TW201011112A - Roller body component for use in molten metal plating liquid and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a roller body component for use in high temperature molten metal plating liquid and its manufacturing method. A metal oxide, which has more powerful chemical affinity to oxygen than chromium, covers over the surface of melting spray coating of a tungsten carbide-metal boride-cobalt cermet coated on the surface of a parent material. Alternatively, while sintering the coating from the mixture mixed by its oxide with nitride, the sintered micro-particles of the foregoing oxide or the mixture mixed by oxide with nitride are filled within micro pores existing in the vicinity of the surface of the aforementioned melting spray coating as well. Accordingly, the surface defects of the plating metal caused by the roller surface property can be prevented so that foreign bodies are difficult to attach and may be easily peeled off.

Description

.201011112 IX. Description of the invention: [Technical field to which the invention belongs]

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a roller assembly for use in guiding a metallized material to be conveyed in a plating tank of a continuous molten metallization apparatus, and a method of manufacturing the same, such as a refining clock metal. The tank is immersed in the roll body ("Sink Roll" or "Supp Roll"), especially for molten galvanizing, melt plating, and molten lead-plated aluminum alloy. An in-slot roll body or a support roll body used in a plating solution for a non-ferrous metal molten gold plating apparatus such as molten tin plating, and a method for producing the same, and a surface material improving technique for the roll body. [Prior Art] As shown in the first figure, the in-slot roller body (2) and the supporting roller body for metallizing equipment (1) such as a hot-dip galvanizing device or a molten aluminum-plating device for plating a metal strip surface (3) etc., which have been used in molten metal such as zinc or aluminum and are subjected to severe environmental conditions, so it is basically required to have the following properties: 1 with molten metal, the surface of the roller is not easily Erosion; 2 contact with the passing steel strip, the surface is also not easy to wear, can maintain the initial shape accuracy; 3 although it is subordinate (four), its long life and can suppress equipment costs. In addition, the roller body in the groove will change the direction of the guide steel strip while the plating tank is being conveyed, so the steel strip will be used for the use of the steel strip. Therefore, the following performances are required for the advancement step: 4 the floating alloy of the floating bath in the plating tank or the like Particles, or ": mainly iron-zinc" particles, which melt into: the mechanical properties of the sub- and gold-plated metal components... the particles are in the metal, the shape defects of the gold layer are not easy to Μ base +, + 霄 lead plating +Easy to be attached to the metal strip to be plated; 5 - 4 and 201011112, as shown in the second and second B diagrams, a spiral groove (Groove) for discharging the foreign matter is engraved on the outer peripheral surface of the inner roller of the groove. (4) (4') The shape of the spiral groove is required to have a property of a metal-plated surface defect (i.e., a so-called r Groove Mark) which is less likely to cause unevenness of the metal of the steel strip, uneven color tone, and uneven gloss. In order to meet these requirements, 'a' has previously adopted a coating layer excellent in resistance to molten metal corrosion on the outer peripheral surface of the roll; (b) improving the groove shape of the outer peripheral surface of the roll. In the prior art, the prior art is described as '1 having a high-temperature flame (HV〇F) method for coating tungsten carbide-cobalt gold (WC-Co cermet); 2 for proposing a chemical coating on the molten slope a densification treatment method is applied with a chromium trioxide (Cr〇3) solution, and the chromium oxide (Crd3) microparticles are filled with fine pores impregnated into the molten film by heat treatment to make them practical; As shown in Fig. A and Fig. 2B, in the case of the latter, the roller body can be engraved on the surface of the roller body in addition to the grooves of the spiral groove (4) (4) on the surface of the roller body. (Processing) depth φ 〇 · 05 〇 · 5 mm, width 0. 05 〜 l 6 mm, pitch (Pitch) O. 5 ~ 10mm continuous or non-continuous groove; 5 forming a 5 ~ concave surface on the peripheral surface of the roller body In order to avoid the in-slot roller body in which the conveying material is in direct contact with the outer peripheral surface of the roller. These various technologies in the past have long-term stability of the surface shape of the roll body, prevention of adhesion of the zinc-aluminum-iron intermetallic compound, growth on the roll surface, and metallization of the spiral groove for discharging foreign matter due to contact with the steel sheet. The reduction in color tone or uneven gloss can exert considerable effects. However, in recent years, the quality of mines required for anti-recording steel sheets for π vehicles has become higher and higher, and past improvements may not be met. That is to say, the mechanical properties of the 5 201011112 for the key metal steel plate are self-evident, and for the metallized layer of the coating base of the object of the invention, such as the metal plating defect or the trace defect, the surface quality requirement is actually It is also more demanding.

