TWI302949B - - Google Patents

Description

1302949 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a tool for hot working, and more particularly to a tool for hot working used in a step of hot working of a metal. [Prior Art] In the step of processing the representative metal of the steel material with heat, the tool for hot working is used for Φ. The tool for hot working is, for example, a skew roll or a guide block or a disc roll or a plug used in a piercing mill for manufacturing a jointless pipe. The guide blocks used in the hot rolling step of steel sheets or sections or strips are also tools for hot working. Since these tools for hot working come into contact with or collide with the material to be processed from 1273K to 1523K, they are subjected to a high load from the material to be processed. Therefore, the surface of the tool for hot working is liable to be worn or sintered, and sometimes cracks or cracks are formed on the surface. For example, the φ plug installed in the piercing mill is used to press the broken core of the high temperature, which is the high temperature of the material to be rolled, to open the hole. At this time, the surface of the plug is subjected to a sliding friction from the round steel. This sliding friction causes the surface of the plug to be biased to wear or burn. When the surface of the hot working tool is excessively worn or burnt on the surface, the hot working tool is replaced. As a result, wear or sintering of the surface shortens the service life of the tool for hot working, and therefore it is important to measure the wear resistance of the tool for hot working and the countermeasure against sintering. In recent years, anti-wear measures and anti-sintering measures, for example, have been opened in Japan -5- (2) (2)

