 centrifugally cast composite cylinder and method of production thereof
专利摘要:
Patent Specification: "Centrifugally Cast Composite Rolling Mill Cylinder and Production Method". The present invention relates to a centrifugally cast composite rolling mill cylinder obtained by joining metal of: an outer layer obtained from a cast iron having a chemical composition containing on a mass basis 2,7-3 0.5% c, 1.5-2.5% Si, 0.4-1.0% Mn, 3.7-5.1% Ni, 0.8-2.2% Cr, 1.5-4.5% mo, 2.0-4.5% v and 0.5-2.0% nb, and the remainder is obtained from f and inevitable impurities, the mass ratio of nb / v is 0.18-0.65 and the mass ratio of mo / v is 0.7-2.5, and a structure that has, on a basis area, 15-45% of a cementite phase and 1-10% of a graphite phase; and an inner layer obtained from a cast iron of excellent mechanical strength, virtually no splash segregation from bainite and / or martensite dendrites of 1.5 mm diameter or more is present in the usable region of the outer layer at depths of 10 mm or more. more from the surface. 21315840v1 公开号:BR112014012076B1 申请号:R112014012076-5 申请日:2012-11-21 公开日:2018-12-26 发明作者:Takayuki Segawa；Yasunori NOZAKI；Nozomu Oda 申请人:Hitachi Metals, Ltd.； IPC主号:
专利说明:
Descriptive Report of the Patent of Invention for CENTRIFUGALLY CASTED COMPOSITE CYLINDER AND PRODUCTION METHOD OF THE SAME. FIELD OF THE INVENTION [001] The present invention relates to a composite cylinder comprising an outer layer formed by a centrifugal casting method, which is integrally fused to a resistant inner layer, and the method of producing it. BACKGROUND OF THE INVENTION [002] Due to the fact that cylinders for hot strip laminators are subject to wear and surface roughness on their outer layer surfaces due to a mechanical thermal load due to contact with the sheets being laminated, deteriorating the dimensions, shapes and surface qualities of laminated sheets, they must be changed periodically. Used cylinders are ground to remove wear and surface roughness caused by rolling, and then used for the next rolling. When such a cylinder change cycle is short, lamination is often interrupted, resulting in low productivity. Therefore, cylinders with good wear resistance and resistance to surface roughness are required. [003] In a hot strip laminator, a sheet being laminated can go through the so-called folding lamination problem, in which the sheet is folded when moving between the laminating cages and laminated in a state folded by upper rollers and lower. In particular in downstream rolling cages, for example, mainly after a fifth rolling cage in a finishing rolling mill that has seven rolling cages, such a problem tends to occur because of a high rolling speed. Petition 870180138646, of 10/08/2018, p. 6/58 2/45 [004] Due to the fact that a laminated sheet adheres to a surface of the outer layer of the cylinder in such a rolling problem, an excessive mechanical thermal load is applied to the cylinder, so that the outer layer of the cylinder can be cracked. When the cracked cylinder continues to be used, the cracks are likely to propagate, causing the cylinder to rupture, which is called a fracture or chipping. Therefore, once the folding lamination problem occurs, a surface of the cylinder is cut to remove the cracks. Deep cracks need a deep cut, which results in a large cylinder loss and a high cost cylinder. Therefore, cylinders which have good failure resistance, which suffer little crack damage in such a rolling problem are desirable. [005] Thus, in rolling mill cages downstream in a finishing plant, grain cylinders containing graphite are used for excellent resistance to failures (resistance to binding). However, due to the fact that conventional grain laminating cylinders have poor wear resistance and thus a short service life, changing and rectifying the cylinders must be carried out frequently, resulting in low productivity. On the other hand, high-speed steel cylinders that comprise the outer layers that have compositions similar to those of high-speed tool steels have a high wear resistance, but due to the fact that they do not contain graphite, they suffer from jamming and cracking by large thermal shock in the folding lamination problem. Therefore, high-speed steel cylinders cannot be used in downstream rolling cages in a finishing plant. Thus, an improvement in wear resistance is required for grain rolling cylinders used in downstream rolling cages at a Petition 870180138646, of 10/08/2018, p. 7/58 3/45 hot finish lamination. [006] Against such demand, the patent JP 2005-105296 A presents an external layer for a hot rolling cylinder that has an excellent wear resistance and resistance to surface roughness, which has a composition that comprises, in mass, 2, 53.5% C, 1.0-2.5% Si, 0.3-1% Mn, 3-5% Ni, 1.5-2.5% Cr, 1.0-4 % Mo, 1.4-3.0% V, 0.1-0.5% Nb and 0.0005-0.2% B, and the rest consists of Fe and unavoidable impurities, and a structure which contains 50,000-1,000,000 / mm 2 of fine carbides having maximum lengths of 0.1-5 pm at least in one part of the matrix. This outer layer for the cylinder is produced by a centrifugal casting method at a melting temperature of 1,320Ό and a centrifugal force of 160 G. [007] However, it has been found that when an outer layer of grain cast iron that contains an increased amount of V, a hard carbide forming element, as described in JP 2005-105296 A, is melted centrifugally, secreted dendrites such as splashes of bainite and / or martensite grow as much as 1.5 mm or more in diameter, in a region as deep as about 10 mm or more from the surface of the outer layer. Segregated dendrites of the splash type with few carbides are predominantly worn out than an environmental structure, and the worn parts of the splash type are transferred to a laminated plate, deteriorating its quality. Such splash-type segregation is caused by the segregation of solidification in the centrifugal casting. That is, when solidified under a centrifugal force, the crystallized low-carbon austenite phases that make up the dendrites have a specific gravity greater than that of a liquid phase, so that they move towards the outer surface side by a centrifugal force. Coarse splash dendrites are Petition 870180138646, of 10/08/2018, p. 8/58 4/45 formed by the following mechanism: The austenite phases crystallized in a molten mass that has an increased carbon concentration due to the migration of austenite phases to the outer surface side cannot move in a molten mass with concentrated carbon which has an increased viscosity due to the increase in a solid phase ratio, so that they grow large and are transformed into bainite and / or martensite. Therefore, the composite cylinder that has an outer layer of grain cast iron, which is described in JP 2005-105296 A, cannot be used in downstream rolling mill cages in a finishing plant. [008] JP patent 6-335712 A discloses a wear-resistant and jam-resistant hot-rolled cylinder that has a chemical composition comprising, by weight, 2.0-4.0% C, 0.5- 4.0% Si, 0.1-1.5% Mn, 2.0-6.0% Ni, 1.0-7.0% Cr and 2.08.0% V, and the rest consists of Fe and impurity elements, and a metal structure comprising a matrix, 0.5-5% in graphite area, 0.2-10% in MC carbide area, and 10-40% in cementite area. JP 6-335712 A also states that, in addition to the above components, it may also contain, by weight, one or more of 0.3-4.0% Mo, 1.0-10% Co, 1 , 0-10% Nb, 0.01-2.0% Ti, 0.002-0.2% B and 0.02-1.0% Cu. However, even this cylinder contains segregated dendrites of the splash type of bainite and / or martensite. This appears to be due to the fact that, as in JP patent 2005-105296 A, a phase of crystallized austenite during centrifugal casting is secreted by a centrifugal force. [009] JP 2004-323961 A discloses an outer layer for a hot rolled composite cylinder, which has a composition comprising 2.6-3.5% by weight of C, 1.5-2.5% by weight of Si, 0.2-1.5% by weight of Mn, 1.0-2.5% by weight of Cr, 1.0-3.0% by weight of Mo, 2.0-7, 0% by mass of Ni, 1.3-2.5% in Petition 870180138646, of 10/08/2018, p. 9/58 5/45 mass of V, 0.1-0.8% by weight of Nb, 0.020-0.2% by weight of B, and one or two of 0.05% or less by weight of Ti and 0.1 % or less by mass of Al, and the remainder consists of Fe and unavoidable impurities, and a structure comprising graphite particles having diameters equivalent to circles of 20 pm or more at 10 / mm 2 or more, where the ratio of spheroidization of the graphite particle that has diameters equivalent to circles of 20 pm or more is 15-75%. Although this reference contemplates the segregation of carbides, it does not specifically present the conditions of the composition of V, Nb and Mo and the conditions of production to prevent the generation of segregated dendrites of the splash type of bainite and / or martensite within the outer layer. [0010] JP 2004-162104 A discloses an outer layer for the hot rolled composite cylinder which has a composition comprising, by weight, 2.6-3.5% C, 1.0-2.5 % Si, 0.2-1.5% Mn, 0.8-2.7% Cr, 1.0-3.0% Mo, 2.0-7.0% Ni, 1.3-2.5% V, 0.1-0.8% Nb, and 0.020-0.2% B, and the quantities of C, Cr, Nb and V satisfy the following formulas (1) a (3): 2.0 <C - (0.24 xV + 0.13 x Nb) <3.0 ... (1), Cr / C <1.0 ... (2), and 3.0 <Cr + V <4.5 ... (3), [0011] where each of C, V, Nb and Cr represents the quantity (% by mass) of each element, and also comprises one or two of less than 0.05% Ti and 0.1% or less Al, with the remainder consisting of Fe and unavoidable impurities. Although this reference contemplates the segregation of carbides, it does not specifically present the conditions of the composition of V, Nb and Mo and the conditions of production to prevent the generation of segregated dendrites