WO1993005192A1 - Material of outer layer of roll for rolling and compound roll manufactured by centrifugal casting - Google Patents
Material of outer layer of roll for rolling and compound roll manufactured by centrifugal casting Download PDFInfo
- Publication number
- WO1993005192A1 WO1993005192A1 PCT/JP1992/000400 JP9200400W WO9305192A1 WO 1993005192 A1 WO1993005192 A1 WO 1993005192A1 JP 9200400 W JP9200400 W JP 9200400W WO 9305192 A1 WO9305192 A1 WO 9305192A1
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- WO
- WIPO (PCT)
- Prior art keywords
- less
- outer layer
- resistance
- roll
- hardness
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/06—Cast-iron alloys containing chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B27/00—Rolls, roll alloys or roll fabrication; Lubricating, cooling or heating rolls while in use
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12958—Next to Fe-base component
- Y10T428/12965—Both containing 0.01-1.7% carbon [i.e., steel]
Definitions
- the present invention relates to a composite roll made of JEEEffl low 1 ⁇ layer material having excellent resistance to cracking and cracking.
- rolls for hot rolling that require abrasion resistance are composite rolls consisting of an outer layer and an inner layer, and the outer layer material is made of cementite-based carbides.
- Iron and internal scraps are made by centrifugal force truss method, using the tough rodent Tetsu-Tetsu or Ductai Jl ⁇ Iron.
- Japanese Patent Application Laid-Open No. 96355/96 can use only the isot method such as the Natsuki or Kakei build-up and the centrifugal force manufacturing method, and has a problem in terms of economic efficiency.
- an object of the present invention is to provide an eyebrow material having a uniform crack resistance and a composite roll having a distance of 5 mm. Disclosure of the invention
- the JESffl low hat material of TO according to claim 1 is: C: 1.5 to 3.5%, Si: 1.5% ⁇ 3 ⁇ 4, ⁇ : 1.2% or less, Cr: 5.5 to 12.0%, Mo: 2.0 to 8.0%, V: 3 .! ) To 10.0%, Nb: 0.6 to 7.0%, and add the following equations (1) and (2),
- the balance consists of Fe and evasive impurities.
- g is C: 1.5-3.5%, Si: 1.5% or less. Bottom, Mn: 1.2% or less, Cr: 5.5 to 12.0%, Mo: 2.0 to 8.0%, V: 3.0 to 10.0%, Nb: 0.6 to 7.0%, Ni: 5.5% or less, Co: 10.0% or less Of 1
- 3 ⁇ 4X is 2 types! And satisfy the following formulas (1) and (2),
- the remainder is composed of Fe and evasive impurities.
- the low layer material of the fiber is C: 1.5 to 3.5%, Si: 1.5% or less, Mn: 1.2% or less, Cr: 5.5 to 12.0%, Mo: 2.0 to 8.0%, V : 3.0 to 10.0%, Nb: 0.6 to 7.0%, Cu: 2.0% or less, W: 1.0% or less, Ti: 2.0% or less, Zr: 2.0% or less, B: 0.1% or less And satisfy the following expressions (1) and (2),
- the remainder is composed of Fe and ⁇ I evasive impurities.
- the low layer material for ffl according to claim 4 is: C: 1.5 to 3.5%, Si: 1.5% or less, Mn: 1.2% or less, Cr: 5.5 to 12.0%, Mo: 2.0 to 8.0%, V: 3.0 to 10.0%, Nb: 0.6 to 7.0%, Ni: 5.5% or less, Co: 10.0% or less, one or more types, Cu: 2.0% or less, W: 1.0% or less, Ti: 2.0 % Or less, Zr: 2.0% or less, B: 0.1% or less 13 ⁇ 4X contains two types: Lb, and satisfies the formulas (1) and (2).
- the balance consists of Fe and ⁇ ⁇ J evading impurities.
- the distance roll of B3 ⁇ 4 according to claim 5 is the same as that of claim 1 It is composed of an outer layer material and molten iron or duck iron.