1302949, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The surface of the processing tool is coated with a coating (PTA surfacing 丨. PTA surfacing coating is a so-called Co-based or Fe-based bonding: hard particles containing so-called WC or NbC, these hard particles enhance the wear resistance of the coating Damage resistance and sinter resistance. Therefore, compared with the high C-high Cr steel or SKD equivalent steel used in previous thermal tools, the service life of the hot working tool with PTA surfacing coating is improved. However, hot working The service life of the tool is necessary. Therefore, the longer the service life, the frequency of replacement of the tool for hot working. Therefore, it is possible to improve the productivity in order to replace the stop time of the processing device or the like. The tool for hot working is replaced by the work of the factory. Therefore, it is better to consider the frequency of the work load to be changed. If the use of the tool for hot working is to be improved, it is necessary to improve the wear resistance. [Problem to be Solved by the Invention] An object of the present invention is to provide a tool for superior wear resistance. [Means for Solving the Problems and Effects of the Invention] The present inventors have hard particles in a bonded metal. Kaizhao technology: PTA layer) can work in the genus, with 0 innings. The less the less, the more the layer is added, the -6 - (3) 1302949 mechanism is the metallization layer and the strength of the particles being processed, and the bonding of the gold metal from the pre-crushing damage caused by the bonding. Adhesive wear is cracked or missing until the hard part of the wear mechanism is investigated. The investigation results found that the abrasion of the coating was formed by two steps. Referring to Figure 1 (a), the coating is composed of hard particles and sticky. Some of the hard particles are exposed on the surface of the coating. When the coated material is in contact, the exposed hard particles and the bonding metal contact the material to withstand the load from the material to be processed. Bonded metals, because they are harder than hard particles, are more likely to wear than bonded metals. The more the bonded metal wears, the more the load on the processed material will be increased by the hard particles. This is because the bonded metal will wear and the metal will not come into contact with the material to be processed. When the hard particles are subjected to the load of the material to be processed beyond the specified range, the hard particles are destroyed. As shown in Fig. 1(b), when hard particles are received, the contact area between the hard particles and the bonding metal becomes small. Therefore, the binding force to the hard particles is reduced, and the hard particles will stick. This is the first step. After the hard particles are detached, the bonding metal will bond with the material to be processed because the strength and hardness are lower than that of the hard particles, so that it is contained. In addition, the bonded metal is impacted by the material to be processed and is easily muzzle. Therefore, as shown in Fig. 1(C), the coating will continue to wear until the particles are exposed. This is the second step. The first step and the second repeat will continue the wear of the coating. Based on the above findings, the inventors believe that if the hard particles are prevented from falling off in the first step, the bonding metal is soft and effective. In other words, the bonded metal needs to have high toughness and high ductility. Hard particles exposed on the surface, (4) 1302949 is in contact with or impacted by the material to be processed and subjected to high loads. If the toughness and ductility of the bonded metal are low, the bonded metal cannot absorb the load on the hard particles. Therefore, the hard particles are destroyed. If the toughness and ductility of the bonded metal are high, the bonded metal can absorb the load on the hard particles. This is because the bonded metal can be plastically deformed or elastically deformed when the hard particles are subjected to a load. Therefore, the hard particles are not damaged and become difficult to fall off from the bonded metal. In addition, if the toughness of the bonded metal is superior, even if the hard particles are damaged, the bonded metal can restrain the hard particles that have been destroyed. In addition, if the toughness of the bonded metal is superior, the bonded metal around the broken hard particles is deformed, thereby restraining the hard particles. Therefore, the shedding of the hard particles can be suppressed. By suppressing the detachment of the hard particles, it is possible to suppress the abrasion of the coating by the presence of hard particles. Further, the inventors of the present invention thought that it is necessary to improve wear resistance and impact resistance in order to suppress the wear of the bonded metal in the second step. Specifically, it is necessary to increase the strength and hardness of the bonded metal. The present inventors believe that if the strength of the bonding metal is to be increased and the toughness and ductility of the bonding metal are increased, it is preferable that the bonding metal is not reinforced by the solidification of the bonding metal. This is because the solid-melt strengthening can increase the strength of the bonded metal, but the ductility and toughness decrease as the strength increases. In contrast, the dispersion strengthening can maintain the original ductility and toughness of the bonded metal. The fine particles dispersed in the bonded metal can also increase the strength. As a result of the above review, the inventors of the present invention have thought that as shown in Fig. 2, the -8-(5) 1302949 bonded metal contains fine hard particles which contribute to the degree of dispersion strengthening. In order to disperse and strengthen the bonded metal, it is more effective to use a hard particle having a particle size of 20 // m or less as a fine hard particle contained in the bonded metal. In order to achieve this effect, the volume fraction of the fine hard particles in the coating layer needs to be at least 5% or more. On the other hand, the "excessive fine hard particles contained in the right" cannot maintain the ductility and toughness of the bonded metal. When the volume fraction of the fine hard particles exceeds 30%, the ductility and toughness of the bonded metal are remarkably lowered. Therefore, the volume ratio of the fine hard particles contained in the coating of the tool for hot working of the present invention is 5% to 30%. Further, in order to improve the abrasion resistance and the seizure resistance, coarse hard particles are required. When the wear resistance and the sinter resistance are taken into consideration, it is more effective to use a hard particle having a particle diameter of 50 // m as a coarse hard particle in the bonded metal. Further, when the wear resistance is taken into consideration, the volume ratio of the coarse hard particles in the coating layer needs to be 20% or more. On the other hand, if the coarse hard particles are excessively added, the toughness of the coating layer is lowered, and when the volume ratio of the coarse hard particles exceeds 60%, the toughness is remarkably lowered. Therefore, the volume ratio of the coarse hard particles contained in the coating of the tool for hot working of the present invention is 20% to 60%. In addition, the total volume fraction of hard particles in the coating has a significant effect on the service life of the coating. As described above, in order to improve the service life of the coating, the fine hard particles in the coating should be 5% or more, and the volume ratio of the coarse hard particles should be 20% or more. That is, the total volume fraction of hard particles in the coating needs to be at least 25 % or more. On the other hand, if the total amount of hard particles in the coating is excessive, the toughness is lowered, resulting in frequent occurrence of abrasion and surface defects. When the total volume fraction of hard particles exceeds 70%, the toughness is remarkably lowered. Therefore, the total volume fraction of hard particles in the coating of -9 - (6) 1302949 must be 2 5 % ~ 7 〇 %. Further, the inventors of the present invention thought that it is possible to suppress the abrasion of the coating layer by using the precipitation to form the coating layer with the fine hard particles when the coating is formed on the hot working tool. When the coating is formed by a powder metallurgy method such as hot melt spraying or HIP treatment, it is a fine hard particle containing 2 Å/m or less in the raw material of the coating. In these methods, the fine hard particles of the raw material are contained in the coating as they are. On the other hand, when a coating is formed by a welding method such as a PTA method, an MIG welding method, or a TIG welding method, the hard particles are first melted, and then the fine hard particles can be precipitated. Since the interface between the fine hard particles and the binder metal is high, the precipitation of the fine hard particles can improve the mechanical properties such as strength, toughness, and ductility of the bonded metal. Therefore, it is possible to further suppress the wear of the coating. Based on the above knowledge, the inventors completed the following invention. The tool for hot working of the present invention has a coating on the surface, and the coating layer contains a transition metal or a transition metal-based alloy, that is, a bonding metal; and a hard particle having a volume ratio of 25% to 70% in the coating layer. . The hard particles have a volume fraction of 5% to 30% in the coating layer and a fine hard particle having a particle diameter of 20//m or less; and the volume fraction in the coating layer is 20% to 60%, and the particle diameter is 20% to 60%. It is a coarse hard particle of 50 / zm or more. Here, the alloy mainly composed of a transition metal is, for example, an alloy containing 50% or more of a transition metal in mass%. The particle size and volume fraction in the coating layer can be calculated by the following method. From the cladding profile of the surface of the hot working tool, a plurality of region ranges are selected. At this time, the total area of the selected area is larger than 3 mm x 3 mm. Using an optical microscope or a sweeping cat -10- (7) (7)