of the splash type of bainite and / or martensite in the outer layer. [0012] JP patent 2003-342669 A has an outer layer Petition 870180138646, of 10/08/2018, p. 10/58 6/45 for a hot rolling cylinder which has excellent wear resistance, resistance to jamming and resistance to surface roughness, which has a composition comprising, by mass, 2.4-3.2% C, 0, 9-2.5% Si, 0.2-1.5% Mn, 0.8-2.5% Cr, 1.2-4.0% Mo, 2.0-7.0% Ni, 1.5-2.7% V, 0.1-0.8% Nb, 0.0200.2% B, and 0.0006-0.040% REM, and the amounts of C, Cr, Nb and V satisfy the following formulas (1) to (3): 1.8 <C - (0.236 xV + 0.129 x Nb) <2.6 ... (1), Cr / C <1.0 ... (2), and 3.0 <Cr + V <4.6 ... (3), [0013] where each of C, V, Nb and Cr represents the quantity (% by mass) of each element, and also comprises one or two of less than 0.05% Ti and 0.1% or less Al, and the rest consists of Fe and unavoidable impurities, and a structure that comprises graphite. Although this reference contemplates the segregation of carbides, it does not specifically present the conditions of the composition of V, Nb and Mo and the conditions of production to prevent the generation of segregated dendrites of the splash type of bainite and / or martensite in the outer layer. [0014] JP 2004-68142 A discloses an outer layer for a hot rolling cylinder which has an excellent resistance to binding and wear resistance, which has a composition comprising, in mass, 2.9-3.8 % C, 0.8-2.0% Si, 0.2-1.5% Mn, 1.5-3.5% Cr, 0.8-3.5% Mo, 3, 0-7.0% Ni, 1.0-3.5% V, 0.1-0.8% Nb, 0.020-0.2% B and 0.002-0.030% REM, and the following formulas (1) and (2) are satisfied: 2.5 <C - (0.236 xV + 0.129 x Nb) <3.2 ... (1), and 0.5 <Cr / C <1.0 ... (2), [0015] where each of C, V, Nb and Cr represents the quantity (% by mass) of each element, of which the rest consists in Fe and Petition 870180138646, of 10/08/2018, p. 11/58 7/45 unavoidable impurities. Although this reference contemplates the segregation of carbides, it does not specifically present the conditions of the composition of V, Nb and Mo and the conditions of production to prevent the generation of segregated dendrites of the splash type of bainite and / or martensite in the outer layer. [0016] JP patent 8-209299 A discloses a hot rolling cylinder which has a high resistance to binding, which comprises, by weight, 2.0-4.0% C, 1.0-5.0% Si, 0.1-2.0% Mn, 0.1-6.0% Cr, 0.1-6.0% Mo, 0.1-6.0% V and 1.0 -8.0% Ni, with the remainder consisting of Fe and unavoidable impurities. This cylinder can also contain at least one of 0.1-6.0% W, 0.1-4.0% Nb and 0.1-10.0% Co. However, this reference does not show the carbide segregations nor the conditions of the composition of V, Nb and Mo nor the conditions of production to prevent the generation of segregated dendrites of the splash type of bainite and / or martensite in the outer layer. [0017] EP 1190108 B discloses a method for the production of a composite cylinder comprising (1) the preparation of a melt mass comprising 2.0-3.5% by weight of C, 1.02.0 % by weight of Si, 0.5-2.0% by weight of Mn, 1.0-3.0% by weight of Cr, 3.5-4.9% by weight of Ni and 0.20-2 , 9% by weight of Mo, the remainder consisting of Fe and impurities, (2) the dissolution of more than 0.5% by weight and 5.9% or less by weight of V, a part of which can be replaced by Nb, etc., in the melting mass, (3) adjusting the composition of the melting mass in such a way that its solidification forms a fine structure comprising 1.0-3.0% by volume of graphite, 8 -35% by volume of eutectic carbide and at least 1% by volume of V carbide, and the remainder consists substantially of martensite, (4) casting the melt into a centrifugal casting mold, and (5) treating thermal. However, this reference does not Petition 870180138646, of 10/08/2018, p. 12/58 8/45 specifically presents the conditions of the composition of V, Nb and Mo and the conditions of production to prevent the generation of segregated dendrites of the splash type of bainite and / or martensite in the outer layer. [0018] JP patent 2004-82209 A discloses a centrifugally molten hot-rolled composite cylinder, which comprises an outer wrap layer that has a composition comprising, by mass, 3.0-4.0% C, 0.8-2.5% Si, 0.2-1.2% Mn, 3.0-5.0% Ni, 0.5-2.5% Cr, 0.1-3, 0% Mo and 1.0-5.0% V, and the rest consists of Fe and unavoidable impurities, and an inner layer made of the usual cast iron or spheroidal graphite cast iron containing 2.5-4.0 % of C, where the thickness T of the outer wrap layer and the radius R of the inner layer satisfy the ratio expressed by the formula of 0.03 <T / R <0.5. However, this reference does not in fact present the conditions of the composition of V, Nb and Mo and the conditions of production to prevent the segregation of carbides and the generation of segregated dendrites of the splash type of bainite and / or martensite in the outer layer. [0019] JP 8-302444 A discloses an outer layer cast at 1400Ό or more for a centrifugal casting cylinder, where the outer layer comprises 2.5-4.7% C, 0.8-3.2 % Si, 0.1 2.0% Mn, 0.4-1.9% Cr, 0.6-5% Mo, 3.0-10.0% V and 0.6-7 , 0% Nb, and meets the following formulas (1) to (4); 2.0 + 0.15V + 0.10 Nb <C (%) ... (1), 1.1 <Mo / Cr ... (2), Nb / V <0.8 ... (3), and 0.2 <Nb / V ... (4), [0020] where the rest consists of Fe and unavoidable impurities, and contains granular MC carbide and graphite. Although this reference contemplates the segregation of carbides, it does not present Petition 870180138646, of 10/08/2018, p. 13/58 9/45 specifically the conditions of the composition of V, Nb and Mo and the conditions of production to prevent the generation of segregated dendrites of the splash type of bainite and / or martensite in the outer layer. [0021] As a centrifugally cast cylinder comprising an outer layer made of grain cast iron, which does not contain splash-type segregations that have diameters of 1.5 mm or more, the JP 2001-321807 A patent features a lamination cylinder comprising an outer layer made of grain cast iron comprising 2.8-3.5% by weight of C, 1.5% or less by weight of Si, 1.5% or less by weight of Mn, 3- 5% by weight of Ni, 1-3% by weight of Cr, and less than 1.0% by weight of Mo, and the remainder consists substantially of Fe, 90% or more of splash-type segregations that have diameters of 1 , 0 mm or more that have diameters of less than 2.0 mm in a rolling region to a depth of 20-30 mm. The outer layer contains 2.0% or less by weight in total of at least one element selected from the group consisting of 2.0% or less by weight of V, 2.0% or less by weight of Nb, 1.0 % or less by weight of Ti, 1.0% or less by weight of Zr, and 1.0% or less by weight of Ta, and has carbide of the type M1C1. However, due to the fact that the total amount of V and Nb is 2.0% or less by weight, the generation of segregated dendrites of the splash type of bainite and / or martensite in the outer layer cannot be sufficiently prevented. [0022] In this way, it is difficult to improve the wear resistance of a grain rolling cylinder to obtain a centrifugally cast composite cylinder that has good wear resistance and resistance to failure with the segregated dendrites of the splash type of bainite and / or suppressed martensites. OBJECTIVE OF THE INVENTION [0023] Therefore, an objective of the present invention is to provide a composite cylinder comprising a layer Petition 870180138646, of 10/08/2018, p. 14/58 10/45 external centrifugally cast that has an excellent wear resistance and resistance to failures (resistance to binding) substantially free of segregated dendrites of the splash type of bainite and / or martensite, and the method of production thereof. SUMMARY OF THE INVENTION [0024] As a result of intensive research in view of the above objective, it was found that (a) due to the fact that in a centrifugal casting process of the cast iron in grain that contains large amounts of carbide forming elements, a phase of heavy austenite (γ phase) moves to the side of the outer surface by centrifugal force, an austenite phase (γ phase) formed as a primary crystal in a melt mass with remaining concentrated carbon (low eutectic melt mass) melting point) is retained in the melting mass with increased viscosity by decreasing temperature, and grows to large dendrites, and that (b) to prevent the γ phase from moving to the side of the outer surface and being concentrated in the initial stage of solidification, it is necessary to regulate not only the quantities of V, Nb and Mo, carbide-forming elements, but also the mass ratios of Nb / V and Mo / V, and to control the temperature casting and centrifugal force during centrifugal casting. The present invention has been completed on the basis of such findings. [0025] The centrifugally cast composite cylinder of the present invention comprises an outer layer made of cast iron that has a chemical composition comprising, by mass, 2.7-3.5% C, 1.5-2.5% Si, 0.4-1.0% Mn, 3.7-5.1% Ni, 0.8-2.2% Cr, 1.5-4.5% Mo, 2.0-4.5% V and 0.5-2.0% Nb, and the rest consists of Fe and unavoidable impurities, a mass ratio of Nb / V that is 0.18-0.65, and a mass ratio of Mo / V that is 0.7-2.5, and a structure that comprises, in area, 15-45% of a cementite phase Petition 870180138646, of 10/08/2018, p. 15/58 11/45 and 1-10% of a graphite phase, and an inner layer made of cast iron that has excellent mechanical strength and is metallurgically bonded to the outer layer; a usable region of the outer layer as deep as 10 mm or more from the surface that does not contain substantially any segregated dendrite of the bainite and / or martensite splash type having diameters of 1.5 mm or more. The term usable region of the outer layer used here refers to a region in the direction of