- the 5 ′ far ' ⁇ t abutment has an intermediate layer between the outer layer material of tarn and the outer layer material of claim 5, and the outer layer material and the shaft material are interposed via the intermediate layer. It is made by welding.
- C is necessary to form a hard carbide to improve the durability of the Jl ⁇ layer material, and is required 1.5.However, if it exceeds 3.5%, the crack resistance is remarkably reduced, so the upper limit is 3 ⁇ . 5%.
- ⁇ is necessary for the same purpose as that of Si described above, but if it exceeds 1.2%, the crack resistance is reduced, so the upper limit is not preferred, and the upper limit is set to 1.2%.
- Ci forms carbides and adds 5.5% iilt with ⁇ to improve abrasion resistance. If it exceeds 12.0%, V and Nb which is the object of the present invention are added when JEJD is added. The upper limit is set to 12.0% because of the deterioration of ⁇ resistance.
- Mo forms carbides in the same way as Cr and improves the resistance to ⁇ . In addition, it improves the hardenability and temper softening resistance of the base, and is 2.0% lilb ⁇ because it is a crane to strengthen the base. However, if it exceeds 8.0%, the crack resistance decreases, so m is set to 8.0%.
- Ni is turned to improve hardenability and strengthen the base female weave. However, if it exceeds 5.5%, it is not preferable because it forms an unstable structure such as the presence of residual ⁇ .
- Co is added to stabilize the structure at a high temperature, but if it exceeds 10.0%, its heat resistance tendency is saturated, so the upper limit is set to 10.0% from the viewpoint of ecology.
- Both Cu and W are added to strengthen the base structure and improve the high-temperature hardness.However, if Cu exceeds 2.0%, the surface properties of the roll will be deteriorated, and the resistance to cracking and cracking resistance will be reduced. Is set to 2.0%, and W is added to a large amount of i® to promote segregation of V-based carbides by centrifugation, so the upper limit is set to 1.0%.
- Ti, Zr, and B are all added to suppress the formation of coarse eutectic carbides and to improve the corrosion resistance and crack resistance.However, if Ti and Zr exceed 2.0%, V, Nb The upper limit is set to 2.0 to degrade the shape and conversely reduce the wear resistance.
- V 3.0 to 100%
- Nb 0.6 to 7.0%
- V and Nb are the most important ⁇ in the present invention, and these compounds and The weight limit ⁇ is the maximum m of the present invention.
- the upper limit is set to 10.0% due to the decrease in production and problems in manufacturing.
- Nb also forms a hard MC carbide with abrasion resistance similar to V, but Nb becomes a large agglomerate and not only does not have the effect, but also has crack resistance.
- the experiment shown in Fig. 1 was made from a molten metal containing 0.5% of Si, 0.5% of Mn, 0.5% of Cr, 6.8% of Mo and 3.2% of Mo, and varied C, V and Nb. 1000 ° C normalizing process for YZ block, 550.
- the experiment in Fig. 2 contained 0.5% of Si, 0.5% of Mn, 2.7% of Ni, 2.7% of Cr, 7.2% of Mo, and 3.5% of Mo.
- a sample subjected to 1000 ° C normalizing treatment and 550C tempering treatment was used.
- r ⁇ 3 ⁇ 4i (inner / outer layer) J is the wear amount (Iw) of the test piece taken from the inner layer side of the ring material and the amount of the test piece ⁇ ⁇ ⁇ from the outer layer side.
- the maximum depth j of the thermal shock crack is the maximum depth of the crack in the m test.
- the experiment in Fig. 7 shows C: 2.3%, Si: A melt containing 0.4%, Mn: 0.5%, Ni: 0.5, Cr: 5.5%, Mo: 3.2%, V: 5.4%, Co: 5.2%, Nb: 0-7.2% is centrifuged (140 G The ring Sil with a thickness of 100 lots was normalized at 1050 ° C and tempered at 550.