Under such background art, the inventors investigated the surface defects of the metal plated steel sheet in an attempt to improve the quality of the metallized surface, because the contact surface of the steel plate and the wheel body is produced, in particular, the extremely small shape of the roll surface. Defects (face, line, point) cause. Further, with respect to these shape defects, in addition to the shape defects of the surface of the film itself, components such as foreign matter adhered to the grooves on the surface of the film were investigated in particular. Further, it has been found that these plating liquid components are fine iron-aluminum or iron-aluminum-zinc intermetallic compounds. As far as the prior art such as carbonized town-drilling gold-soled plastic media is known, 'because of materials resistant to (four) metality, (iv) body-mother (four) protection should be effective. n (4) film ^ 绕 light diffraction method is known A small amount of a non-identical metal 35 phase is present. This aphid has affinity with molten zinc, which becomes the core of the iron-aluminum or iron-aluminum-zinc intermetallic compound and promotes adhesion. In addition, the effect of chromium oxide ((iv)), which is known to the prior art, especially in the surface layer of the roll body, which is in contact with the molten layer, is oxidized in a relatively microscopic field. Chromium ((iv) 3) restores 'generating gold secrets. Therefore, in the 'plating solution', the durability in the molten galvanizing bath, which also contains the inscription, is unstable in the force-(4), and the mechanical chromium oxide (Cr203) will change = the deterioration of the film And 1, will also promote the adhesion of the above intermetallic compounds. As the above description (Macro) protection, 'there is a method, although the surface of the base metal is actually a giant in the micro (Micro) point of view. 6 201011112 can suppress iron -|g or iron _ [ SUMMARY OF THE INVENTION Ming-Zinc intermetallic compound adhesion and growth

In view of the fact that the above-mentioned microscopic view is the iron core of the metal, it is sufficient to suppress the iron-inscription or to provide an effective roller body part that prevents the surface of the roller from being damaged. The main h, especially for the other purpose of the surface skin structure and its _„ω ^ month, is to provide a metal body with a metallized foreign body which is not easily attached to the roll surface and which is easy to peel off the surface structure of the roll and the roll body thereof. Method for forming a surface film. In order to achieve the above object, the present invention reviews the microstructure of the surface of a tungsten carbide-cobalt molten film formed on the surface of an existing roll body to remove iron-aluminum which is generally referred to as a foreign matter in a foreign body. Or the adhesion growth of the iron-aluminum-zinc intermetallic compound on the surface of the roll. The inventors have diligently studied the results of the invention relating to the following points. That is, the present invention provides a surface coated with a steel base material. a roll body member formed by coating a carbonized gold-soled spray film or a carbonized crane-metal boride-cobalt-gold alloy sprayed leather, in the aforementioned tungsten carbide-cobalt-gold alloy spray film or tungsten carbide-metal boride-cobalt porcelain The surface of the molten film forms a mixed calcined film of chromium oxide and nitride, and the fine pores existing in the vicinity of the surface layer of the molten film are filled with the above-mentioned mixture of chromium oxide and nitride. Roller member for molten metal plating bath formed by microparticles. On the other hand, the present invention provides a tungsten carbide-cobalt powder which is sprayed on the surface of a steel base material to be coated with a sinister crane. a molten film, followed by coating a surface of the tungsten carbide-cobalt molten film with a foreign matter containing a chromium oxide water-soluble 7 201011112 liquid and a nitride to heat the baked product, thereby providing the carbonization in the foregoing A method for producing a roll material for a molten metal plating bath characterized by having a tungsten-cobalt-gold alloy molten film and small pores existing in the vicinity of the surface layer of the film, which is covered by the baking mixture, and which is characterized by the present invention. The surface of the steel base material is coated with a powder of tungsten carbide-metal boride-cobalt-based porcelain gold to form a tungsten carbide_metal boride_cobalt-solubilized film, followed by tungsten carbide-metal boride _ The surface of the cobalt-gold alloy molten film is coated with a metal oxide having a chemical affinity with oxygen than chromium or a mixture of the oxide and the nitride and a suspension of the aqueous metal salt solution, and then fired by heating. 