the depth of the outer layer usable for lamination, which is called the lamination layer. [0026] The structure of the outer layer preferably comprises, in area, 0.9-9.5% of graphite particles that have diameters equivalent to circles of 5 pm or more, 1-20% of particles based on carbide V that have diameters equivalent to circles of 1.5-50 pm, and 0.3-15% in total particles based on Nb carbide that have diameters equivalent to circles of 1.5-100 pm and particles based on Mo carbide having diameters equivalent to 1.5-100 pm circles; the number of particles based on V carbide is 50-10,000 / mm 2 , and the total number of particles based on Nb carbide and particles based on Mo carbide is 50-10,000 / mm 2 . [0027] The outer layer can also contain, by mass, at least one selected from the group consisting of 0.1-5.0% W, 0.015.0% Ti, 0.01-2.0% Al , 0,01-0,5% of Zr, 0,001-0,5% of B and 0, ΙΙΟ, 0% of Co. [0028] The chemical composition of the outer layer preferably satisfies, by mass, the conditions of 1.7% <C - (0.06 Cr + 0.063 Mo + 0.033 W + 0.2 V + 0.13 Nb) <2 , 7%, 1.8% <C + Si / 3 + Ni / 18 - [(Mo + W + Nb) / 15 + (Cr + V) / 3] <2.8%, and a mass ratio of 0.8-5.0 Mo / Cr. [0029] The outer layer preferably has a chemical composition comprising 2.8-3.5% C, 1.5-2.3% Si, 0.5-1.0% Petition 870180138646, of 10/08/2018, p. 16/58 12/45 Μη, 3.9-5.0% Ni, 0.9-1.9% Cr, 1.7-4.2% Mo, 2.0-4.0% V and 0.5- 1.3% Nb, and the rest consists of Fe and unavoidable impurities; a mass ratio of Nb / V which is 0.2-0.6, and a mass ratio of Mo / V which is 0.7-2.0. [0030] The outer layer preferably fulfills the requirement that V + 1.2 Nb is 2.7-4.5% by mass. [0031] The inner layer is preferably made of nodular cast iron. [0032] The method of the present invention for the production of the above-cast centrifugal composite cylinder comprises melting a molten mass to the outer layer which has a chemical composition comprising, by mass, 2.7-3.5% C , 1.5-2.5% Si, 0.4-1.0% Mn, 3.7-5.1% Ni, 0.8-2.2% Cr, for 1.5- 4.5% Mo, 2.0-4.5% V and 0.5-2.0% Nb, and the rest consists of Fe and unavoidable impurities, a mass ratio of Nb / V which is 0.180.65, and a mass ratio of Mo / V which is 0.7-2.5, in a centrifugal casting mold at a temperature in the range of its initial austenite precipitation temperature + 30Ό up to its temperature initial precipitation of austenite + 180Ό; and the formation of the outer layer under a centrifugal force that has a number of gravity in the range of 60-150 G. [0033] The centrifugal casting mold is preferably formed of nodular cast iron that has a thickness of 120-450 mm. [0034] It is preferable that after an internal surface of the centrifugal casting mold is coated with a coating material as thick as 0.5-5 mm, which mainly comprises silica, alumina, magnesia or zirconia, the outer layer is centrifugally shaped. BRIEF DESCRIPTION OF THE DRAWINGS [0035] Fig. 1 is a schematic view showing a machine Petition 870180138646, of 10/08/2018, p. 17/58 13/45 rolling wear test. [0036] Fig. 2 is a schematic view showing a thermal shock test machine for friction. [0037] Fig. 3 is an optical photomicrograph A showing the structure of the specimen of Example 1 taken in step 2. [0038] Fig. 4 is a photograph B of a BSE image showing the structure of the specimen of Example 1 taken in step 3. [0039] Fig. 5 is an optical photomicrograph C showing the structure of the specimen of Example 1 taken in step 5. [0040] Fig. 6 is an optical photomicrograph D showing the structure of the specimen of Example 1 taken in step 7. [0041] Fig. 7 is an optical photomicrograph E that shows the structure of the specimen of Example 1 taken in step 9. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0042] The modalities of the present invention will be explained in detail below without intention of limitation, and various modifications can be made within the scope of the present invention. Ml Centrifugally molten composite cylinder (A) Composition of the outer layer [0043] In the centrifugally molten composite cylinder of the present invention comprising an outer layer formed by a centrifugal casting method and a hard inner layer integrally fused to the outer layer, the layer external has the following chemical composition (% by mass), (1) indispensable composition (a) C: 2.7-3.5% by mass [0044] OC is combined with V, Nb, Cr, Mo and W to form hard carbides, contributing to the improvement of the wear resistance of the outer layer, and acts with accelerating elements of graphite formation such as Si and Ni to precipitate graphite in the structure, Petition 870180138646, of 10/08/2018, p. 18/58 14/45 giving the outer layer a resistance to binding. When C is less than 2.7% by mass, the precipitation of graphite is insufficient, and the amount of precipitated hard carbides is too small to provide sufficient wear resistance to the outer layer. [0045] Furthermore, when C is less than 2.7% by mass, there is a large difference in temperature between the crystallization of austenite and the precipitation of eutectic carbide, so that the austenite moves outward by a centrifugal force , which results in the concentration of carbon in the molten mass in an inner part of the outer layer. As a result, large austenite dendrites are generated and grow in the mass in fusion with concentrated carbon. Austenite dendrites are transformed into bainite and / or martensite, which results in large splash-type segregations. In the present invention, the uniformity of the structure is determined by whether or not there are large splash-type segregations that have diameters of 1.5 mm or more. On the other hand, when C exceeds 3.5% by mass, the stranded graphite is precipitated in excess, which results in deteriorated mechanical properties, such as strength. Excessive carbide precipitation gives the outer layer a low hardness and resistance to cracking, which results in deep cracking by rolling, and further damage to the cylinder. The lower limit of the C content is preferably 2.8% by weight, more preferably 2.9% by weight, and even more preferably 3.0% by weight. In addition, the upper limit of the C content is preferably 3.5% by weight, more preferably 3.4% by weight, and even more preferably 3.35% by weight. (b) Si: 1.5-2.5% by mass [0046] Si has the function of deoxidizing the melting mass to reduce oxide defects, and accelerates the formation of graphite, Petition 870180138646, of 10/08/2018, p. 19/58 15/45 contributing to resistance to binding. Less than 1.5% by weight of Si has an insufficient deoxidation function of the melting mass, as well as a poor graphite formation function. On the other hand, more than 2.5% by weight of Si makes the alloy matrix fragile, thereby giving the outer layer a low hardness. The lower limit of the Si content is preferably 1.5% by weight, more preferably 1.6% by weight, and even more preferably 1.8% by weight. The upper limit of the Si content is preferably 2.3% by mass, more preferably 2.2% by mass, and even more preferably 2.2% by mass. (c) Mn: 0.4-1.0% by mass [0047] Mn has the function of deoxidizing the melting mass, and fixes S, an impurity, like MnS. When Mn is less than 0.4% by mass, such effects are insufficient. On the other hand, even if Mn exceeds 1.0% by mass, an additional increase in effects cannot be obtained. The lower limit of the Mn content is preferably 0.5% by weight, more preferably 0.6% by weight, and even more preferably 0.75% by weight. The upper limit of the Mn content is preferably 1.0% by weight, more preferably 0.9% by weight, and even more preferably 0.85% by weight. (d) Ni: 3.7-5.1% by weight [0048] Ni has the function of precipitating graphite, contributing to the resistance to binding. When Ni is less than 3.7% by mass, such effects are insufficient. On the other hand, more than 5.1% by weight of Ni makes austenite too stable, making transformation into bainite or martensite unlikely. The lower limit of the Ni content is preferably 3.9 wt%, more preferably 4.0 wt%, and even more preferably 4.2 wt%. The upper limit of the Ni content is preferably 5.0% by weight, more preferably 4.8% by weight, and even more preferably Petition 870180138646, of 10/08/2018, p. 20/58 16/45 4.4% by mass. (e) Cr: 0.8-2.2% by weight [0049] Cr is an effective element to provide a matrix of bainite or martensite to have a high hardness, thus maintaining resistance to wear. When Cr is less than 0.8% by mass, such effects are insufficient. On the other hand, when Cr exceeds 2.2% by weight, Cr carbides (M7C3, M23C6) are easily formed, resulting in reduced amounts of V-based carbide and Nb-based carbide that contribute to the wear resistance. The lower limit of the Cr content is preferably 0.9% by weight, more preferably 1.0% by weight, and even more preferably 1.1% by weight. The upper limit of the Cr content is preferably 2.0% by weight, more preferably 1.9% by weight, and even more preferably 1.8% by weight. (f) Mo: 1.5-4.5% by weight [0050] Mo is combined with carbon to form hard Mo carbides (MeC, M2C), increasing the hardness of the outer layer, and improving the temperability of the matrix of the league. In addition, Mo increases the specific gravity of an eutectic melting mass remaining in the alloy melting solidification process, thereby preventing centrifugal separation of a γ-phase primary crystal, and suppressing segregation of dendrite-type splash of bainite and / or martensite. Mo is dissolved in MC carbides to form hard MC carbides with V and Nb, thereby improving wear resistance. When Mo is less than 1.5% by mass, such effects are insufficient. On the other hand, when Mo is greater than 4.5% by mass, the outer layer has a poor hardness and a strong white