1302949 Electron microscopy (SEM), particle size and area ratio were determined for selected area range particles. The length of each hard particle was measured (long diameter + short diameter) / 2 = particle diameter. The measurement of each hard area ratio is, for example, image analysis. Based on the measured particle size and area ratio, the following is proved: the volume ratio of a phase is equal to the surface of the profile. Refer to the Japanese Society of Metals Society Vo 1.1, No. 5, 279, and therefore, particle size 5 0 # The area ratio of hard particles above m is larger than the volume of hard particles. Further, the particle size of 2 0 // m is the total area ratio of the sub-particles, and the volume 微 is the volume of the fine hard particles. The area ratio of the hard particles in the whole portion is a large solid hard particle of the hard particles, and it is preferable to form at least one of the carbides, oxides, and nutrients, and a mixture of these and a composite compound of these. The bonding metal is preferably one selected from the group consisting of a Co-based alloy and a Ni-based alloy; The coating is preferably formed by a welding method. Here, the fingerprint method, the MIG welding method, the TIG welding method, and the like are used. The fine hard particles are preferably precipitates. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the preferred embodiment of the present invention will be described in detail with respect to the same or a part of the same figure, all of which are hard and short-path. Particle size and volume ratio. Rate (for example: , page 289). The total 値 is the hard plasmid under the coarse plus the full rate. Among the compounds and boronization groups: the Fe-based alloy welding method is a form. The figure is not repeated for the same -11 - (8) 1302949 or equivalent. 1. Composition of the coating The tool for hot working according to the first embodiment of the present invention has a coating on the surface in contact with the workpiece. The coating is composed of a bonding metal and a hard particle. 1.1 Bonding metal Bonding metal, which is a transition metal or an alloy mainly composed of transition metals. The bonding metal is, for example, a Co-based alloy, a Ni-based alloy, a Fe-based alloy, or the like. The C bismuth based alloy is, for example, a chrome-tungsten alloy (s t e 11 i t e ). Mingluo tungsten alloy has excellent heat resistance and ductility. The N i based alloy is, for example, IN 6 2 5, C276, 50Cr - 50Ni, COLMONOY, or the like. Fe-based alloys such as stainless steel, tool steel, carbon steel, and Cr steel. The environment in which the tool for hot working is used is required to be resistant to corrosion and abrasion. With this in mind, the bonded metal is preferably a C-based alloy and a Ni-based alloy having superior corrosion resistance and wear resistance. 1.2 Hard particles Hard particles are used to improve the abrasion resistance of the coating. Among the hard particles, the coarse hard particles having a particle diameter of 50 or more are in contact with the material to be processed. Therefore, it is preferable that the coarse hard particles have excellent wear resistance and toughness. The coarse hard particles are, for example, carbides, oxides, nitrides, borides, or a mixture of these or a composite compound of these. Carbides are, for example, NbC, TiC, VC, WC, W2C, Cr3C2 -12-(9) 1302949, Mo2C, ZrC, TaC, HfC, Fe3C, and the like. The carbide may also be a composite carbide such as Nb or Cr) C. Oxides, such as Al2〇3, MgO, Zr02, SiO2,

Cr203 and the like. The oxide may be a composite ruthenium nitride such as 3Al203. 2Si02, such as TiN, ZrN, VN, NbN, TaN, BN, AIN or the like. The nitride may also be a complex such as (Ti, Cr) N. The boride is, for example, TiB2, ZrB2, HfB2, VB2, TaB2, CrB, CrB2, Mo2B, MoB, Mo2B5, WB, LaB6 or the like. The boride may be a composite carbide such as Nb or C〇B, and is a compound of two or more kinds among carbides, oxides, nitrides, and boron. For example, Nb (C, Ν), etc. In the aspect, the fine hard plasmid having a particle diameter of 20 // m or less is required to disperse and strengthen the bonding metal. That is, the bonding metal is finely hard to maintain ductility and toughness, and at the same time, the strength can be improved. The abrasion resistance of the bonded metal Lifting and preventing the coarse hard particles from falling off. The fine hard particles are of any kind. Fine hard particles, examples, oxides, nitrides, borides, or a mixture of these or a composite compound of these. Fine hard particles can also be used. It is an intermetallic compound of the class of Ni-A1 and Ni-Si. It is thought that (Ti02, oxide, Si3N4, NbB2, W2B5, borohydride, etc., SiAlON) is a particle to make a bond from carbon. Also, Ti-A1 -13- (10) 1302949 2 ·Manufacturing method &T is a description of the manufacturing method of the tool for hot working of the present invention. First, a tool for hot working is prepared, The coating is formed on the surface of the hot working tool @$. The material of the hot working tool to be coated on the surface is not particularly limited, and examples thereof include carbon steel, tool steel, stainless steel, and Ni-based heat resistant alloy. The formation method may be a PTA method or a MIG welding method or a TIG welding method, or a hot-melt spraying method such as an atmospheric plasma hot melt spraying method or a reduced pressure plasma hot melt spraying method or an HVOF method. Alternatively, a powder metallurgy method such as HIP treatment may be used. In addition, when casting a tool steel for hot working, hard particles and a bonding metal may be added to form a coating. For example, when a PTA method is used, a bonding metal is used. The powder and the hard-particle powder are used as raw materials to carry out the surfacing. At this time, the raw material is adjusted so that the total volume ratio of the hard layer containing the formed coating is 25% to 70%, and the coarse hard particles are occupied. The layer volume fraction is 20% to 60%, and the fine hard particles are 5% to 30 ° / 〇 of the coating volume ratio. On the other hand, the fine hard particles can be contained in the raw material in advance, but Precipitating fine hard particles to form In this case, the manufacturing method is a welding method such as PTA method, MIG welding method or TIG welding method, etc. The hard particles for which fine hard particles are to be precipitated are preferably those having a lower melting point. In the case of solder joints, it is necessary to melt first. For example, in terms of carbides, it is preferably VC, WC, W2C, Cr3C2, Mo2C, etc. In the case of nitride-14-(11) 1302949, it is VN, NbM. In terms of boride, it is preferably CrB, CrB2, etc. These melting points are all 3 〇〇〇 κ or less, and the PTA method or the ΜI G welding method or the T 〗 G welding method Fine hard particles can be precipitated, but among them, fine hard particles of PTA method are preferred. Since the PTA method uses a plasma arc to form a layer, it is possible to melt a hard particle having a high melting point. Further, when the fine particles are in a precipitated state, it is not suitable for the fine hard particle preparation to be precipitated. This is because the adhesion of the metal and the toughness are lowered when the oxide is melted. According to the above work, the tool for hot working of the present invention can be completed by forming the surface of the tool for hot working. [Example 1] A hot working tool for rough hard particles and fine hard particles in a coating layer was produced, and the properties and sinter resistance of these tools for hot working were examined. VB2 〇 any welding to form a hard-coated oxidative ductile coating, the rate is not resistant to wear -15· 1302949 2) [一撇] Wear test results sinter resistance X 〇〇〇〇〇〇〇〇 Ο 〇 wear loss 1 inch · inch · inch (N cn inch cn inch · r - Η m ο rn inch cn ^ sO total volume fraction of hard particles. (vol%) m Ο Ο Ο un VO o * 5. VII main component U Ο X) 2 U u ZU u UUZ NbC, WC υ Ο 2 U uz \ NbC, WC NbC, WC NbC, WC NbC, WC ft 趔k . 陛 藜 藜 volume rate (vol%) * cn coarse hard particles ( ^50//m) Principal Component NbC NbC NbC NbC NbC NbC NbC NbC NbC NbC NbC NbC Volume Rate (vol%) * ▼-Η o § * 〇 Bonded Metal Dimensional Pressure Diamond Hardness ί (Ην) 320 330 380 450 510 280 360 420 480 520 500 ο (N m inch 00 ON or < test body comparison product The present invention product of the invention The present invention product comparison product comparison product The invention product invention invention product comparison product comparison product - 16 - (13 1302949 The test piece 表 ο 1 1 Ν ο · 1 1 in Table 1 is manufactured as follows. The carbon steel (S45C) block of the working tool is surfacing to form a PTA surfacing coating to be coated. The PTA surfacing coating is a 2-layer stack with a thickness of about 6 mm. The conditions for forming a weld overlay are shown in Table 2. [Table 2]