- a centrifugal force (140 G) centrifugal force (140 G) was used to obtain a ring sample with a thickness of 100 mm and a thickness of 100 mm. The sample was subjected to 1050 ° ⁇ treatment and 550 ° C tempering. Was.
- the mating material was heated to 800 ° C in a two-disc sliding wear method with a mating material of ⁇ 190 ⁇ 15 and a test material of ⁇ 50 ⁇ 10, and the test material was pressed at 800 rpm with a load of 100 kgf. , The slip rate was 3.9%, and ⁇ M after 120 minutes was settled.
- the thermal shock test is performed by pressing a roller of 55X40X15 on a roller rotating at 1200 rpDi with a load of i50kgf and a contact time of i5s.
- the crack length was determined.
- the heat J3 ⁇ 4S ⁇ applied to the roll material of the present invention after austenitizing at 1000 to 150 ° C, controlled cooling is performed so that the structure after cooling becomes bainite. Therefore, depending on the shape and size of the roll material to be processed, the cooling rate may be different from that of the roll material.
- the size of the material to be treated is small, so normalizing (air cooling after austenitizing) and quenching (austenitic pia quenching) Both processes are possible.
- tempering is carried out by selecting ⁇ with 500-600 ° C® thigh. Brief description of the drawings ''
- Fig. 1 shows the effect of the combined amount of V and Nb and the amount of C on the base metal hardness
- Fig. 2 shows the combined amount of V and Nb with the amount of Si and C on the base metal hardness
- Fig. 3 shows the composite of V and Nb (Fig. 3) shows the relationship between the JD content and the C content affecting the base metal hardness
- Fig. 4 shows the composite of V and Nb and the C content.
- Fig. 5 shows the hot wear ratio between the outer layer and the inner layer caused by the carbide distribution of the link material made by centrifugal gun, and the Nb / V content ratio Nb / V which affects the maximum crack depth in the thermal shock test.
- Fig. 6 shows the wear ratio between the outer layer and the inner layer due to the carbide distribution of the ring material made by centrifugal force, and the relationship between the Nb / V content ratio Nb / V that affects the maximum crack depth in the thermal shock test.
- Fig. 7 shows the wear ratio between the outer and inner layers caused by the carbide distribution of the ring material made by centrifugal force, and the Nb / V content ratio Nb / V on the maximum crack depth in the thermal shock test.
- Fig. 8 is a diagram showing the wear ratio of the outer and inner layers caused by the carbide distribution in the ring material produced by centrifugal force, and the relationship between the content of Nb and V and the fiit Nb / V affecting the maximum crack depth in the thermal shock test.
- FIG. 9 is a longitudinal sectional view of the composite roll according to Example 7,
- FIG. 10 is a diagram showing a comparison of JE @ in a difficult-to-mill mill of the composite roll obtained in Examples 6 and 7 with that of the roll.
- the molten metal shown in Table 1 was made by centrifugal force-forming (140G), and the thickness was 100 sq.m. A ring sashipur was prototyped and subjected to Shore hardness, hot and thermal shock tests.
- the entrainment test was carried out under the same conditions as those described above, with the knowledge of ⁇ 50 ⁇ 10 from the inner layer side and the outer layer side of the ring material.
- the thermal impulse ⁇ ! ⁇ was obtained by performing the plate test described above from the outer layer side of the ring material.
- Table 2 shows the results of these tests and thermal shock tests. According to Table 2, this month's material has the same hardness as the other Ni-grain material (A material), but it is recognized that both the oil resistance and crack resistance are significantly improved. .
- the G material has a reduced resistance to the outer layer due to carbides, and the H material has insufficient hardness and resistance. Cracking property is low, hardness of material I is insufficient and hardness of outer layer is deteriorated due to unevenness of carbide, and hardness of material J is insufficient.
- the K material has an excessive amount of C and therefore has a low crack resistance
- the L material has an excessive amount of Si and has a low crack resistance
- the M material has an excessive amount of Mn and has a crack resistance.