solidification, thereby preventing the precipitation of graphite. The lower limit of the Mo content is preferably 1.7% by weight, more preferably 1.8% by weight, and Petition 870180138646, of 10/08/2018, p. 21/58 17/45 with greater preference of 2.0% by mass. The upper limit of the Mo content is preferably 4.2 wt%, more preferably 4.1 wt%, and even more preferably 3.9 wt%. (g) V: 2.0-4.5% by mass [0051] Ο V is an element combined with carbon to form hard V-based carbides (MC carbides). V-based carbides are carbides in which the largest amount of an element combined with C is V. V-based carbides are not restricted to carbides that contain only V, but may contain elements other than V. V-base have a Vickers HV hardness of 2,500-3,000, the hardest carbide. When V is less than 2.0% by mass, the amount of precipitated MC carbides is insufficient. On the other hand, when V is greater than 4.5% by mass, large MC carbides are formed, which results in a heavy alloy structure, which is likely to cause surface roughness during lamination. The lower limit of the V content is preferably 2.1 wt%, more preferably 2.2 wt%, and most preferably 2.3 wt%. The upper limit of the V content is preferably 4.0% by weight, more preferably 3.5% by weight, and even more preferably 3.0% by weight. (h) Nb: 0.5-2.0% by weight [0052] Nb is combined with carbon to form Nb-based carbides (MC carbides). Nb-based carbides are carbides in which the largest amount of an element combined with C is Nb. Nb-based carbides are not restricted to carbides that contain only Nb, but may contain elements other than Nb. Added together with V and Mo, Nb is dissolved in MC carbides to reinforce, thereby improving the wear resistance of the outer layer. In addition, Nb Petition 870180138646, of 10/08/2018, p. 22/58 18/45 increases the specific gravity of a eutectic melting mass remaining in the melting mass of the alloy, and prevents centrifugal separation of a γ-phase primary crystal, thereby suppressing the segregation of splash-type dendrites. bainite and / or martensite, which are transformed from austenite. Due to the fact that there is a smaller difference in density between Nb-based MC carbides and melting mass than between V-based MC carbides and melting mass, Nb reduces MC carbide segregation in the centrifugally fused outer layer. When Nb is less than 0.5% by mass, these effects are insufficient. On the other hand, more than 2.0% by mass of Nb gives a strong white solidification, preventing the precipitation of graphite, and forming larger MC carbides and accelerating their segregation, thus giving the outer layer a weak resistance to surface roughness. . The lower limit of the Nb content is preferably 0.55% by weight, more preferably 0.6% by weight, and even more preferably 0.65% by weight, in particular 0.7% by weight. pasta. The upper limit of the Nb content is preferably 1.3% by weight, more preferably 0.9% by weight, and even more preferably 0.8% by weight. [0053] Nb / V: 0.18-0.65, Mo / V: 0.7-2.5, and V + 1.2 Nb: 2.7-4.5 [0054] Due to the fact that any one of V, Nb and Mo has a function of increasing the amount of hard MC carbides indispensable for wear resistance, the total amount of these elements must be equal to or greater than a predetermined level. Vanadium is an element that decreases the specific gravity of the melting mass, while niobium and molybdenum are elements that increase the specific gravity of the melting mass. Therefore, without a balance between the amount of V and the amount of Nb and Mo, there must be a big difference in Petition 870180138646, of 10/08/2018, p. 23/58 19/45 specific gravity between the molten mass and austenite, so that austenite moves to the outer layer by a centrifugal force, which results in a marked concentration of carbon. As a result, austenite dendrites are likely to be segregated. [0055] Therefore, it is necessary that a mass ratio of Nb / V is 0.18-0.65, a mass ratio of Mo / V is 0.7-2.5, and V + 1.2 Nb is 2.7-4.5% by weight. With Nb / V, Mo / V and V + 1.2 Nb within these ranges, the appropriate amounts of Nb and Mo are contained in V-based carbides, so that the heavier carbides are dispersed evenly, thereby preventing generation of segregated dendrites of the splash type of bainite and / or martensite. The lower limit of the mass ratio of Nb / V is preferably 0.2, more preferably 0.21, and even more preferably 0.24. The upper limit of the mass ratio of Nb / V is preferably 0.6, more preferably 0.4, and most preferably 0.30. The lower limit of the Mo / V mass ratio is preferably 0.7, more preferably 0.8, and even more preferably 0.9. The upper limit of the Mo / V mass ratio is preferably 2.0, more preferably 1.5, and most preferably 1.4. The lower limit of V + 1.2 Nb is preferably 2.7% by mass, more preferably 2.8% by mass, and even more preferably 2.9% by mass. The upper limit of V + 1.2 Nb is preferably 4.2% by weight, more preferably 4.0% by weight, and even more preferably 3.9% by weight. (2) Optional composition [0056] The outer layer of the centrifugally cast composite cylinder of the present invention preferably fulfills, in addition to the requirements above the essential composition, the following composition requirements depending on the applications. Petition 870180138646, of 10/08/2018, p. 24/58 20/45 (a) W: 0.1-5.0% by weight [0057] W is combined with carbon to form hard ΜδΟ and M2C carbides, contributing to improving the wear resistance of the outer layer. This is also dissolved in MC carbides to increase their specific gravities, which results in reduced segregation. The preferred amount of W is 0.1-5.0% by weight. When W is less than 0.1% by mass, it gives insufficient effects. On the other hand, when W exceeds 5.0% by mass, the melting mass is provided with a greater specific gravity, which probably results in the carbide segregation. The upper limit of the W content is more preferably 4.0% by weight, and even more preferably 2.0% by weight. (b) Ti: 0.01-5.0% by weight [0058] Ti is combined with nitrogen and oxygen, elements that prevent the formation of graphite, to form oxynitrides. Oxy nitrides dispersed in the melting mass form nuclei, providing finer and more uniform MC carbides. The preferred amount of Ti is 0.01-5.0 mass%. When Ti is less than 0.01% by mass, it gives insufficient effects. On the other hand, when the ti exceeds 5.0% by mass, the melting mass has an increased viscosity, probably causing melting defects. Therefore, the Ti content is preferably 0.01-5.0% by weight. The upper limit of the content of ti is more preferably 2.0% by mass, and even more preferably 1.0% by mass. (c) Al: 0.01-2.0% by weight [0059] Al is combined with nitrogen and oxygen, elements that prevent the formation of graphite, to form oxynitrides. The oxynitrides dispersed in the molten mass form nuclei, which results in a uniform precipitation of fine MC carbides. When Al is less than 0.01% by mass, its effects are not expected. Petition 870180138646, of 10/08/2018, p. 25/58 21/45 On the other hand, when Al exceeds 2.0% by mass, the outer layer is fragile. In view of the amounts of N and O contained in the molten mass, more than 2.0 mass% of Al is unnecessary. Therefore, the Al content is preferably 0.01-2.0 wt%. The upper limit of the Al content is more preferably 0.5 wt%, and even more preferably 0.1 % in large scale. (d) Zr: 0.01-0.5% by weight [0060] Zr is combined with carbon to form MC carbides, improving the wear resistance of the outer layer. In addition, a Zr oxide formed in the melting mass works like crystal nuclei, making the solidification structure thin, and increasing the specific gravity of the MC carbides, thus preventing segregation. When the Zr is less than 0.01% by mass, this effect is insufficient. On the other hand, when the Zr exceeds 0.5% by mass, inclusions are formed in an undesirable manner. Therefore, the Zr content is preferably 0.01-0.5% by weight. The upper limit of the Zr content is more preferably 0.3% by mass, and even more preferably 0.1% by mass. (e) B: 0.001-0.5% by weight [0061] B has the function of making carbides thinner, and contributes to the precipitation of graphite when added in a small amount. When B is less than 0.001% by mass, its effects are not sufficient. On the other hand, when B exceeds 0.5% by mass, the carbides are unstable. Therefore, the B content is preferably 0.001-0.5% by weight. The upper limit of the B content is more preferably 0.1% by mass, and even more preferably 0.05% by mass. (f) Co: 0.1-10.0% by weight [0062] Co is an effective element to reinforce the matrix structure. In addition, Co facilitates graphite precipitation. When the Co Petition 870180138646, of 10/08/2018, p. 26/58 22/45 is less than 0.1% by mass, its effects are not expected. On the other hand, when the Co exceeds 10.0% by mass, the outer layer decreased the hardness. Therefore, the Co content is preferably 0.1-10.0% by weight. The upper limit of the Co content is more preferably 5.0% by weight, and even more preferably 2.0% by weight. (g) Mo / Cr: 0.8-5.0 [0063] The mass ratio of Mo / Cr is preferably within a range of 0.8-5.0. When the mass ratio of Mo / Cr is less than 0.8, the Mo content is insufficient in relation to the Cr content, which results in the precipitation of Cr carbide particles such as M7C3, etc.,. As a result, the area ratio of Mo-based carbide particles decreases. On the other hand, when the Mo / Cr mass ratio is 5.0 or more, the Mo-based carbide particles are excessive. Therefore, the mass ratio of Mo / Cr is preferably 0.8-5.0. The lower limit of the mass ratio of Mo / Cr is most preferably 0.9. The upper limit of the Mo / Cr mass ratio is most preferably 4.5, and