0429796A1 - Hitzebeständige Werkstoffe - Google Patents

Hitzebeständige Werkstoffe Download PDF

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Publication number
EP0429796A1
EP0429796A1 EP90118741A EP90118741A EP0429796A1 EP 0429796 A1 EP0429796 A1 EP 0429796A1 EP 90118741 A EP90118741 A EP 90118741A EP 90118741 A EP90118741 A EP 90118741A EP 0429796 A1 EP0429796 A1 EP 0429796A1
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EP
European Patent Office
Prior art keywords
alloy
heat
resistant
skid
grain size
Prior art date
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Granted
Application number
EP90118741A
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English (en)
French (fr)
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EP0429796B1 (de
Inventor
Hideo Fujita
Jun Funakoshi
Takahiro Kaba
Akira Shinosaki
Hiroyuki Araragi
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Kubota Corp
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Kubota Corp
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Application filed by Kubota Corp filed Critical Kubota Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium

Definitions

  • the present invention relates to heat-resistant materials suitable for use in heating furnaces, especially in heating furnaces of the walking beam type.
  • Heating furnaces of the walking beam type are used in the hot rolling process for heating steel materials such as steel pieces or slabs. These furnaces are equipped with skid beams in a plurality of rows for supporting and transporting steel pieces, slabs or like materials to be heated. These skid beams include movable beams and fixed beams. The movable beams periodically repeat an upward and downward movement and a horizontal reciprocating movement, whereby the material to be heated is transported while being transferred to the movable beam and the fixed beam alternately.
  • FIG. 1 shows a skid beam 1 which comprises a hollow skid pipe 10 provided on the top of its periphery with a plurality of skid buttons 12 arranged axially thereof at a specified spacing.
  • a refractory lining 5 covers the outer peripheral surface of the skid pipe 10 and the base to upper portion of each skid button 12 for use in the interior of the heating furnace.
  • the skid button 12 is a block in the form of a truncated cone, truncated pyramid or the like to support on the top thereof the material 3 to be heated.
  • Materials heretofore used for skid buttons are heat-resistant alloy steels such as high Ni high Cr alloy steels and high Co alloy steels (e.g., 50 Co-20 Ni-Fe steel).
  • Cooling water is forcibly passed through the skid pipe to diminish the thermal influence of the high-­temperature oxidizing internal atmosphere of the furnace on the skid button and to prevent the rise in the temper­ature of the skid button. This assures the skid button of strength capable of withstanding the load of the material to be heated and prevents the surface of the skid button from oxidation damage.
  • the skid button is subject, for example, to deformation or oxidation damage.
  • the cooling action if excessive, entails the problem that the material to be heated and supported on the top of the skid button is locally cooled by contact with the skid button, which produces a so-called skid mark and permits uneven heating of the material.
  • skid buttons of conventional heat-resistant alloy have the problem of failing to withstand high operating temperatures and undergoing deformation due to the load of the material to be heated or oxidation damage or the like.
  • sintered ceramic bodies as skid buttons, ceramics are brittle materials, are therefore liable to crack or chip, and are not usable with good stability.
  • the present invention has been accomplished in view of the above problems.
  • An object of the present invention is to provide a heat-resistant material capable of exhibiting excellent strength and high resistance to oxidation at high temperatures in excess of 1300 o C.
  • Another object of the present invention is to provide a skid button capable of exhibiting excellent high-temperature strength and high resistance to oxida­tion for operation at high temperatures in excess of 1300 o C even if the cooling action of the skid pipe is not enhanced greatly.
  • the present invention provides a heat-resistant material which is a heat-resistant alloy comprising at least 60% (by weight, the same as hereinafter) of Cr, and the balance substantially Fe (which, however, is present in an amount of at least 5%), the hreat-resistant alloy being at least 50 ⁇ m in the mean grain size of the alloy structure and at least 1600 o C in melting point.