Condition 値 Current 値 (A ) 2 10 Distance between torches (mm) 12 ～13 Wire oscillating joint width (mm) 1 0 〜1 2 Bead overlap (mm) 4~5 Powder supply (g / mi η 60 Welding speed (mm/min) 85 Preheating temperature (t) 250 ± 50 The raw material of the carrier gas Ar coating is the following materials. The bonding metal was a nitrogen atomized powder (cobalt-chromium-tungsten alloy #6 powder) using a cobalt-chromium-tungsten alloy #6 which is a Co-based alloy. The particle size of the cobalt chromium tungsten alloy #6 powder is m 150 150 / m. The coarse hard particles are NbC powder having a particle diameter of 75//m to 100/zm. Further, as the fine hard particles, NbC powder having a particle diameter of 1 5 // m or less is used. Among these powders, each sample was changed in the amount of NbC powder of coarse hard particles and fine hard particles. This is to change the volume fraction of coarse hard particles and fine hard particles contained in the PTA surfacing coating of each sample for -17-(14) 1302949. In addition, at this time, for the samples No. 1 to No. 5, the raw material was adjusted to have the same volume fraction of the fine hard particles in the PTA surfacing coating, and for the sample No. 6 to No. 10, the raw material was adjusted to PTA. The volume ratio of coarse hard particles in the surfacing coating is the same. After the PTA surfacing coating was formed, the 10 mm x 20 mm x 25 mm specimen shown in Fig. 3 was obtained by machining and honing. Next, the particle diameter and the volume ratio in the deposited PTA overlay layer of each of the prepared samples were measured. Further, based on the measurement results, the volume ratio of the coarse hard particles and the volume fraction of the fine hard particles and the total volume fraction of the hard particles were calculated. Specifically, a plurality of arbitrary region ranges are selected from the cladding cross section of the surface of the tool for hot working. At this time, the total area of the selected area range is greater than 3 mm X 3 mm. The particle size and area ratio of each of the hard particles in the selected region range were measured using an optical microscope or a scanning electron microscope (SEM). The long diameter and the short diameter of each hard particle were measured (long diameter + short diameter) / 2 = particle diameter. The particle size and area ratio of each hard particle were measured using image analysis. The area ratio of the hard particles having a particle diameter of 5 〇 or more is equal to the volume 粗 of the coarse hard particles. Further, the area ratio of the hard particles having a particle diameter of 20 // m or less is the volume 微 of the fine hard particles. The area ratio of all the hard particles measured was 値 as the total volume fraction of the hard particles. The hard particles in the sample were identified by EDX (Energy Dispersive X-ray Microanalyzer). In addition, the Vickers hardness of the bonded metal in the PTA overlay coating is measured by JIS Z2244. -18- (15) 1302949 Referring to Table 1, all the test pieces ο ο . 1~Ν ο · 1 1 of the coarse hard particles are all NbC. On the other hand, the fine hard particles are NbC and WC. When surfacing by the PTA method, the W and C of the cobalt-chromium-tungsten alloy #6 are combined, and then the WC 〇 test body Νο·1~Νο·5 is precipitated, and the volume ratio of the fine hard particles in the PTA surfacing coating is 5%. The sample Νο·2~Νο·4, the volume fraction of the coarse hard particles, the volume fraction of the fine hard particles, and the volume fraction of the hard particles were all within the prescribed range of the present invention. On the other hand, in the sample No. 1, the volume ratio of the coarse hard particles was less than the lower limit (20%) of the range prescribed by the present invention. Further, in the sample No. 5, the volume ratio of the coarse hard particles was an upper limit (60%) exceeding the range prescribed by the present invention. Further, the hardness of the bonded metal of the sample Nos. 1 to No. 5 became higher as the volume fraction of the coarse hard particles increased. In the sample No. 5 in which the volume ratio of the coarse hard particles exceeded the upper limit 値 (60%) of the range specified in the present invention, the hardness of the bonded metal exceeded Hv 5.00. This is because the larger the volume fraction φ of the coarse hard particles is, the more the amount of carbides melted into the bonded metal is increased, so that the hardness of the bonded metal becomes high. In the sample No. 6 to No. 10, the volume ratio of the coarse hard particles in the PTA surfacing coating layer was 30%. In the samples No. 7 to No. 9, the volume ratio of the coarse hard particles and the volume fraction of the fine hard particles and the volume fraction of the hard particles were within the range defined by the present invention. On the other hand, in the sample Νο·6, the volume fraction of the fine hard particles was less than the lower limit 5 (5 %) of the range specified by the present invention. Further, in the sample No. 10, the volume fraction of the fine hard particles