even more preferably 4.0. (h) Impurities [0064] The remainder in the composition of the outer layer consists substantially of Fe and unavoidable impurities. Among the unavoidable impurities, the amounts of P and S that deteriorate the mechanical properties are preferably as small as possible. Specifically, the P content is preferably 0.1% or less by weight, and the S content is preferably 0.1% or less by weight. Like other unavoidable impurities, the total amount of elements such as Cu, Sb, Te, Se, etc., can be 0.7% or less by weight. (B) Outer layer structure [0065] The outer layer of the composite cylinder centrifugally Petition 870180138646, of 10/08/2018, p. 27/58 The cast of the present invention has a structure comprising 1545% area of a cementite phase and 1-10% area of a graphite phase. It is preferable that the matrix structure of the outer layer is composed substantially of martensite, bainite or perlite. [0066] It is preferable that the area ratio of graphite particles having diameters equivalent to circles of 5 pm or more is 0.99.5%, than the area ratio of the V-based carbide particles having diameters equivalent to 1.5-50 pm circles is 1-20%, and that the total area ratio of Nb-based carbide particles that have diameters equivalent to 1.5-100 pm circles and base of Mo that have diameters equivalent to circles of 1.5-100 pm is 0.3-15%. In addition, it is preferable that the number of V-based carbide particles having diameters equivalent to 1.5-50 pm circles per unit area (1 mm 2 ) of the alloy structure is 50-10,000 / mm 2 , and that the total number of Nb-based carbide particles having diameters equivalent to 1.5-100 pm circles and Mo-based carbide particles having diameters equivalent to 1.5-100 pm circles is 50-10,000 / mm 2 . (1) Cementite: 15-45% in area [0067] Cementite inevitably precipitated when carbides are contained for wear resistance is a relatively soft carbide that has not only the effect of improving binding resistance, but also contributing for the graphite precipitation necessary for the resistance to binding. When the ratio of the cementite area is less than 15%, the effect of improving the resistance to binding is insufficient. On the other hand, when the cementite area ratio exceeds 45% in area, the outer layer has decreased hardness. Cementite is preferably 20-40% in area. [0068] To obtain 15-45% in cementite area, the composition of Petition 870180138646, of 10/08/2018, p. 28/58 24/45 outer layer desirably fulfills the requirement of 1.7% by mass <C - (0.06 Cr + 0.063 Mo + 0.033 W + 0.2 V + 0.13 Nb) <2.7% by mass . When the value of the above formula is less than 1.7% by mass, carbide-forming elements such as Cr, Mo, etc., are excessive in relation to the C content, so that C is consumed by the Cr carbide, Mo carbide, etc., which results in a cementite area ratio of less than 15%. On the other hand, when the value of the formula above is greater than 2.7% by mass, the ratio of the cementite area exceeds 45%. (2) Graphite phase: 1-10% in area [0069] The area ratio of the graphite phase (graphite particle) precipitated in the outer structure of the layer is 1-10%. When the graphite phase is less than 1% in area, the effect of improving the resistance of the outer layer to binding is insufficient. On the other hand, when the graphite phase exceeds 10% in area, the outer layer has significantly decreased the mechanical properties. The area ratio of the graphite phase is preferably 1-7%, and more preferably 1-5%. [0070] To obtain 1-10% in area of the graphite phase, the composition of the outer layer satisfactorily fulfills the requirement of 1.8% by mass <C + Si / 3 + Ni / 18 - [(Mo + W + Nb) / 15 + (cr + V) / 3] <2.8% by weight. When the value of the formula above is less than 1.8% by mass, elements that prevent the formation of graphite such as Mo, W, Nb, Cr and V are excessive in relation to C, Si and Ni, so that the graphite area ratio is less than 1%. On the other hand, when the value of the formula above is greater than 2.8% by mass, the quantities of the elements that prevent the formation of graphite are too small, so that the ratio of the graphite area is greater than 10% . (3) Graphite particles that have diameters equivalent to circles of 5 µm or more: 0.9-9.5% in area Petition 870180138646, of 10/08/2018, p. 29/58 25/45 [0071] Due to the fact that graphite particles having diameters equivalent to circles of 5 pm or more exhibit great lubricating effects, their area ratio is preferably 0.9-9.5% in area. The term circle-equivalent diameter used here refers to an outer diameter expressed by a diameter of a circle that has the same area as that of each graphite particle. When graphite particles having diameters equivalent to circles of 5 pm or more are less than 0.9% in area, the outer layer has insufficient resistance to binding. On the other hand, when graphite particles having diameters equivalent to circles of 5 pm or more are greater than 9.5% in area, the outer layer has insufficient wear resistance. The area ratio of the graphite particles having diameters equivalent to circles of 5 pm or more is most preferably 0.9-6.5%, and even more preferably 0.9-4.5%. (4) V-based carbide particles that have diameters equivalent to 1.5-50 µm circles [0072] V-based carbide particles increase wear resistance. Among them, V-based carbide particles that have diameters equivalent to circles of 1.5 pm or more have a major contribution to improving wear resistance. Carbide particles that have diameters equivalent to circles of less than 1.5 pm are probably detached from the surface of the outer layer, failing to confer a sufficient effect to improve wear resistance. On the other hand, due to the fact that the Bse de V carbide particles are granular, those that have diameters equivalent to circles exceeding 50 pm make the laminated surface rough. [0073] The area ratio of the V-based carbide particles that have diameters equivalent to 1.5-50 pm circles is 1-20%. Petition 870180138646, of 10/08/2018, p. 30/58 26/45 When its area ratio is less than 1%, the outer layer does not have sufficient wear resistance. In addition, coexistence with graphite makes it difficult to have more than 20% in area of V-based carbide particles that have diameters equivalent to 1.5-50 pm circles. The preferred area ratio of the above carbide particles is 2-15%. [0074] The number of V carbide particles having diameters equivalent to 1.5-50 pm circles per unit area (1 mm 2 ) of the alloy structure is preferably 50-10,000 / mm 2 . When the carbide particles above are less than 50 / mm 2 , there are too many openings between the adjacent carbides, so that the relatively soft parts of the matrix between carbides are worn away quickly, probably resulting in surface roughness. On the other hand, when the carbide particles above are greater than 10,000 / mm 2 , the adjacent carbides are likely to be in contact, so that the outer layer has a low roughness. The area ratio of the above carbide particles is preferably 50-5,000 / mm 2 , and more preferably 100-5,000 / mm 2 . (5) Nb-based carbide particles and Mo-based carbide particles both with diameters equivalent to 1.5-100 µm circles [0075] Nb-based carbide particles and N-based carbide particles Mo improve wear resistance. Among them, Nb-based carbide particles that have diameters equivalent to circles of 1.5 pm or more and Mo-based carbide particles that have diameters equivalent to circles of 1.5 pm or more have a major contribution for improved wear resistance. When their diameters equivalent to circles are less than 1.5 pm, they are probably detached from the surface of the outer layer, not giving a sufficient effect of Petition 870180138646, of 10/08/2018, p. 31/58 27/45 improve wear resistance. Due to the fact that the Nb-based carbide particles and the Mo-based carbide particles probably form network structures, their diameters equivalent to circles exceeding 100 pm are likely to roughen the laminated surface. The area of these carbide particles is preferably 0.3-15%. When the ratio of the total area of these carbide particles is less than 0.3%, the outer layer does not have sufficient wear resistance. In addition, the coexistence with graphite makes it difficult to have more than 15% in area of these carbide particles. [0076] The total number of these carbide particles in one unit area (1 mm 2 ) of the alloy structure is preferably 5010,000 / mm 2 . When the total number of these carbide particles is less than 50 / mm 2 , the adjacent carbides are too far apart, and the softer parts of the matrix between the carbides are likely to be worn away, which results in surface roughness. On the other hand, when the total number of these carbide particles exceeds 10,000 / mm 2 , the adjacent carbides are probably in contact, giving the outer layer a reduced hardness. The total number of such carbide particles is preferably 100-10,000 / mm 2 , and more preferably 1005,000 / mm 2 . (6) Other carbides [0077] The outer layer may contain, in addition to the V-based carbide particles, Nb-based carbide particles, Mo and cementite-based carbide particles, M7C3 carbide particles at a ratio 0.2-10% of the area. [0078] Due to the fact that the outer layer of the centrifugally molten composite cylinder of the present invention has the above composition range, and contains V-based carbide particles, Petition 870180138646, of 10/08/2018, p. 32/58 28/45 Nb-based carbide particles and Mo-based carbide particles in the above ranges, it has excellent wear resistance and failure resistance (binding resistance), with little segregation of the splash type of bainite dendrites and / or martensite in it. (C) Inner