'In the above-mentioned tungsten carbide-metal boride-cobalt-based porcelain gold-soled film and small pores existing in the vicinity of the surface layer of the film, the fired oxide or the sintered mixture of the oxide and the nitride is covered and A method for producing a roll member for a molten metal plating bath plating liquid characterized by the same. In the present invention, the aforementioned boride is made of titanium boride (TiB2), brominated (ZrB2), and boride. Give (HfB2), boring hunger (VB2), lanthanum boride (TaB2), lanthanum boride (NbB2), nickel boride (NiB2), tungsten boride (W2B5 or WB), and shed chromium (CrB2) One or more selected from the group consisting of the above-mentioned oxides are Nb, Mn, Si, Zr, Mg, Ca, Ti And an oxide obtained by selecting one or more of the groups consisting of aluminum (A1) and yttrium (Y); the aforementioned nitride Titanium nitride (TiN), tantalum nitride (ZrN), vanadium nitride (VN), tantalum nitride (TaN), aluminum nitride (A1N), boron nitride (BN), tantalum nitride (NbN) More than one selected from the group consisting of cerium nitride (Si3N4) and cerium dioxide-Si Nitrogen (Si02-A1N). 8 201011112 Further, in the present invention, the tungsten carbide-metal boride-cobalt-gold alloy powder is first fired from a mixed powder of tungsten carbide and cobalt to form a metal compound or tungsten carbide therebetween. The composite compound is then added to the tungsten carbide-cobalt intermetallic compound or the tungsten carbide composite compound, and a mixed metal boride is added to make a particle size of 5 to 50 μm through a binder.

Further, the present invention is particularly effective in the use of a roll member for a molten metal plating bath containing A1 in a plating solution component. [Embodiment] The molten metal plating tank, particularly a material having durability against molten zinc-aluminum alloy, is most widely known as a carbide, an oxide, a nitride, a boride, etc., and of course, the inventor's research will naturally It is desirable to have a mixture of these materials in the molten metal plating bath parent material, such as refining a carbonized ore-metal boride-cobalt-based porcelain gold, etc., but it is not enough to do so, and it is necessary to make the molten film. Surface treatment of pore sealing. That is to say, the method of the present invention for sealing is effective, and it is necessary to coat and fill a metal oxide having a more affinity with oxygen than the oxygen, or a mixture of the oxide and the nitride, which will be described in detail below. . Further, a method of sealing a hole of a tungsten carbide-cobalt-gold alloy spray film coated on a surface of a steel substrate may be employed, and a mixture of a complex oxide and a nitride may be used, which will be described in detail later. Referring to the third drawing, a standard generation free energy temperature diagram of a representative of the aforementioned metal oxide used in the present invention is disclosed. Also related to molten metallization, for example, in the zinc-min alloy, it is well known that molten metal is a very active component, and when it coexists with other metal oxides 9 201011112, it will gradually reduce other metal oxides and change its metal. The bear, it will become a more stable oxidation mark (ΑΙΑ3) ^ This phenomenon also relates to the standard generation free energy of oxide formation in metal thermodynamics and temperature. That is to say, according to this relationship, for example, chromium oxide (CqO3), which is known to be a tungsten-cobalt spray film, is thermodynamically more unstable than alumina (Abo3) in the case of metal plating temperature (46 〇t). In the case of balance, there is a reduction in coexistence with metallic aluminum and the possibility of generating metallic chromium. Therefore, the inventor in this context - first of all, to replace the carbonized crane, a gold, must use carbonization that is not easy to wet the molten metal and has heat resistance. Tungsten-metal boride-cobalt porcelain gold is premised, The work is the sealing agent or