  • the present invention further provides a heat-­resistant material which is a composite material composed of an alloy and a ceramic, the alloy being in the form of a metal matrix and comprising at least 60% of Cr, and the balance substantially Fe (which, however, is present in an amount of at least 5%), the alloy being at least 50 ⁇ m in the mean grain size of the alloy structure and at least 1600 o C in melting point, the composite material containing up to 40% by volume of a dispersed ceramic phase present in the metal matrix.
  • a heat-­resistant material which is a composite material composed of an alloy and a ceramic, the alloy being in the form of a metal matrix and comprising at least 60% of Cr, and the balance substantially Fe (which, however, is present in an amount of at least 5%), the alloy being at least 50 ⁇ m in the mean grain size of the alloy structure and at least 1600 o C in melting point, the composite material containing up to 40% by volume of a dispersed ceramic phase present in the metal matrix.
  • heat-resistant material of the invention which is a heat-resistant alloy.
  • the heat-resistant alloy of the present invention contains at least 60% of Cr.
  • the Cr content should be at least 60% to ensure a melting point of at least 1600 o C and to obtain stable resistance to oxida­tion for use at high temperatures in excess of 1300 o C.
  • the melting point of at least 1600 o C is a prerequisite for giving excellent high-temperature strength.
  • the heat-resistant alloy of the invention contains at least 5% of Fe.
  • the Fe content of at least 5% renders the alloy composition amenable to sintering and permits use of moderate sintering conditions when the alloy composition is to be sintered into an alloy while serving to moderate the thermal conditions for melting and casting operations when the composition is to be cast into an alloy. These effects are not available if the content is less than 5%.
  • the heat-resistant alloy of the invention has a Cr-Fe composition comprising at least 60% of Cr, and the balance substantially Fe (which, however, should be present in an amount of at least 5%).
  • the alloy may further comprise one or at least two elements selected from the group consisting of up to 10% of W, up to 10% of Mo, up to 10% of Nb, up to 10% of Ta, up to 10% of Hf, up to 10% of Co, up to 10% of Ni, up to 10% of Ti, up to 10% of Al, up to 10% of V, up to 10% of Mn and up to 10% of a rare-earth element, in a combined amount of up to 35%, preferably up to 30%.
  • intermetallic compounds such as Cr2Nb, Cr2Zr, Cr2Ta and Cr2Ti
  • Cr2Nb, Cr2Zr, Cr2Ta and Cr2Ti then formed serve to strengthen the alloy more effectively by particle or fiber dispersion to give still improved alloy strength.
  • Al or rare-earth elements are expected to produce further improved resistance to oxidation in addition to an alloy strengthening effect.
  • the presence of excessive amounts of the above elements is likely to lower the melting point of the alloy below 1600 o C and to impair the workability thereof, so that the upper limit of the combined amount should be 35%, preferably 30%.
  • the heat-resistant alloy is allowed to contain P, S and other impurities insofar as such impurities are inevitably incorporated into the alloy by usual alloy preparation techniques. Further up to 0.8% of C and up to 5% of Si are allowed to be present in the alloy.
  • thermoresistant material of the present invention up to about 40% by volume of a ceramic can be present as a dispersed phase in the above heat-resistant alloy when so required.
  • Ceramics which can be present as dispersed in the alloy are oxides such as Cr2O3, Al2O3, SiO2, Y2O3, LaO and Sc2O3, nitrides such as Si3N4, TiN, BN and AlN, carbides such as B4C, Cr3C2, WC and SiC, silicides such as Mo2Si and Cr2Si, and borides such as CrB2 and TiB2.
  • oxides such as Cr2O3, Al2O3, SiO2, Y2O3, LaO and Sc2O3, nitrides such as Si3N4, TiN, BN and AlN, carbides such as B4C, Cr3C2, WC and SiC, silicides such as Mo2Si and Cr2Si, and borides such as CrB2 and TiB2.
  • oxides such as Cr2O3, Al2O3, SiO2, Y2O3, LaO and Sc2O3, nitrides such as Si3N4, TiN, BN and AlN, carb
  • the heat-resistant alloy or the heat-resistant material of the present invention must be not only at least 1600 o C in melting point but also at least 50 ⁇ m in the mean grain size of the alloy structure.
  • the crystal grains must be at least 50 ⁇ m in means size to give sufficient strength, especially satisfactory resistance to compressive deformation, in atmospheres having a high temperature in excess of 1300 o C.