layer [0079] The inner layer attached to the outer layer above is preferably made of resistant nodular cast iron. The nodular cast iron preferably has a composition comprising, by mass, 3.04.0% C, 1.5-3.0% Si, 0.2-1.0% Mn, 0.1% or less than P, 0.1% or less than S, 0.7-5.0% Ni, 0.1-1.0% Cr, 0.1-1.0% Moe 0.020.08% of Mg, and the remainder consists substantially of Fe and unavoidable impurities. An intermediate layer can exist between the outer layer and the inner layer, for the purposes of suppressing the diffusion of its components, removing the tension between them, etc. (D) Cylinder size [0080] The size of the centrifugally cast composite cylinder of the present invention is not particularly restricted, and its preferred example is that the outer layer has an outer diameter of 2001,300 mm and a cylinder body length of 500- 6,000 mm, and the usable thickness of the outer layer is 50-200 mm. Γ21 Production method of centrifugally cast composite cylinder [0081] The centrifugally cast composite cylinder of the present invention is produced by (a) melting a melt mass that has the above composition for the outer layer into a rotating cylindrical mold for centrifugal casting, and (b) melting a melt to the inner layer in the resulting hollow outer layer during or after solidification of the outer layer. In step (a), the melting temperature of the melting mass for the outer layer is in a range Petition 870180138646, of 10/08/2018, p. 33/58 29/45 of an initial temperature of austenite precipitation + 30Ό to the initial temperature of austenite precipitation + 180Ό, and the centrifugal force of the rotation of the cylindrical mold for the centrifugal casting is in a range of 60-150 G. (A) Formation of the outer layer (1) Melting mass [0082] The melting mass for the outer layer has a chemical composition comprising, by mass, 2.7-3.5% C, 1.52.5 % Si, 0.4-1.0% Mn, 3.7-5.1% Ni, 0.8-2.2% Cr, 1.5-4.5% Mo, 2, 0-4.5% V and 0.5-2.0% Nb, and the rest consists of Fe and unavoidable impurities, a mass ratio of Nb / V that is 0.180.65, and a mass ratio of Mo / V which is 0.7-2.5. (2) Smelting temperature [0083] The melting temperature of the melting mass for the outer layer is in a range from the initial temperature of the austenite precipitation + 30Ό to the initial temperature of the austenite precipitation + 180Ό. The melting temperature within this range can shorten a period of time that the liquid phase remains, suppressing the centrifugal separation of a primary crystal from a γ phase to reduce segregation. When the melt temperature is lower than the initial temperature of austenite precipitation + 30Ό, the melt has a speed of solidification too high, so that foreign matter, such as fine inclusions, is probably solidified before centrifugal separation , which results in defects due to foreign matter. On the other hand, when the melting temperature is higher than the initial temperature of austenite precipitation + 180Ό, splash-like regions (segregation regions) of aggregated coarse dendrites are formed in the outer layer. The melting temperature is preferably the initial temperature of the austenite precipitation + (30Ό to 100Ό), and most preferably at Petition 870180138646, of 10/08/2018, p. 34/58 30/45 initial temperature of austenite + precipitation (80Ό to 100Ό). Incidentally, the initial temperature of the austenite precipitation is an initial temperature of the exothermic solidification measured by a differential thermal analyzer. (3) Centrifugal force [0084] When the outer layer is cast by a centrifugal casting mold, the centrifugal force is in the range of 60150 G by a number of gravity. When fused to the gravity number in this range, the acceleration can be limited at the moment of solidification, which results in a low movement speed of a γ-phase primary crystal, thereby suppressing the centrifugal separation (segregation) of the primary crystal from a γ phase. At a gravity number of less than 60 G, the melting mass of the outer layer is not sufficiently attached to an internal surface of the mold. On the other hand, when the gravity number exceeds 150 G, too much centrifugal separation of the primary crystal from a γ phase occurs, so that the large dendrites are formed in a remaining melting mass with a smaller γ phase. As a result, segregated dendrites of the splash type of bainite and / or martensite are formed in the outer layer. The severity number (G No.) is expressed by the formula of G No. = N χ N x D / 1,790,000, where N is the number of revolutions (rpm) of the mold and D is the inner diameter (mm) of the mold (which corresponds to the outer diameter of the outer layer). (4) Centrifugal casting mold [0085] The centrifugal casting mold is preferably formed of resistant nodular cast iron as thick as 120-450 mm. When the mold is as thin as less than 120 mm, the mold has insufficient cooling capacity, probably resulting in contraction cavities in a part of the outer layer of the surface layer. On the other hand, even if the thickness of the mold Petition 870180138646, of 10/08/2018, p. 35/58 31/45 exceeds 450 mm, its cooling capacity must be saturated. The most preferred thickness of the mold is 150-410 mm. The centrifugal casting mold can be horizontal, inclined or vertical. (5) Coating material [0086] To prevent the layer from adhering to the mold, the inner surface of the mold is preferably coated with a coating material based on silica, alumina, magnesia or zirconia to a thickness of 0.5 -5 mm. When the coating material is thicker than 5 mm, the melt is cooled slowly, so that the liquid phase remains for a longer period of time, which results in more primary crystal centrifugal separation of a γ phase. , and thus more segregations. On the other hand, the coating material thinner than 0.5 mm gives an insufficient effect of preventing the outer layer from adhering to the mold. The most preferred thickness of the coating material is 0.5-3 mm. (6) Inoculant [0087] To adjust the amount of precipitated graphite, an inoculant such as Fe-Si, Ca-Si, etc., can be added to the melt. In this case, the composition of the melting mass is determined, taking into account the change in composition by adding the inoculant. (7) Formation of the intermediate layer and the inner layer [0088] During or after solidification of the outer layer, a melting mass for an intermediate layer can be melted on an inner surface of the outer layer. After the intermediate layer is formed, the mold containing the outer layer and the intermediate layer is assembled, and provided at its upper and lower ends with an upper mold and a lower mold to constitute a stationary casting mold, in which a mass melting to the inner layer is fused. Due to the fact that the layer Petition 870180138646, of 10/08/2018, p. 36/58 32/45 inner is solidified after the inner surface of the outer layer (or intermediate layer) is remelted, they are metallurgically bonded. (8) Heat treatment [0089] Due to the fact that the outer layer containing 3.7-5.1 wt% Ni has a good hardenability, it does not need to be hardened after casting. However, to decompose the remaining austenite and to remove tension, the resulting composite cylinder is preferably subjected to heat treatment at 550 tratamento or less. After heat treatment, the composite cylinder is preferably cooled at a rate of less than 10000 / hour. [0090] The present invention will be explained in more detail by the following examples, with no intention of restricting the present invention to them. EXAMPLES 1-8 AND COMPARATIVE EXAMPLES 1-4 [0091] Each melting mass having the composition (% by mass) shown in Table 1 was cast in a high speed rotating cylindrical mold made of nodular cast iron having a diameter internal diameter of 400 mm, a length of 1,500 mm and a thickness of 276 mm, which was coated on its internal surface with a 3 mm thick zirconia-based coating material, to form an external layer by centrifugal casting. The melting temperature of the melt was between the initial temperature of the austenite precipitation + 80Ό and the initial temperature of the austenite precipitation + 100Ό. The gravity number on an outer surface of the layer was 120 G. The resulting outer layer had an average thickness of 96 mm. [0092] After the hollow outer layer was solidified, the rotation of the centrifugal casting mold was stopped, and an upper mold and a lower mold were arranged at the upper and lower ends Petition 870180138646, of 10/08/2018, p. 37/58 33/45 of the centrifugal casting mold to form a stationary casting mold. A melting mass of nodular cast iron for an inner layer was poured over the outer layer, so that the outer layer and the inner layer were metallurgically bonded. After the solidification of the inner layer was completed, the mold was disassembled to remove a cylinder, which was annealed at 500Ό. Table 2 shows the amount of carbon remaining Cbai = C - (0.06 Cr + 0.063 Mo + 0.033 W + 0.2 V + 0.13 Nb), the amount of graphitized carbon AA = C + Si / 3 + Ni / 18 - [(Mo + W + Nb) / 15 + (Cr + V) / 3], Mo / Cr, Nb / V, and Mo / V in each outer layer. TABLE 1-1 No. Outer Layer Composition (% by mass) Ç Si Mn Ni Cr Mo V Nb Example 1 2.90 1.80 0.80 4.30 1.00 3.90 3.00 0.75 Example 2 3.30 2.20 0.80 4.18 1.10 2.90 3.00 0.70 Example 3 3.30 1.88 0.80 4.25 1.75 2.80 2.50 0.50 Example 4 3.35 1.75 0.80 4.25 1.80 1.70 2.20 0.50 Example 5 3.35 1.75 0.71 4.42 1.81 1.72 2.20 0.51 Example 6 3.30 1.85 0.79 4.25 1.75 2.80 2.52 0.52 Example 7 3.21 2.05 0.59 4.17 2.17 3.61 2.11 1.20 Example 8 3.30 2.21 0.48 4.25 1.15 2.90 3.00 0.80 Ex.Compar. 1 2.20 2.10 0.68 4.11 2.32 3.35 2.81 1.40 Ex.Compar. 2 3.24 1.30 0.80 4.30 1.52 0.41 0.50 - Ex.Compar. 