sealing material on the spray film, and the metal oxide which is more stable than chromium oxide (cr203) is discussed. According to the inventor's research, the so-called metal oxide which is thermodynamically more stable than chromium oxide (Cr2G3) t, which is formed by the reduction of the molten metal, suggests that it is entangled with the key solution. The affinity between them has the effect of preventing the adhesion and growth of iron-aluminum, iron-aluminum, metal compounds on the surface of the cavity in the bath which is impregnated in the plating solution. The above metal oxide layer is coated on the tantalum carbide-metal material-Ming-type molten skin medium with the above metal ion-containing aqueous solution and the mixed suspension of the aqueous solution disk nitride to cause water and reaction, and hydrolyzed The condensation is carried out by a heat-firing method, which is formed by permeating the surface of the molten film and the pores of the surface layer of the film. In addition, those which are more susceptible to oxidation than chromium and form the genus of the genus Quercus include: niobium (Nb), manganese 201011112 (Μη), bismuth (Si), zirconium (ζΓ), magnesium (Mg), calcium (Ca). , titanium (Ti), aluminum (A1) and bismuth (Y). That is, in the present invention, a metal salt such as an aqueous solution of a metal salt or an alkoxide such as a metal as a substrate is used as a suspension of a mixture of aggregates, and the suspension is applied to the suspension. After the above-mentioned molten film is dried on the upper surface, it is formed by a firing method. ❹ Table 1 is a 90gm thick tungsten carbide-metal boride-cobalt-based porcelain gold spray film on the surface of 25ιηιηφχ300 mml carbon steel. Then, the surface of the sprayed film is coated with chromic acid aqueous solution (Comparative case number) 5), wall acid wrong aqueous solution (suitable for case number 丨), cerium nitrate aqueous solution (suitable for case number 2), magnesium nitrate (suitable for case number 3), aluminum nitrate (not case number 4), and then 55 (rcxl hour) The condition is fired and placed in a bath of zinc-0.1% aluminum, 46 ° C plating bath, soaked for 3 〇〇 hours to compare the surface of the crystalline iron - aluminum or iron - aluminum - zinc metal The degree of adhesion of the compound. As shown in the table, there is no obvious adhesion or accumulation of intermetallic compounds in the description of each test material; these test materials were sliced, and the presence of the surface of the film was quantitatively analyzed by SEM X-ray image. Case (No. 5), the obvious case of the present invention (number I 2' 3) is superior. This can be considered as the oxidation of the above metal by impregnation on the tungsten carbide-metal boride-cobalt-solubilized film. And (iv) molten lead to differences in the reduction reaction caused by #. That is, the microscopic point of view, regardless of which kind of case, although there will dazzle ^ +

If, the dissolution of the metal component in the film, but because the tb is less than the % of the case 5, the thermodynamic reactivity of the chromium oxide is poor. The metal chromium provides a growth site similar to the iron-aluminum intermetallic compound. ), resulting in increased adhesion of the compound. 11 201011112 Table 1 Division number 1 Suitable case 2 3 Not case 4 Comparative case 5 Chromic acid aqueous solution coating solution Zirconium nitrate aqueous solution - Aluminum adhesion after immersion in Ming solution (SEM) Treatment of carbonized 4-20wt% rotten town) Comprehensive judgment of the adhesion state of -l2wt% drill film

Aluminum nitrate water soluble 〇 X (- part peeled off) 〇: good for practical use X: practically impossible ◎: excellent

Further, the present invention is not limited to the above-mentioned metal oxides, as described above, 'a mixture of these oxides and nitrides may be used; that is, a tungsten carbide-metal boride-cobalt-based molten film sealant As the coating material and the sealing material used, a mixture of the above metal oxide and nitride may also be used. According to the investigation by the inventors, 'these nitrides have a large contact angle of 90 ° C or more for the molten zinc-aluminum alloy, and have a characteristic β which is very difficult to infiltrate, and the thermodynamic reaction with the coexisting molten aluminum compared with the chromium oxide. Low and stable. For the nitride, titanium nitride (TiN), zirconium vapor (ZrN), vanadium nitride (VN), tantalum