  • the heat-resistant alloy or material of the present invention can be prepared by sintering, melt casting or other process, the crystal structure must be at least 50 ⁇ m in mean size regardless of the process resorted to.
  • the hot isostatic press sintering process in view of the homogeneity and compactness of the sintered alloy obtained.
  • This process can be practiced, for example, by heating the starting composition at a temper­ature of about 1000 to about 1500 o C under a pressure of about 1000 to about 2000 kgf/cm2 for about 2 to about 5 hours.
  • the grain size of the sintered alloy is dependent on the particle size of the powdery starting composition. We have found that when the starting composition is at least about 200 ⁇ m in mean particle size, the sintered alloy can be given a mean grain size of at least 50 ⁇ m.
  • the ceramic When a ceramic is to be made present in the alloy as a dispersed phase, the ceramic is used conjointly with the powdery starting alloy composition.
  • the ceramic can be of any desired size.
  • Useful particulate ceramics are, for example, about 0.1 to about 10 ⁇ m in particle size.
  • Examples of fibrous ceramics usable are about 1 to about 1000 ⁇ m in fiber length and about 10 to about 50 in aspect ratio.
  • the present alloy is to be prepared by casting, for example, a high-frequency melting furnace is usable.
  • the ceramic can be incorporated into the alloy as a dispersed phase by adding the ceramic as finely divided to the alloy in a molten state before the melt is poured into a mold or to the molten alloy as placed in the mold, and solidifying the mixture with the solid uniformly mixed with the melt.
  • the grain size of the alloy to be cast is adjustable with ease by controlling the solidification velocity of the mixture within the mold.
  • a sufficiently coarse crystal grain structure can be obtained by decreasing the solidification velocity with use of a sand mold, refractory mold or the like.
  • the heat-resistant alloy or material obtained by sintering or casting can be heat-­treated for the adjustment of the grain size.
  • the mean grain size was determined by the following method. Five areas as desired were selected from the microstructure of the specimen, and photomicrographs (x50) was taken at each of the selected areas. Two vertical lines and two horizontal lines were drawn over each of the field of views, and the number of crystal grains were counted up. The total length of the lines was divided by the number of crystal grains to obtain a value as a mean of grain sizes. The average of the mean values for the five view fields was calculated as the mean grain size. TABLE 1 Specimen No. Chemical Composition (wt%) Ceramic (by vol.) (%) Alloy melting point (°C) Mean grain size ( ⁇ m) Remarks Cr C Si W Mo Al Ni Co Fe 1 89.2 0.02 1.5 -- -- -- -- -- -- Bal.
  • FIG. 9 shows a 12-second loading cycle comprising 4 seconds for the application of the compression load of 0.5 kgf/mm2, 4 seconds for allowing the test piece to stand free of the load, 2 seconds as a loading transition period and 2 seconds as an unloading transition period. This cycle was repeated 10000 times.
  • D (%) The amount of plastic deformation, D (%), due to compression was calculated from the following equation. D (%) : (Lo - L)/Lo x 100 where Lo is the length of the test piece before testing, and L is the length thereof after testing.
  • a solid cylindrical test piece (8 mm in diameter and 40 mm in length) was cut out from each specimen and held in a heating furnace (with air as atmosphere) at 1350 o C for 100 hours. The test piece was then withdrawn from the furnace, scales were removed from the surface of the test piece with an alkali solution and an acid solution, and the oxidation loss (g/m2hr) was determined from the resulting change in the weight of the test piece.
  • Table 2 shows the results of the high-tempera­ture compressive deformation test and the high-tempera­ture oxidation test.
  • Table 2 Specimen No. Amount of compressive deformation, D (%) Oxidation loss (g/m2hr) 1 0.5 4.2 2 1.25 4.1 3 0.38 3.8 4 3.0 3.9 5 0.25 3.9 6 0.40 3.5 7 0.35 5.5 8 0.45 3.2 9 0.30 5.0 10 4.3 67.0 11 3.5 4.5
  • specimens No. 1 to No. 3 and No. 5 to No. 9 are examples of heat-resistant materials of the invention.
  • Specimens No. 4 and No. 11 are comparative examples; with the former, the mean grain size is outside the range of the invention, and with the latter, the Cr content is outside the range of the invention.
  • Specimen No. 10 is Co-Ni-Cr alloy heretofore used for skid buttons.
  • Specimen No. 4 is great in compressive deforma­tion at a high temperature presumably because it is small in mean grain size.