was an upper limit 3 (30%) exceeding the range prescribed by the present invention. -19- (16) 1302949 In addition, the hardness of the bonded metal of the sample No. 6 to No. 10 becomes higher as the volume fraction of the fine hard particles increases. The volume fraction of the fine hard particles is 试ο·6, which is the lower limit of the range (5%) of the range specified by the present invention, and has a low hardness of Ην2 80. In the sample No. 10 in which the volume fraction of the fine hard particles exceeded the upper limit 値 (30%) of the range of the present specification, the degree of the bonding metal exceeded Hv 5.00. This is because the more the volume fraction of the fine hard particles is increased, the more the amount of carbides melted into the bonded metal is increased, so that the hardness of the resulting metal becomes high. In the sample No. 11, the volume fraction of the coarse hard particles and the volume fraction of the fine hard protons were within the range specified by the present invention, but the volume of the hard particles was an upper limit 値() exceeding the range prescribed by the present invention. The hardness of the bonded metal of the sample No. was high and was Hv5 00. Further, in each of the samples, the total volume fraction of the hard particles showed a higher enthalpy than the total of the large hard particle volume ratio and the fine hard particle volume ratio. This is because there are hard particles larger than 20/zm but smaller than // m in the PTA surfacing coating. In the PSA method for surfacing, a part of the coarse particles of the raw material is melted, and since the particle diameter thereof becomes small, hard particles are generated between 20 #m and 5 0 /z m. [Abrasion Test] The abrasion test was carried out using the test pieces No. 1 to No. l 1 . The abrasion test was carried out as described below. Referring to Fig. 4, the diameter of the center of the rotating shaft is l〇〇mm, the width of the circumferential surface is 30mm, and the cylinder of material S25C is heated to 1 027K after high frequency, and will remain as a cylinder of 1 027K. Unfinished hard hardened cohesive product 11 coarse This 50 hard is the outer circle rotated by -20- (17) 1302949 1 OOrpm (circumferential speed about 0.52m / sec). The surface of the solder coating layer of the test piece was pressed at 50 kgf on the circumferential surface of the rotating cylinder to maintain such a state for 1 hour. The contact slip after the test was 1885 m. As shown in Fig. 5, a concave portion was formed on the PTA surfacing surface after the abrasion test. After the test, the calculation of the surface wear loss of the PTA surfacing coating of the test piece was calculated as follows. For the measurement before and after the test of each test piece, the weight obtained by subtracting the weight of the sample before the test from the test and the density of the PTA surfacing layer is equal to the amount of wear (m I plus, investigation of the wear test) In the case of the subsequent test piece, whether or not the sintered body is produced is observed by a SEM (scanning electron microscope) at a 50-degree rate (the concave surface of the PTA surfacing coating surface) to determine whether or not there is a S25C (cylinder). Transfer if there is no transfer (〇 in Table 1), if it is confirmed that there is transfer, it is rated as X in the list. [Test result] Figure 6 shows the sample in Table 1. The relationship between the volume fraction of the particles of No. 1 to No. 5 and the amount of wear. Referring to Table 1 and Fig. 6 to No. 2 to Νο·4, the amount of wear was less than 3.5 mm 3 and there was no knot. On the one hand, the sample No. 1 has a low wear of 15% of the coarse hard particles, so the amount of wear of the overlay weld layer is more than 4, and the volume ratio of the coarse hard particles is low. The wearable PTA stack of the sample N 〇·5 with a hard particle volume fraction of 65% was continuous for the surface amount of the coating. The I3). Knot. With multiple times), it is rated (table 1 is coarse and hard, and the test piece produces a burn rate of mm3 ° knot. The amount is also (18) more than 1302949, which has exceeded 4 mm3. Figure 7 shows the table The relationship between the volume fraction of micro-plasmids and the amount of wear of the test medium Νο·6~Νο·10. Referring to Tables 1 and 7, Νο·7~No.9, the wear amount is less than 3.5 mm3. On the other hand, the sample Νο·6 has a lower volume fraction f of the fine hard particles, so the wear of the overlay weld layer is more than 4 mm3. The volume fraction of the fine hard particles is 35%. Test No. 10 'The wear of the PTA coating is also large, and has exceeded 4 mm 3 . In addition, the test piece of the wear amount less than 3.5 mm 3 Νο··2~Νο·4 and ~No.9 of the bonded metal Vickers The hardness of the diamond was in the range of 300 -. [Example 2] The same hot working test as in Example 1 was carried out to produce a hot working method in which the type of coarse hard particles in the coating was different, and the hard test was performed. 2% additionally surfacing No.7 ^ 490 tools