nitride (TaN), aluminum nitride (A1N), boron nitride (BN), Niobium nitride (NbN), tantalum nitride (Si3N4), and hafnium oxide-aluminum nitride (Si02-AlN) (Sialon). On the other hand, the metal collar compound in the molten film covering the surface of the base metal can be suitably used for TiB2, ZrB2, HfB2, vanadium boride (VB2). ), a boronized button (TaB2), lanthanum boride (NbB2), nickel boride (NiB2), tungsten boride (W2B5 or WB), and chromium boride (CrB2). These metal borides are added to a ratio of 5 to 60% by weight. The reason is that when the amount of the compound is less than 5% by weight, the shed compound is difficult to exert the wetting property for the molten zinc, and on the other hand, even if it is higher than 60% by weight, the characteristic 12 • 201011112 is not particularly improved. Further, cobalt (c〇) mixed in the above film was added in the range of 5-20% by weight. The reason is that when the content is less than 5%, the bonding strength between the tungsten carbide and the metal boride particles constituting the molten film is weakened, and the crack is reduced and the adhesion to the base material of the steel is generated. On the other hand, when it is more than 2% by weight, the diffusion reaction of the inside of the film of the molten metal becomes large, and the adhesion of the foreign matter component also increases. Lu Next, the related manufacturing method of the present invention will be described. First, the suspension to be coated or sprayed on the surface of the base material is adjusted. The suspension is prepared by mixing the metal oxide and the nitride powder with a metal salt aqueous solution to form 〇. 5~1. 〇// m The average particle size, and then it is necessary to add the same powder as a suspension of the required concentration of the aggregate (1 〇 to 35 wt%), and the suspension is coated on the steel mother by dipping, coating or spraying. Tungsten carbide - metal boride - cobalt spray film. Then, it is heated and fired at a temperature of 550 ± 1 (TC), and the fine particles are fired on the molten film, and the micropores in the vicinity of the surface layer are also infiltrated and sealed. The method of the present invention will be described in detail. The formation of the underlying porcelain gold spray film: for the steel base material (roller base material) which needs to be subjected to the necessary surface treatment such as degreasing, washing, roughening, etc., coating and spraying Tungsten carbide-metal boride _Cobalt is a gold alloy. Here, the powder used for the spraying is a mixed powder of various raw material powders such as tungsten carbide, metal boride, cobalt, etc. , a mixture of tungsten carbide and cobalt and a method of firing & the intermetallic compound between the two, such as carbonized cobalt (Co^C) or tungsten carbide (wc) decomposition of 13 201011112 W6c2.54, W2C, etc. Next, the metal carbide compound is directly mixed in the tungsten carbide-drilling intermetallic compound powder, or mixed with an organic binder to make a powder having an average particle size of 5 to 5 Mm. Method that can be mixed out and The specific gravity of tungsten carbide has significantly different metal records, titanium boride (TiB2), nickel boride (NiB2), and chromium boride (CrB2). The spraying method of the present invention can use a plasma spraying method. Any of the methods in the high-speed flame (HV0F) spray method or the burst spray method is not particularly limited. ^ Table 2 shows the use of tungsten carbide (ffc)_2〇wt% chromium boride (CrB2)—丨5^% tungsten boride (Wed-Uwt% cobalt (Co) porcelain gold spray film with 9 (^m thick, covering 25ιηιηφχ300 with 1 carbon steel, these with the comparative case 3 using chromic acid aqueous solution, and the appropriate case 丨 nitric acid wrong aqueous solution plus nitrogen A suspension of boron (βν) mixed, suitable case 2 aqueous solution of zirconium nitrate and yttrium nitride (ShM mixed suspension, respectively coated and impregnated with 55 ° C for 1 hour as conditions Test materials. Then, these test materials were loaded into the end of the roller in the bath of zinc-0.1% 460 °C, and after 300 hours of flow impregnation, the iron/aluminum on the surface was observed. It is the adhesion of iron-aluminum-metal compound. As a result, when impregnated with the above metal oxide As such, the present invention is suitable for the case number i, the level of the number 2 is comparable to the comparative case number 3, and it can be considered that the adhesion amount of