  • Specimen No. 11 is also great in compressive deformation at a high temperature. This appears attributable to a low Cr content and low melting point.
  • Specimen No. 10 is very low in melting point, great in compressive deformation and inferior in oxida­tion resistance.
  • heat-resistant alloys or materials of the invention are very excellent in high-temperature strength and oxidation resistance.
  • FIG. 3 shows the relationship between the number of repetitions of compression load application and the variation in the amount of compressive deforma­tion as determined by a high-temperature compression test.
  • FIG. 4 shows the relationship between the heating temperature and the oxidation loss as established by a high-temperature oxidation test. The specimens were tested for 100 hours at each of varying temperatures.
  • FIGS. 5 to 7 show the relation­ship between crystal grains and microstructure.
  • the photo­micrographs (at a magnification of X50) of specimen No. 2 (50 ⁇ m in mean grain size), specimen No. 5 (200 ⁇ m in mean grain size) and specimen No. 4 (15 ⁇ m in mean grain size) are shown in FIGS. 5, 6 and 7, respectively.
  • Skid buttons were prepared from the heat-­resistant alloy or material of the present invention and attached to a skid pipe by support members as seen in FIG. 2.
  • the illustrated embodiment is adapted to prevent scales separating off the surface of the material heated from wedging into the support members and to preclude the skid buttons from chipping, cracking and like faults by giving consideration to the difference in the amount of thermal expansion due to the difference in material between the skid buttons and the support members.
  • the skid button 12 shown in FIG. 2 is in the form of a truncated cone and has a flange 14 at its bottom.
  • the skid button 12 can be in the form of a solid cylinder, truncated pyramid or the like.
  • a support member 4 comprises a seat portion 44 formed with an annular cavity 42 for the flange 14 of the skid button 12 to fit in loosely, and a ring member 46 having an inside diameter slightly larger than the outside diameter of the shank of the skid button 12.
  • the bottom of the seat portion 44 is secured to a skid pipe 10 as by a weld W.
  • the ring member 46 is secured to the seat portion 44 as by a weld W, whereby the skid button 12 is held to the support member 4.
  • the outer periphery of the skid pipe 10 and the base to upper portion of the support member 4 are covered with a refractory layer 5 and are thereby protected from the high-temperature oxidizing atmosphere within the furnace.
  • the refractory of the layer 5 fills the clearance C between the skid button 12 and the ring member 46, so that the scales separating off a material 3 heated and placed on the skid button 12 are prevented from falling into the clearance C. Consequently, the ring member 46 is prevented from deformation due to the ingress of scales.
  • the skid button 12 is about 100 to about 200 mm in height.
  • the height of the skid button 12 projecting upward beyond the ring member 46 of the support member 4 is preferably about 50 to about 100 mm.
  • the heat-resistant alloy or heat-resistant material of the present invention is excellent in high-­temperature strength and in resistance to oxidation, and these excellent characteristics are in no way available with high Co alloy steels and like materials heretofore used. Accordingly, the skid buttons prepared from the heat-resistant alloy or material of the invention exhibit sufficient durability even under such high-­temperature operating conditions as employed recently, diminishing the maintenance effort and thereby contrib­uting a great deal to improvements in operation efficiency.
  • the excellent high-temperature characteristics of the present material serve to moderate the cooling conditions for the cooling water to be passed through the skid pipe. This reduces the like­lihood of occurrence of skid marks on the material to be heated and achieves uniform heating for the production of materials of improved quality.
  • the heat-resistant alloy or heat-resistant material of the present invention which is well-suited for skid buttons for use in heating furnaces of the walking beam type, is not limited to such use but is of course usable for applications where resistance to compressive deformation and to oxidation at high temper­ature is essential.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
  • Powder Metallurgy (AREA)
EP90118741A 1989-11-17 1990-09-28 Hitzebeständige Werkstoffe Expired - Lifetime EP0429796B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP300091/89 1989-11-17
JP1300091A JP2607157B2 (ja) 1989-11-17 1989-11-17 加熱炉内の被加熱鋼材支持部材用耐熱合金