- N material has too much Cr content, so its resistance to cracking and cracking deteriorates.No. 0 material has too much Mo, it has low crack resistance. ⁇ resistance because you are, resistance to clutch click resistance decreases, Q material 0 example crack resistance deteriorated because the amount of V is too large 2)
- G, R were manufactured by centrifugal force (140G), and a link 'sample having a thickness of 100 mm was prototyped, and subjected to a Shore hardness test, a hot test, and a thermal test.
- the release test was conducted in the same manner as in the previous operation, with knowledge of ⁇ 50-10 from the inner layer side and outer layer side of the ring material. '
- thermal shock test was conducted under the same conditions, using the above-mentioned plate-like testing station from the outer layer side of the ring material.
- Table 4 shows the results of the ⁇ test and the convergence ⁇ 1 test. According to Table 4, this material has the same hardness as the Mi-Dallen material (A material), It can be seen that both the crack resistance and remarkably improved.
- the ratios of the iG to J materials are not limited to those of the present invention, the hardness of the G and J materials is reduced, and the hardness of the outer layer of the H material is reduced due to the unevenness of the carbide.
- the crack resistance of the material is low.
- the comparative materials K to R the crack resistance of the K material is reduced due to the excessive amount of Cfi ⁇ ', and the crack resistance of the L material is reduced due to the excessive amount of Si.
- N material has too much Nifi ⁇ ', so hardness, resistance, and crack resistance are reduced, and No. 0 material has excessive Cr content Oil resistance and crack resistance are reduced, P material has an excessive amount of Mo, so crack resistance is reduced, and Q material is insufficient in V amount, which results in reduced ⁇ and crack resistance. Since the R material has an excessive V content, the crack resistance is reduced. Difficult case 3)
- the molten metal shown in Table 5 (materials of the present invention: B-F, jt ⁇ ti: A, G-R) was made by centrifugal casting, and a ring sample of 100 marauder thickness was prototyped. A hot and hot shock test was performed.
- the Lin test was conducted under the same conditions as those described above by collecting IW of ⁇ 50 ⁇ 10 from the inner layer side and the outer layer side of the ring material, respectively.
- thermal shock test was carried out under the same conditions by applying the above-mentioned plate-like test to the ring material from the outer layer side at KK.
- Table 6 shows the results of the wear test and the thermal shock test. According to Table 6, although the hardness of this B month steel is the same as that of the Ni-Dallen material (A material) of 2, it is recognized that both the resistance to cracking and the resistance to cracking are significantly improved. Can be
- the G material has a hardness of CftO and the resistance of the outer layer decreases due to the unevenness of the carbide.
- the segregation of carbides reduced the outer layer's resistance, for material I, the crack resistance was reduced, and for material J, the hardness was insufficient.
- the K material has an excessive amount of C and thus has a low crack resistance.
- the L material has an excessive amount of Si and therefore has a poor cracking resistance. Cracking resistance is reduced, N material has too much NiS ⁇ , so its resistance to cracking and cracking is reduced. Material 0 has too much Cr, and it has reduced resistance to cracking and cracking.
- the P material has an excessive amount of Mo and therefore has a reduced crack resistance.
- the Q material has an insufficient amount of V, and therefore has a low H and crack resistance.
- the R material has an excessive amount of V. Therefore, crack resistance is reduced.
- Example 4 The molten metal shown in Table 7 (Materials of the present invention: B to E, Q, Comparative materials: A, F to P) was made by centrifugal force casting, and the wall thickness was 100 Ring samples were prototyped and subjected to Sho-HI, hot and thermal shock tests.
- 3 ⁇ 4 50 ⁇ 10 3 ⁇ 4 ⁇ were collected from the inner layer side and outer layer side of the imit.
- thermal shock test was performed using the same rice cake, with the above-mentioned plate-like sample removed from the outer layer side of the ring material.