-22- 1302949

US

Wear test results sinter resistance 〇〇〇〇〇〇〇〇O 〇O wear loss shame (Ν rn cn cn ο rn m cn m rn o rn (N rn hard particle total volume ratio (vol%) fine hard particles (S20 //m) Principal component TiC TiC TiC I TiC TiC TiC TiC TiC TiC TiC TiC Volume ratio (vol%) ο ο ο ο ο o ο O 〇〇o Coarse hard particles (2 50 // m) Principal component NbC we Al2 〇3 Zr02 TiB2 MoB Si3N4 TiN Z PQ SiAlON Nb(C,N) Volume ratio (vol%) ο ο ο ο ο o ο o O oo Bonded metal dimensional diamond hardness (Hv) 360 350 360 340 390 380 380 360 340 360 370 Test ο (Ν ν νο 00 ON (N -23- (20) 1302949 The test piece 表ο·12~No.22 in Table 3 is manufactured as follows HlP (Hot Isostatic Processing) This is a detailed description of the block 1 of the carbon steel (SCC) for hot working tools. First, it is a block of S45C at the bottom of the mild steel shell shown in Fig. 8. After fixing In the soft steel shell, the coating material is filled in the block space. The coating material is the following raw materials. Bonding metal, Co-based Gold ingot tungsten alloy #21 nitrogen atomized powder (Cobalt #21 powder). Cobalt chromium tungsten alloy #21 powder has a particle size of 63 A m. Fine hard particles are used with a particle size of 1 5 // m or less. For the coarse and hard particles, a particle size of 75//m to 100/zm is used. The coarse hard particle powder used in each test is shown in the column of the main component of the coarse hard particles in Table 3. Specifically, the test and No. 13, the coarse hard particles are selected carbides (NbC test No. 14 and No. 15, the coarse hard particles are selected Al2〇3, Zr02). The test bodies Νο·16 and Νο·17, the coarse is the choice of boron Compound (TiB2, M〇B). Test Νο·18~No. Large hard particles are selected nitrides (Si3N4, TiN, BN No. 21, and the coarse hard particles are selected oxides and nitrides SiAlON. The body Νο·22, the coarse hard particles are a mixture of the substance and the nitride Nb (C, Ν). After the raw material is filled, the raw material is vacuum-pumped from the exhaust pipe, and the raw material is vacuum-sealed in the soft steel shell. Then, Use the soft described. The method is to form a coating. The upper part of the material is the coarse and hard type of the Tie powder used for the complex alloy // m ~ 1 50 Tie powder; the body N0.12, WC). Oxide (hard particles .20, coarse). Compounding of the test piece Selection of carbonized air After the air evacuation, the steel shell was subjected to HIP treatment under the conditions of -24- (21) 1302949 Table 4. Condition 値 Processing temperature (°c) 1 200 A treatment time (hr) 3 Pressure (atm) 1500 Pressurized gas Ar Heating rate (°C / mi η ) 10 Cooling rate FC (in-furnace cooling) Coating thickness after implementation It is about 3mm. After machining and honing, the 10mm X 2 0 mm X 2 5 mm sample shown in Figure 3 is obtained. N〇"2~ No.22 °

After the preparation of the test piece Νο·12~Νο·22, the particle size and volume fraction of the hard particles in the coating of each test piece were measured in the same manner as in Example 1 Μ and the Vickers diamond of the bonded metal in the coating layer. hardness. In addition, hard particles are identified by EDX. The volume ratio of the coarse hard particles of the sample Nos. 12 to No. 22 was 40%, which is within the predetermined range of the present invention. Further, the fine hard particle volume fraction is 10%, which is also within the range specified by the present invention. Further, the total volume fraction of the hard particles is 50%, which is also within the range specified by the present invention. In addition, the hardness of the Vickers diamond of the bonded metal of each test piece is in the range of 340 to 390 'is with the test body>1〇.2~]^〇.4,]^〇.7~]^〇.9 -25- (22) 1302949 Vickers diamond hardness to the same extent. Using the samples No. 2 to No. 22, the abrasion test of Example 1 was carried out, and the amount of wear and sintering were evaluated. [Evaluation Results] Referring to Table 3, the wear amount of all the test pieces was less than 3.5 mm3, and no sintering occurred. From this, it is known that even if the coarse hard particles are made of a carbide, an oxide, a nitride, a boride, or a mixture of these, the processing tool is far from or a composite compound of these, the present invention is superior in aggregation. Wear resistance. The tool for hot working was carried out. [Example 3] The same abrasion test as in Example 1 was carried out after the type of the bonding metal in the coating layer was not wide.