Publications (2)

Publication Number Publication Date
EP0429796A1 true EP0429796A1 (de) 1991-06-05
EP0429796B1 EP0429796B1 (de) 1995-12-13

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EP90118741A Expired - Lifetime EP0429796B1 (de) 1989-11-17 1990-09-28 Hitzebeständige Werkstoffe

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EP (1) EP0429796B1 (de)
JP (1) JP2607157B2 (de)
KR (1) KR0134182B1 (de)
AU (1) AU632166B2 (de)
DE (1) DE69024179T2 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000073523A1 (fr) * 1999-05-27 2000-12-07 Japan Science And Technology Corporation Alliage a base de chrome dote d'un excellent equilibre resistance-ductilite a haute temperature
EP1681361A1 (de) * 2003-10-10 2006-07-19 National Institute for Materials Science Hochduktile silberhaltige chromlegierung
CN108546860A (zh) * 2018-04-27 2018-09-18 苏州弗士曼精密机械有限公司 一种高温抗氧化性不锈钢金属
CN115323234A (zh) * 2022-08-09 2022-11-11 东睦新材料集团股份有限公司 一种无磁低膨胀铬基合金材料的制备方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2571640Y2 (ja) * 1991-09-20 1998-05-18 株式会社クボタ 加熱炉用スキツドボタン
JP2571641Y2 (ja) * 1991-09-20 1998-05-18 株式会社クボタ 加熱炉用スキツドボタン
JP2702631B2 (ja) * 1991-12-12 1998-01-21 株式会社クボタ 炉床開口カバー支持用部材
JPH05271840A (ja) * 1992-03-27 1993-10-19 Kobe Steel Ltd 超高温耐熱部材用Ｃｒ基合金
JPH062065A (ja) * 1992-06-15 1994-01-11 Kubota Corp 加熱炉内支持面部材用耐熱合金
JPH062066A (ja) * 1992-06-15 1994-01-11 Kubota Corp 加熱炉内支持面部材用耐熱合金
KR100396368B1 (ko) * 2001-04-17 2003-09-03 부공산업 주식회사 고온강도와 고온내산화성이 우수한 초내열합금
KR101030222B1 (ko) * 2010-11-18 2011-04-22 부공산업 주식회사 내식성이 우수한 스키드레일용 초내열합금
KR102365404B1 (ko) * 2019-12-04 2022-02-21 (주)영신특수강 로부품용 고크롬 내열합금 및 그 제조방법
CN113621842A (zh) * 2021-08-05 2021-11-09 烟台百思特炉管厂 一种轧钢加热炉加热段垫块材料的生产工艺