- Table 8 shows the results of the ⁇ test and the ripening test. According to Table 8, it can be seen that, although the hardness of this lumber is about the same as that of the conventional Ni-grain material (A material), the crack resistance is significantly improved.
- the comparative materials F to P are out of the scope of the present invention, the F material moves, and thus the hardness is reduced.
- the wear resistance of the outer layer decreases due to the precipitation of carbides, the crack resistance of the H material decreases, and the hardness of the I material is insufficient.
- J material has too much C
- crack resistance decreases because of the excessive Si content of K material, crack resistance decreases due to excessive Mn content of L material, and Cr content of M material decreases.
- N material has excessive Mo content, and therefore crack resistance is reduced.
- 0 material has insufficient V content, and has ⁇ resistance and crack resistance.
- the P material has an excessive amount of V, and the crack resistance is reduced.
- the molten metal with the chemical composition shown in Table 9 (material of the present invention: B5 to J5, comparative material, K5 to ⁇ 5) was made by centrifugal force truss, and a ring sample with a wall thickness of lOOmra was prototyped, and Shore hardness A hot and hot impact test was performed.
- the ⁇ 50X10 was obtained from the inner and outer layers of the Link 'material, respectively.
- Table 10 shows the results of the ⁇ test and the thermal shock test. According to Table 10, the hardness of the material of the present invention is the same as that of the Ni-Dallen material (material A), but the wear resistance and crack resistance are remarkably improved.
- the K5TOCufi content is excessive, so that the resistance to nucleation and cracking is reduced. Due to the eccentricity, the resistance of the outer layer decreases, and the 1 ⁇ 5 material has an excessive number of 1 ⁇ and 8 units.] The resistance and crack resistance are reduced, and the N5 material has an excessive amount of Zr. Has reduced wear resistance
- a composite roll having an outer layer and an inner layer having the composition shown in Table 11 and having a body diameter of 670 and a body length of 1450 was produced by the following procedure.
- the melt of the outer eyebrow material was melted in the observation melting furnace, and the melt of the outer layer material was poured into a centrifugal rifle gun rotating at a centrifugal force of 140 G to a thickness of 75 mm at 1490 ° C.
- the inner layer leak was filled at 1420 ° C. After cooling to room temperature, the mold was dismantled, and the mold was subjected to buffing.
- the temperature was reduced from 1050 ° C;! ⁇ ⁇ , and then tempering was performed at 550 ° C. Despite the fact that heat treatment and sound were performed, the roll had no defects and was a healthy roll.
- the outer layer thickness after finishing was 45 NOTE, and the surface hardness was 78-82 in Shore hardness.
- a composite roll having an outer layer, an intermediate layer, and an inner layer having the composition shown in Table 12 and having a body diameter of 670 m and a body length of 1450 m shown in FIG. 9 was subjected to the following procedure.
- the melt of the outer layer material was melted in the observation melting furnace, and the melt of the outer layer material was poured into a long distance rotating at a centrifugal force of 140 G at 1490 ° C to a thickness of 75 °.
- the molten metal was poured at 1540 ° C to a thickness of 40 thighs.
- an fflW composite roll excellent in resistance to cracking and resistance to segregation is obtained without segregation even when a centrifugal force method with excellent properties and warpage is applied. be able to.