-26- 1302949

[£] Face test results sinter resistance 〇〇〇〇〇〇〇〇〇 wear amount (mm1) (Ν rn ΓΝ ΓΝ · inch rn m rn rn rn inch m* i hard particles! Overall vocabulary (vol%) s 沄沄S ! ' p fine hard particles (S2〇/im) Principal component NbC, WC uufu I y << X! z H CQ ZU z NbC NbC NbC uuf Volume ratio (V0|%) Ο 〇〇〇〇〇 o 〇〇 coarse hard particles (250/im) main component NbC NbC NbC NbC NbC NbC NbC NbC NbC volume ratio (vol%) bonded metal dimensional pressure diamond hardness (Hv) 420 490 360 380 460 320 340 380 480 痤 m _ β 1ft I 1 collar m iS s -B- l£ M c 2 t 1 1 1 1 〇<N o tTi 〇CQ 1 1 1 1 <N • 1 1 Η ta I 0.25 1 1 1 1 X) 2 1 1 1 1 1 1 I < 1 1 1 0.25 . 1 t 1 rr 00 1 1 1 1 1 ο 1 VO On 1 rN — υ s fN (N o oo ON Ζ yr\ Ί5 CQ Bal. Bal. fN 1 -Έ CQ Bal. 13 CQ 1 • 1 • o rn • Bal. Bal. Bal. pqp 1 uo rn 1 〇rs o ΓΝ 〇υ p 〇0.05 rn 1 0.03 0.15 o Type Co-based Co-based Co-based Ni-based Ni-based Ni-based Fe-based Fe-based Fe-based test piece (N < N 〇 0 < N Ο iN P; -27- (24) 1302949 A test piece 制造ο·31 was produced by the same manufacturing method as in Example 1. The raw material of the PTA overlay welding layer is a powder using a bismuth bonding metal, and the composition shown in Table 5 is used. The bonding metal having the sample No. 23 to Νο·25 is selected from the group consisting of Co-based Νο·26~No.28. The bonding metal is selected from the Ni-based alloy. The bonding metal of the test No. 31 is a Fe-based alloy. The coarse hard particles are powders having a particle size of 75 // m to 100 μ r. In addition, fine hard particles were prepared using a particle size of 15 # NbC powder. The volume fraction of coarse hard particles in the raw material is 31 to 7. The volume fraction of fine hard particles is 7 to 8%. After the test piece was prepared, the particle size and volume of the hard particles in the PTA surfacing coating in the same manner as in Example 1 were used to determine the Vickers hardness of the bonded metal in the PTA overlay coating. This EDX was used to identify hard particles. The volume ratio of the coarse hard particles of the sample Nos. 23 to No. 31 is within the predetermined range of the present invention. Further, the fine hard plasmids were all 10%, which is also within the scope of the present invention. Further, the total volume fraction of the sub-units is 50%, which is also a specification of the present invention, and the sample Νο·23~No.27 and No.31, and the fine hard particles other than the ones. These fine hard particles are fine hard particles formed by precipitation of a viscous component. Further, the Vickers hardness of the bonded metal of each test piece was in the range of ～3 90, and it was gold with respect to the raw materials of the test pieces Νο··2 to No. 4 and No. 7 - Ν〇·23 〜. The sample body Ν 〇 · 2 9 η N 3 C C m below the 〆 3 3 %, microtest each test rate, and, in addition, the permeability is 30% sub-volume rate, within the hard plasmid. In the NbC junction metal, it is 320-Ν 〇 · 9 -28- (25) (25) 1302949 Vickers diamond hardness is the same degree. Using these test pieces Νο·23 to No. 31, the same abrasion test as in Example 1 was carried out, and the amount of wear and sintering were evaluated. [Evaluation Result] The amount of wear of all the test pieces Νο·23~Νο·3 1 was less than 3·5 mm3, and no sintering occurred. From this, it is understood that the hot working tool of the present invention has superior wear resistance even if the bonding metal is a Co-based alloy or a Ni-based alloy or a Fe-based alloy. [Example 4] A hot working tool containing precipitated fine hard particles was produced in the formed coating layer, and the same abrasion test as in Example 1 was carried out. -29- 1302949