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US1357550A (en) * 1919-08-25 1920-11-02 Frank A Fahrenward Chemical ware or technical apparatus and alloys for making same
US2780545A (en) * 1954-02-03 1957-02-05 Battelle Development Corp High-temperature alloy
US3017265A (en) * 1959-09-25 1962-01-16 Gen Electric Oxidation resistant iron-chromium alloy
DE1608116A1 (de) * 1967-12-14 1970-12-10 Schmid Geb Reiniger Dipl Ing S Legierungen auf Chrombasis fuer Elektroden,insbesondere Zuendkerzenelektroden
FR2137793A1 (de) * 1971-05-12 1972-12-29 Sulzer Ag
US4442067A (en) * 1981-12-22 1984-04-10 Tohoku Tokushuko Kabushiki Kaisha Material for semiconductor holder in electron beam writing apparatus

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US4011941A (en) * 1975-04-28 1977-03-15 Warner-Lambert Company Contact lens capsule
JPS524248A (en) * 1975-06-27 1977-01-13 Dainippon Toryo Co Ltd Liquid crystal glasses
JPS5248090A (en) * 1975-10-14 1977-04-16 Furukawa Electric Co Ltd:The Method of manufacturing a connector
JPS5930781B2 (ja) * 1976-08-31 1984-07-28 財団法人特殊無機材料研究所 シリコンカ−バイド繊維強化クロム基高強度耐熱耐食合金複合材料およびその製造方法

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
US1357550A (en) * 1919-08-25 1920-11-02 Frank A Fahrenward Chemical ware or technical apparatus and alloys for making same
US2780545A (en) * 1954-02-03 1957-02-05 Battelle Development Corp High-temperature alloy
US3017265A (en) * 1959-09-25 1962-01-16 Gen Electric Oxidation resistant iron-chromium alloy
DE1608116A1 (de) * 1967-12-14 1970-12-10 Schmid Geb Reiniger Dipl Ing S Legierungen auf Chrombasis fuer Elektroden,insbesondere Zuendkerzenelektroden
FR2137793A1 (de) * 1971-05-12 1972-12-29 Sulzer Ag
US4442067A (en) * 1981-12-22 1984-04-10 Tohoku Tokushuko Kabushiki Kaisha Material for semiconductor holder in electron beam writing apparatus

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000073523A1 (fr) * 1999-05-27 2000-12-07 Japan Science And Technology Corporation Alliage a base de chrome dote d'un excellent equilibre resistance-ductilite a haute temperature
US7037467B1 (en) 1999-05-27 2006-05-02 Japan Science And Technology Agency Cr-based alloy excellent in balance between strength and ductility at high temperature
US8685315B2 (en) 1999-05-27 2014-04-01 Japan Science And Technology Agency Cr-based alloy having an excellent strength-ductility balance at high temperature
EP1681361A1 (de) * 2003-10-10 2006-07-19 National Institute for Materials Science Hochduktile silberhaltige chromlegierung
EP1681361A4 (de) * 2003-10-10 2008-04-23 Nat Inst For Materials Science Hochduktile silberhaltige chromlegierung
CN108546860A (zh) * 2018-04-27 2018-09-18 苏州弗士曼精密机械有限公司 一种高温抗氧化性不锈钢金属
CN115323234A (zh) * 2022-08-09 2022-11-11 东睦新材料集团股份有限公司 一种无磁低膨胀铬基合金材料的制备方法

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Publication number Publication date
KR910009945A (ko) 1991-06-28
AU632166B2 (en) 1992-12-17
JP2607157B2 (ja) 1997-05-07
DE69024179T2 (de) 1996-08-01
JPH03162545A (ja) 1991-07-12
KR0134182B1 (ko) 1998-06-15
AU6329690A (en) 1991-05-23
EP0429796B1 (de) 1995-12-13
DE69024179D1 (de) 1996-01-25

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