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- Mechanical Engineering (AREA)
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP92907591A EP0562114B1 (en) | 1991-09-12 | 1992-03-31 | Material of outer layer of roll for rolling and compound roll manufactured by centrifugal casting |
US08/050,394 US5316596A (en) | 1991-09-12 | 1992-03-31 | Roll shell material and centrifugal cast composite roll |
KR1019930701420A KR960005598B1 (ko) | 1991-09-12 | 1992-03-31 | 압연용 로울 외층재료 및 원심력 주조제 복합로울 |
DE69227504T DE69227504T2 (de) | 1991-09-12 | 1992-03-31 | Material für aussenschicht einer umformwalze und durch schleuderguss hergestellte verbundwalze |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3260486A JP2832254B2 (ja) | 1991-09-12 | 1991-09-12 | 圧延用遠心鋳造製ロール外層材 |
JP3/260486 | 1991-09-12 | ||
JP27359791A JP2715199B2 (ja) | 1990-10-01 | 1991-09-26 | 圧延用ロール外層材 |
JP3/273597 | 1991-09-26 | ||
JP3/303832 | 1991-10-24 | ||
JP30383291A JP2715205B2 (ja) | 1990-11-21 | 1991-10-24 | 圧延用ロール外層材 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993005192A1 true WO1993005192A1 (en) | 1993-03-18 |
Family
ID=27334921
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1992/000400 WO1993005192A1 (en) | 1991-09-12 | 1992-03-31 | Material of outer layer of roll for rolling and compound roll manufactured by centrifugal casting |
PCT/JP1992/000625 WO1993005193A1 (en) | 1991-09-12 | 1992-05-14 | Material of outer layer of roll for rolling and compound roll manufactured by centrifugal casting |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1992/000625 WO1993005193A1 (en) | 1991-09-12 | 1992-05-14 | Material of outer layer of roll for rolling and compound roll manufactured by centrifugal casting |
Country Status (5)
Country | Link |
---|---|
US (1) | US5316596A (ja) |
EP (2) | EP0562114B1 (ja) |
DE (1) | DE69227504T2 (ja) |
ES (1) | ES2124728T3 (ja) |
WO (2) | WO1993005192A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101281135B1 (ko) | 2005-12-28 | 2013-07-02 | 히타치 긴조쿠 가부시키가이샤 | 원심 주조 복합롤 |
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MX2016016893A (es) * | 2014-06-27 | 2017-03-27 | Jfe Steel Corp | Rodillo de calibre de colada centrifuga para tren de laminacion en caliente. |
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JP6908021B2 (ja) * | 2016-03-31 | 2021-07-21 | 日立金属株式会社 | 圧延ロール用外層及び圧延用複合ロール |
CN107891138B (zh) * | 2017-11-09 | 2020-02-04 | 常州凯达重工科技有限公司 | 一种用于制作金属瓦楞板的超高钒高速钢压辊的制备工艺 |
RU2696119C1 (ru) * | 2018-10-01 | 2019-07-31 | Федеральное государственное бюджетное научное учреждение Федеральный научный агроинженерный центр ВИМ (ФГБНУ ФНАЦ ВИМ) | Наплавочный порошок на железной основе |
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- 1992-03-31 EP EP92907591A patent/EP0562114B1/en not_active Expired - Lifetime
- 1992-03-31 DE DE69227504T patent/DE69227504T2/de not_active Expired - Lifetime
- 1992-03-31 WO PCT/JP1992/000400 patent/WO1993005192A1/ja active IP Right Grant
- 1992-03-31 US US08/050,394 patent/US5316596A/en not_active Expired - Lifetime
- 1992-05-14 EP EP92909738A patent/EP0559899B1/en not_active Expired - Lifetime
- 1992-05-14 WO PCT/JP1992/000625 patent/WO1993005193A1/ja active IP Right Grant
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KR101281135B1 (ko) | 2005-12-28 | 2013-07-02 | 히타치 긴조쿠 가부시키가이샤 | 원심 주조 복합롤 |
Also Published As
Publication number | Publication date |
---|---|
EP0559899A4 (ja) | 1994-01-26 |
DE69227504D1 (de) | 1998-12-10 |
EP0559899B1 (en) | 1998-11-04 |
WO1993005193A1 (en) | 1993-03-18 |
EP0562114A4 (ja) | 1994-01-26 |
DE69227504T2 (de) | 1999-04-08 |
ES2124728T3 (es) | 1999-02-16 |
EP0559899A1 (en) | 1993-09-15 |
US5316596A (en) | 1994-05-31 |
EP0562114A1 (en) | 1993-09-29 |
EP0562114B1 (en) | 1998-11-04 |
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