[9撇] Wear test results resistance to sinter i! j 〇〇〇〇〇〇i wear loss star f-η cn inch · Bu (N ON CN 00 (N 〇v (N hard particle total volume ratio 1 [ (vol %) 丨fine hard particles (^20//m) main component NbC, WC NbC'WC u > uz NbC, Mo2C NbC, VN NbC, CrB2 1- volume fraction (vol%) CM o 00 oo coarse hard particles ( 250/im) Principal component NbC U uz NbC NbC NbC NbC Volume ratio (vol%) oo Bonding metal dimension Diamond hardness (Hv) 280 270 420 440 430 ! 450 2nd hard particle NbC wc U > Mo2C CrB2 test piece ο Ζ (N mm -30-(27) 1302949 Test pieces No. 32 to No. 37 were produced by the same production method as in Example 1. The raw materials of the PTA surfacing coating layer of each test piece were the following raw materials. The metal is the same cobalt chromium-tungsten alloy #6 powder as in Example 1. The coarse hard particles are Nbc powder having a particle diameter of 75//m to 100/zm. Further, a hard material for precipitating fine hard particles is added. The particle powder is a second hard particle powder having a particle diameter of 75//m to 100//m. The second hard particle powder used in each sample is as follows: 6 shows that the volume ratio of the coarse hard particles in the raw material is 3 3 °/〇, and the volume ratio of the second hard particles is 12%. After the test piece is prepared, each sample is measured in the same manner as in Example 1. The particle size and volume fraction of hard particles in the PTA surfacing coating, and the hardness of the Vickers diamond of the bonded metal in the PTA surfacing coating. In addition, the hard particles were identified by EDX. 试ο·32~Νο·37 Among them, the sample ν〇·32 and No. 33, the volume fraction of the fine hard particles precipitated was less than 5%. It is known that the second hard particles: NbC and WC have a high melting point, so the pta is deposited in the cladding layer. The amount of melting of the second hard particles is small, so that the amount of precipitation of the fine hard particles is small. The hardness of the Vickers diamond of the bonded metal of the test pieces ν〇·32 and Νο·33 having a small amount of the second hard particles is low. On the other hand, in the sample Νο·34~Νο·37, the second hard particles are mostly precipitated into fine hard particles, and the fine hard particles precipitated have a volume fraction of 5% or more, which is in compliance with the scope of the present invention. The second hard particles of the sample Νο.34~No.37: VC, Mo2C, VN, CrB2 Its melting point is less than 3 000 K, and its melting point is lower than other hard particles. Therefore, it is known that the hard particles of the first 31 - (28) 1302949 2 are melted when they are deposited by the PTA method, and then precipitated into fine hard particles. In addition, the hardness of the Vickers diamond of the bonding metal of the test piece Νο·34~No.37 in which the second hard particles are melted and then precipitated into fine hard particles is 420 to 450, which is the same as the sample Νο·2~Νο·4. No. 7 to Νο·9, No. 12 to No. 22, and No. 23 to No. 31 have the same degree of Vickers diamond hardness. In addition, some of the test pieces contained fine hard particles: NbC. It is known that when surfacing is performed by the PTA method, a part of the coarse hard particle NbC powder in the raw material is melted and then precipitated into fine hard particles. The volume ratio of the coarse hard particles of the test pieces Νο·34 to No. 37 was 30%, which was within the range specified by the present invention. Further, the total volume fraction of the hard particles in the samples No. 34 to No. 37 was 45%, which is also within the prescribed range of the present invention. The same abrasion test as in Example 1 was carried out using these test pieces. [Evaluation Results] The specimens Νο·32 and Νο·33 have a large amount of wear, which exceeds 4 mm3. On the other hand, the amount of wear of the test pieces Νο·34 to No. 37 was small, which was less than 3.5 mm 3 °, and the test pieces N 〇 · 3 4 to N 〇. 3 7 and the test pieces in the examples. When Νο·7~Νο·9 is compared, the amount of wear of the test pieces Νο·34 to No. 37 is small. From this, it was found that the coating tool contains a hot working tool for depositing fine hard particles, and the wear resistance is superior. Although the embodiments of the present invention have been described above, the above embodiments are merely illustrative of the embodiments of the present invention. Therefore, the present invention is not limited to the above-described embodiments, and the above-described embodiment-32-(29) 1302949 can be suitably modified and implemented without departing from the gist of the invention. [Industrial Applicability] The tool for hot working of the present invention can be utilized in hot working of metal. For example, it is a hot working operation of stainless steel, Ni-based alloy, or general carbon steel which can be utilized in a martensite system or an austenitic system or a two-phase system. In particular, it can be utilized as a plug, a skew roll, a disc roll, a guide block, or the like to be used for a piercing and rolling work. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram for explaining the wear mechanism of a coating containing hard particles. Fig. 2 is a cross-sectional view showing a coating formed on a tool for hot working of the present invention. Fig. 3 is a perspective view showing the shape of a test piece in the present embodiment. Fig. 4 is a schematic view showing the wear test in the present embodiment. Fig. 5 is a perspective view showing the test body after the abrasion test in Fig. 4. Fig. 6 is a graph showing the relationship between the volume fraction of coarse hard particles and the amount of wear in the coating of the hot working tool of Example 1. Fig. 7 is a graph showing the relationship between the volume fraction and the amount of wear of the fine hard particles in the coating of the tool for hot working of Example 1. Fig. 8 is a schematic view for explaining the method of manufacturing the tool for hot working of the second embodiment. -33-

Claims (1)

i 1302949 丨 、 、 申请 申请 、 、 、 、 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 94 : at least one type of binder metal is selected from the group consisting of a Co-based alloy, a Ni-based alloy, and a Fe-based alloy, and the ruthenium in the coating layer is 25% to 70% of hard particles, and the hard particles are contained. The volume fraction in the coating layer is 5% to 30%, the fine hard particles having a particle diameter of 20 //, and the volume ratio in the coating layer are 20. /〃, coarse hard particles with a particle size of 50 // m or more. 2. The thermal processing work according to the first aspect of the invention, wherein the coarse hard particles are selected from the group consisting of carbides, oxides, nitrides, substances, mixtures, and composite compounds. 1 species. 3. The thermal processing according to the first or second aspect of the invention, wherein the coating is formed by a welding method. 4. The hot working tool according to the third aspect of the invention, wherein the fine hard particles are precipitates. Correction layer, group when the product rate m is ^ 60%, its boride at least the tool, its