3 1.92 0.58 0.58 3.66 2.44 5.21 3.47 0.35 Ex.Compar. 4 2.50 1.61 0.58 3.76 1.52 3.51 9.18 0.34 Petition 870180138646, of 10/08/2018, p. 38/58 34/45 TABLE 1-2 No. Outer Layer Composition (% by mass) W You Al Zr B Co Example 1 1.00 - - - - - Example 2 1.00 - - Example 3- - Example 4- - Example 5-0.01 -0.01 Example 6-0.02 - Example 7- - Example 8- - Ex. Compar. 1 1.12 -0.01 -0.01 Ex. Compar. 2 - - - Ex. Compar. 3 0.50 -0.01 - Ex. Compar. 4 1.82 0.01 - TABLE 2 No. Outer Layer Composition (% by mass) Nb / V Mo / V Mo / Cr V +1.2 Nb ChalC) AA (2) Example 1 0.25 1.30 3.90 3.90 1.86 2.03 Example 2 0.23 0.97 2.64 3.84 2.33 2.59 Example 3 0.20 1.12 1.60 3.10 2.45 2.53 Example 4 0.23 0.77 0.94 2.80 2.63 2.69 Example 5 0.23 0.78 0.95 2.81 2.63 2.69 Example 6 0.21 1.11 1.60 3.14 2.45 2.51 Example 7 0.57 1.71 1.66 3.55 2.27 2.38 Example 8 0.27 0.97 2.52 3.96 2.34 2.64 Ex. Compar. 1 0.50 1.19 1.44 4.49 1.07 1.03 Ex. Compar. 2 0.00 0.82 0.27 0.5 3.02 3.21 Ex. Compar. 3 0.10 1.50 2.14 3.89 0.69 -0.06 Ex. Compar. 4 0.04 0.38 2.31 9.58 0.25 -0.70 Grades: (1) Cbai = C - (0.06 Cr + 0.063 Mo + 0.033 W + 0.2 V + 0.13 Nb). Petition 870180138646, of 10/08/2018, p. 39/58 35/45 (2) ΑΑ = C + Si / 3 + Ni / 18 - [(Mo + W + Nb) / 15 + (Cr + V) / 3]. [0093] With respect to a specimen cut from each outer layer of the Examples and Comparative Examples, an optical photomicrograph and a BSE photograph were taken by the following procedure. [0094] Step 1: Each specimen was polished on the mirror in such a way that the carbides did not protrude from the surface. [0095] Step 2: An optical photomicrograph A of each structure of the specimen was taken. [0096] Step 3: A B photograph of a BSE image (electronic backscattered image of a scanning electronic photomicrograph) of each specimen was taken in the same field as that of the photograph in step 2. [0097] Step 4: Each specimen was etched electrolytically with an aqueous chromic acid solution for about 1 minute, and then polished using a 3 μπι diamond paste for 30-60 seconds. [0098] Step 5: An optical photomicrograph C of each structure of the specimen was taken in the same field as that of the photograph in step 2. [0099] Step 6: Each specimen was etched with an aqueous ammonium persulfate solution for about 1 minute. [00100] Step 7: An optical D photomicrograph of each structure of the specimen was taken in the same field as that of the photograph in step 2. [00101] Step 8: Each specimen was heated to 50-70Ό, and then etched by a Murakami reagent for about 1 minute. [00102] Step 9: An optical photomicrograph E of each structure of the specimen was taken in the same field as that of the photograph in step 2. Petition 870180138646, of 10/08/2018, p. 40/58 36/45 [00103] With respect to the sample of Example 1, its optical photomicrograph A is shown in Fig. 3, its optical photomicrograph B is shown in Fig. 4, its optical photomicrograph C is shown in Fig. 5, its optical photomicrograph D is shown in Fig. 6 and its optical photomicrograph E is shown in Fig. 7. The measurable structural elements of the AE photographs are shown by Yes in Table 3. TABLE 3 Photographic Graphite Particles V-based Carbide Particles Nb-based Carbide Particles Mo-based Carbide Particles Heartwood THE Yes - - - - B - - Yes Yes - Ç Yes Yes Yes - - D - - - Yes Yes AND - - - - Yes [00104] When using image analysis software, the area ratios and numbers of cementite, graphite particles and carbide particles were determined from these photographs by the following methods. The results are shown in Table 4. [00105] (1) Due to the fact that the black parts represent graphite particles in optical photomicrography A, the ratio of the area of graphite particles (the ratio of the area of all graphite particles and the ratio of the area of graphite particles that have diameters equivalent to circles of 5 pm or more) was determined from photograph A. [00106] (2) Due to the fact that the white parts represent cementite in optical photomicrography E, the ratio of the cementite area was determined from photograph E. [00107] (3) Due to the fact that the white parts represent particles of carbide based on Mo and cementite in photomicrography Petition 870180138646, of 10/08/2018, p. 41/58 37/45 optics D, the area ratio of the Mo-based carbide particles with diameters equivalent to a circle of 1.5-100 pm and their numbers by a unit area was determined from photographs D and E. [00108] (4) Due to the fact that the black parts represent graphite particles, V-based carbide particles and Nb-based carbide particles in optical D photomicrography, the area ratio of the V-based carbide particles that have diameters equivalent to circles of 1.5-50 pm and their numbers per unit area was determined by subtracting the area ratio of the graphite particles determined in step (1) and the area ratio of the carbide particles to the base of Nb that have diameters equivalent to circles of 1.5- 100 pm and their numbers by an area unit determined in step (4) from the ratio of the area of graphite particles + V-based carbide particles that have diameters equivalent to circles of 1.5- 50 pm + Nb-based carbide particles that have diameters equivalent to 1.5-100 pm circles and their numbers by a unit area determined from photograph D. [00133] When using each melting mass for an outer layer in the Examples and in the Comparative Examples, a test cylinder was produced that has a sleeve structure of 60 mm in the outer diameter, 40 mm in the inner diameter and 40 mm in the width. To assess wear resistance, a wear test was performed on each test cylinder by a rolling wear test machine shown in Fig. 1. The rolling wear test machine comprises a rolling machine 1, the rollers test pieces 2, 3 mounted on the laminating machine 1, an oven 4 to preheat a plate 8 to be laminated, a cooling water bath 5 to cool the laminated plate 8, a winding coil 6 to provide a tension during lamination, and a controller 7 to adjust the tension. Lamination wear conditions are shown below. Petition 870180138646, of 10/08/2018, p. 42/58 38/45 follow. After rolling, the depth of wear generated on the test cylinder surfaces was measured by a stylus surface roughness meter. The results are shown in Table 4. [00134] Sheet to be laminated: SUS304, [00135] Lamination reduction: 25%, [00136] Lamination speed: 150m / min, [00137] Temperature of the sheet to be laminated: 900Ό , [00138] Lamination distance: 300 m / cycle, [00139] Cylinder cooling: Water cooling, and [00140] Number of cylinders: 4. [00141] To assess the resistance to failure, a jam test was performed on each test cylinder by a frictional heat shock testing machine shown in Fig. 2. The frictional heat shock testing machine comprises a rack 11 wherein a weight 12 is dropped to rotate a pinion 13, so that a cutting member 15 is placed in intense contact with a specimen 14. The binding has been assessed by the following standard. The results are shown in Table 4. The lower the jam, the better the failure resistance. [00142] Good: No jamming, [00143] Reasonable: Slight jamming, and [00144] Poor: Extreme jamming. [00145] 10 mm, 30 mm and 50 mm planes, respectively, in the depth of an external surface of each external layer of the Examples and the Comparative Examples were polished on the mirror, and etched with an aqueous ammonium persulfate solution for about 1 minute, and their structures were photographed at 5-10 times magnification. In each structure photographed, the secreted dendrites of the splash type of bainite and / or martensite that have diameters Petition 870180138646, of 10/08/2018, p. 43/58 39/45 of 1.5 mm or more inside the outer layer (in a layer usable in lamination) were observed to evaluate the homogeneity of the structure by the standard below. The results are shown in Table 4. [00146] Good: There were no splash-type segregations with diameters of 1.5 mm or more, and [00147] Poor: There were splash-type segregations with diameters of 1.5 mm or more. Petition 870180138646, of 10/08/2018, p. 44/58 40/45 Outer Layer Structure Nb-based Carbide (2) + Mo-based Carbide (3) Number (/ mm 2 ) 983 894 634 548 725 707 00 CD CD 755 821 O 259 427 Area Reason(%) 3.41 3.24 1.32 0.82 0.75 1.27 6.38 3.56 6.10 0.12 3.20 4.27 V-based Carbide (1) o <z 1771 1964 1872 1203 CD 1727 627 1602 1721 107 2248 1974 Area Ratio (%) 2.63 2.38 2.78 1.57 1.65 2.87 1.52 3.02 2.27 0.32 4.21 21.20 Graphite Area Ratio(%) 2ANDΞ2. bad 1.54 4.28 4.67 5.36 5.56 4.61 4.32 4.71 <0.05 4.42 <0.05 <0.05 Total 1.73 4.41 CO 5.42 5.66 4.72 4.43 4.82 <0.05 4.52 <0.05 <0.05 Cementite Area Reason(%) 25.2 28.3 30.1 32.4 32.1 30.5 27.3 25.3 18.6 36.2 O O The Z the Q. ELU Example 2 Example 3 the Q. ELU Example 5 CD O Q. ELU o o. ANDLU 00 the Q. ELU Ex. Compar. 1 Ex. Compar. 2 Ex. Compar. 3 Ex. Compar. 4 Petition 870180138646, of 10/08/2018, p. 45/58 41/45 TABLE 4-2 No. Outer Layer Structure Wear (pm) Then they get stuck Structure Homogeneity (5) Example 1 15 Good Good Example 2 19 Good Good Example 3 20 Good Good Example 4 23 Good Good Example 5 24 Good Good Example 6 21 Good Good Example 7 23 Good Good Example 8 15 Good Good Ex. Compar. 1 17 Reasonable Poor Ex. Compar. 2 38 Good Poor Ex. Compar. 3 17 Weak Poor Ex. Compar. 4 11 Weak Poor note: [00148] (5) Determined by the presence of segregated dendrites of the splash type that have diameters of 1.5 mm or more at a depth of 10 mm, 30 mm and 50 mm, respectively. [00149] In any of the examples, the outer layer did not contain segregated dendrites of the splash type of bainite and / or martensite, with an excellent homogeneity in the structure as well as an excellent resistance to wear and resistance to binding (resistance to failures). On the other hand, the outer layers of the Comparative Examples contained segregated dendrites of the splash type of bainite and / or martensite, and were poor in any of the wear resistance and resistance to binding. EXAMPLE 9, AND COMPARATIVE EXAMPLE 5 [00150] A molten mass that has the composition (% by mass) shown in Table 5 was cast in a high-speed cylindrical mold made of nodular cast iron that has a Petition 870180138646, of 10/08/2018, p. 46/58 42/45 inner diameter of 400 mm, a length of 1,500 mm and a thickness of 276 mm, which was coated on its inner surface with a coating material based on zirconia 2.5 mm thick, to form an outer layer by centrifugal casting under the conditions shown in Table 6. The initial temperature of the austenite precipitation from the outer layer was 1,216Ό. The gravity number on an outer surface of the outer layer was 120 G. The resulting outer layer had an average thickness of 96 mm. TABLE 5 Melting mass composition for the outer layer (% by mass) Ç Si Mn Ni Cr Mo V Nb Al 3.15 1.76 0.59 3.80 1.25 2.35 2.80 0.53 0.03 TABLE 6 No. Oven Leak Temperature (C) Foundry Temperature (C) Severity Number (G) Example 9 1,440 1,276 120 Ex. Compar. 5 1,460 1,242 120 [00151] After the hollow outer layer was solidified, the rotation of the centrifugal casting mold was stopped, and a melting mass of nodular cast iron to an inner layer was poured over the outer layer in the same way as in Example 1 to bond metallurgically the inner layer to the outer layer. After the solidification of the inner layer was completed, the mold was disassembled to extract a cylinder, which was annealed at 500Ό. [00152] The data of the structure of the outer layer (the ratio of the cementite area, all graphite particles and graphite particles that have diameters equivalent to circles of 5 pm or more, the area ratio and the number of carbide particles based on V that have diameters equivalent to 1.5-50 pm circles, and the ratio of the total area and the number Petition 870180138646, of 10/08/2018, p. 47/58 43/45 of Nb-based carbide particles that have diameters equivalent to 1.5-100 pm circles and Mo-based carbide particles that have diameters equivalent to 1.5-100 pm circles) measured in the same way which in Example 1 are shown in Table 7. In addition, the homogeneity of the structure (presence or absence of segregated dendrites of the splash type of bainite and / or martensite) measured and evaluated at a depth of 50 mm from the surface of the outer layer in the same way as in Example 1 is shown in Table 7. Petition 870180138646, of 10/08/2018, p. 48/58 44/45 Homogeneity ofStructure Good Poor Nb-based Carbide (2) + Mo-based Carbide (3) 2 Λê | o Έ z 869 631 Area Ratio (%) 00 co 1.41 V-based Carbide (1 ) 2 Λê | ο Έ z 1827 1216 Area Ratio (%) 3.2 3.4 Area ReasonGraphite (%) 2ANDΞ2. bad 3.7 3.1 Total 3.8 3.2 Cementite Area Reason(%) 28 39 oN Example 9 Ex. Compar. 5 È Ξ2. ANDΞ2.OO O τ- m1 ι m in T- ~Φ φ Ό Ό CO Φ O O Z3O O l—O O ro ro co ω φ φ ç ç Φ Φ ro ro> >'= 3 '= 3 D D Φ Φ CO CO P O »Φ Φ AND AND <ro <ro AND AND <φ <φ Φ Φ Z3 Z3 D D _Q > Z Φ Φ Ό Ό Φ Φ CO CO ro ro .ω .ω 'TO 'TO O O φ φ ç ç O O -Q -Q ro ro O O φ φ Ό Ό CO CO ro ro Z3 Z3 O Ot ro ro □ _ Q_ s AND Ξ2. O O I LD φ Ό CO O coro O AND O Z3 O roco AND φ Ξ2. ç m Φ φ ro Ό > co '= 3 O DΦ O COO O Φ ro AND co φ <ro çΦ AND ro <φ >'= 3 Φ D Z3 Φ D CO O P»Φ Φ AND Ό <ro Φ COro _q E <φ 'TOO ΦZ3 Φ D c o ro -Q you- s_ ro ro 1Z O σ> φ φ Ό Ό co co ro ro Z3 Z3 O O t t ro ro Q_ □ _ s Petition 870180138646, of 10/08/2018, p. 49/58 45/45 EFFECT OF THE INVENTION [00153] Due to the fact that the centrifugally cast composite cylinder of the present invention comprises an outer layer that has excellent wear resistance and failure resistance (resistance to deep cracks in rolling problems such as rolling of folded back ends , etc.), with few segregated dendrites of the splash type of bainite and / or martensite (which has a homogeneous structure), has an excellent durability with little surface roughness. It is therefore suitable as a working cylinder used in rolling cages downstream in finishing laminating lines for hot strip laminators, which require particularly smooth rolling surfaces.
权利要求:
Claims (8) [1] 1. Cast centrifugal composite cylinder, characterized by the fact that it comprises an outer layer made of cast iron that has a chemical composition that consists of, by weight, 2.73.5% of C, 1.5-2.5 % Si, 0.4-1.0% Mn, 3.7-5.1% Ni, 0.8-2.2% Cr, 1.5-4.5% Mo, 2, 0-4.5% V and 0.5-2.0% Nb, optionally further comprising, by weight, at least one selected from the group consisting of 0.1-5.0% W, 0.01 -5.0% Ti, 0.01-2.0% Al, 0.01-0.5% Zr, 0.001-0.5% B and 0.1-10.0% Co, the rest being Fe and unavoidable impurities, a mass ratio of Nb / V being 0.18-0.65, a mass ratio of Mo / V being 0.7-2.5, and V + 1.2 Nb being 2.7-4.5% by weight, and a structure comprising, in area, 15-45% of a cementite phase and 1-10% of a graphite phase, and an internal layer made of iron cast that has excellent mechanical strength and is metallurgically bonded to said outer layer; a usable region of said outer layer as deep as 10 mm or more from the surface that does not contain segregated dendrites of the splash type of bainite and / or martensite having diameters of 1.5 mm or more. [2] 2. Centrifugally cast composite cylinder according to claim 1, characterized in that said outer layer structure comprises 0.9-9.5% in area of graphite particles that have diameters equivalent to circles of 5 pm or more , 1-20% by area of V-based carbide particles that have diameters equivalent to 1.5-50 pm circles, and 0.3-15% by area of the total Nb-based carbide particles that have diameters diameters equivalent to 1.5-100 pm circles and Mo-based carbide particles having diameters equivalent to 1.5-100 pm circles; the number of said V-based carbide particles being 50-10,000 / mm 2 , and the total number of said Nb-based carbide particles and said Petition 870180138646, of 10/08/2018, p. 51/58 2/3 Mo-based carbide particles being 50-10,000 / mm 2 . [3] 3. Centrifugally cast composite cylinder according to claim 1 or 2, characterized by the fact that the chemical composition of said outer layer satisfies the conditions of 1.7% <C (0.06 Cr + 0.063 Mo + 0.033 W + 0 , 2 V + 0.13 Nb) <2.7%, and 1.8% <C + Si / 3 + Ni / 18 - [(Mo + W + Nb) / 15 + (Cr + V) / 3] <2.8% by mass, a mass ratio of Mo / Cr being 0.8-5.0. [4] 4. Centrifugally cast composite cylinder according to any one of claims 1 to 3, characterized in that said outer layer has a chemical composition comprising 2.8-3.5% C, 1.5-2.3 % Si, 0.5-1.0% Mn, 3.9-5.0% Ni, 0.9-1.9% Cr, 1.7-4.2% Mo, 2, 0-4.0% V and 0.5-1.3% Nb, the remainder being Fe and unavoidable impurities, a mass ratio of Nb / V being 0.2-0.6, and a ratio in mass of Mo / V being 0.7-2.0. [5] A centrifugally cast composite cylinder according to any one of claims 1 to 4, characterized in that said inner layer is made of nodular cast iron. [6] 6. Method for the production of the centrifugally molten composite cylinder as defined in any one of claims 1 to 5, characterized in that it comprises the melting of a melt mass for said outer layer which has a chemical composition consisting of, in mass, 2.7-3.5% C, 1.5-2.5% Si, 0.4-1.0% Mn, 3.7-5.1% Ni, 0.8-2.2% Cr, 1.54.5% of Mo, 2.0-4.5% of V and 0.5-2.0% of Nb, optionally also comprising, by weight, at least one selected from the group consisting of 0.1-5.0% of W, 0.01-5.0% Ti, 0.01-2.0% Al, 0.01-0.5% Zr, 0.001-0.5% B and 0.1-10, 0% Co, the rest being Fe and unavoidable impurities, a mass ratio of Nb / V being 0.18-0.65, a mass ratio of Mo / V being 0.7-2.5, and V + 1.2 Petition 870180138646, of 10/08/2018, p. 52/58 3/3 Nb being 2.7-4.5% by weight, in a centrifugal casting mold at a temperature in the range of its initial temperature of austenite precipitation + 30Ό to its initial temperature of austenite precipitation + 180 +, and the formation of said outer layer under a centrifugal force that has a number of gravity in a range of 60-150 G. [7] Method for the production of a centrifugally cast composite cylinder according to claim 6, characterized in that said centrifugal casting mold is formed by nodular cast iron having a thickness of 120-450 mm. [8] 8. Method for the production of a centrifugally molten composite cylinder according to claim 6 or 7, characterized in that said centrifugal casting mold is coated on its internal surface with a coating material comprising mainly silica, alumina , magnesia or zirconia to a thickness of 0.5-5 mm, to centrifugally mold said outer layer.
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同族专利:
公开号 | 公开日 EP2706128A1|2014-03-12| RU2610645C2|2017-02-14| US9221232B2|2015-12-29| BR112014012076A2|2017-06-13| ES2562625T3|2016-03-07| SI2706128T1|2016-04-29| EP2706128B1|2016-02-03| MX357864B|2018-07-25| RU2014125286A|2015-12-27| CN103946408B|2016-08-24| EP2706128A4|2014-07-02| MX2014006101A|2014-06-23| US20140248511A1|2014-09-04| KR101471502B1|2014-12-10| BR112014012076A8|2017-06-20| WO2013077377A1|2013-05-30| JPWO2013077377A1|2015-04-27| CN103946408A|2014-07-23| JP5423930B2|2014-02-19| KR20140032504A|2014-03-14|
引用文献:
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法律状态:
2018-07-10| B07A| Technical examination (opinion): publication of technical examination (opinion)| 2018-11-27| B09A| Decision: intention to grant| 2018-12-26| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |
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申请号 | 申请日 | 专利标题 JP2011253588|2011-11-21| JP2011-253588|2011-11-21| PCT/JP2012/080231|WO2013077377A1|2011-11-21|2012-11-21|Centrifugally cast composite rolling mill roll and manufacturing method therefor| 相关专利
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