the intermetallic compound is small. Further, the use of the metal salt aqueous solution, for example, a zirconium compound, is not Only limited acid retardation (Zr(N〇3)4), zirconium hydroxide (Ζγ(〇η)4 · ηΗ20), barium sulfate hydrate (Zr(s〇4)2 · “π), carbonic acid Hammer 201011112 (Zr(C03)2), vaporized zirconium (ZrCl4), or a metal salt aqueous solution of other compositions of the present invention, Nb, Mn, Si, Mag (Mg), Nitrate, sulfate, carbonate, hydroxide, etc. of calcium (Ca), titanium (Ti), aluminum (A1), and yttrium (Y). [Table 2] Distinct number tungsten carbide (WC)-20wt% chromium boride (CrB2)-15wt% tungsten boride (W2B5)-12wt% cobalt (Co) porcelain gold spray film soaking solution after zinc-aluminum solution soaking Aluminium state (SEM) Suitable case 1 Mixture of chromic acid aqueous solution and cerium nitride (Si3N4) aqueous solution ◎ 2 Mixture of chromic acid aqueous solution and boron nitride (BN) aqueous solution ◎ Comparative case 4 Chromic acid aqueous solution 〇© 〇: For Practically good ◎: very practical in practice. In addition, the inventors focused on solving the problems that have been solved to achieve the object of the present invention. In addition to the use of chromium oxide (Cr203) as tungsten carbide - The basics of the sealing agent for the metal boride-cobalt-gold alloy spray film, on the one hand, the nitride which is thermodynamically more stable than chromium oxide (Cr203) has been noted for the material of the completion of the defect. Moreover, these mixtures are also prepared as the above-mentioned sealing agent. That is to say, in the study by the inventors, the nitride is a compound which is relatively difficult to wet-impregnate with respect to the molten metal zinc-aluminum® gold at a contact angle of 90 degrees or more. Moreover, this nitride has a lower thermodynamic reactivity with molten aluminum than chromium oxide. Therefore, when such nitride particles are present and close to the chromium oxide (Cr203) particles, the chromium oxide (Cr203) is reduced by the molten aluminum in the plating solution to form metallic chromium; but even so, the minute metal chromium portion is The probability of contact with the bath is also low. As a result, in the field of micro-vision, the metal chromium formed by reduction of molten aluminum exhibits affinity with the plating liquid component, and it can be said that iron-aluminum which prevents the surface of the roller body from being immersed in the plating bath is generated. Iron - 15 201011112 Adhesion and growth of aluminum-zinc intermetallic compounds. The method provided by the present invention is that the suspension of the chromium oxide (Cr〇3)-containing aqueous solution and the nitride mixture coated on the tungsten carbide-cobalt sprayed film is subjected to water and reaction, hydrolyzed, and subjected to condensation polymerization. According to the method of the calcination method, the method of coating the surface of the oxidized complex (Cr 2 〇 3) and the sulphate on the surface of the sinter-fired particle smelting film and simultaneously immersing the pores through the pores of the surface layer portion of the film . In the present invention, ammonium chromate ((NH4)2Cr〇4) or ammonium dichromate (NH4)2Cr2〇7 or the like may be used alone or in combination with the aqueous solution of chromic acid (Cr〇3). These aqueous solutions of chromic acid and chromate compounds are decomposed by calcination by heating, and all of the final products have characteristics of producing fine chromium oxide (Cr2〇3) particles. Therefore, if the final product is a chromium oxide (Cr2〇3) compound, vaporized chromium (CrCl2), chromium sulfate (CrS〇4), chromium carbonate (CrC〇3), or chromium hydroxide (Cr (0H) can be used. ) 3) Wait. Therefore, in the present invention, various chromium compounds of this type are collectively referred to as "chromium oxide-containing mixtures" for convenience of writing.

In the present invention, the above-mentioned chromic acid aqueous solution, that is, the nitride used in combination with the chromic acid is titanium nitride (TiN), nitrided (ZrN), vanadium nitride (VN), or tantalum nitride ( TaN), aluminum nitride (Α1Ν), nitride side (ΒΝ), tantalum nitride (NbN) 'tantalum nitride (Si3N4), and cerium oxide-aluminum nitride (Si〇2_AlN) (Sialon) Select more than one of the groups. Further, the mixed suspension of the chromic acid aqueous solution and the nitride is adjusted so that the powder of the above nitride having an average particle size adjusted to 0.5 to 1. ym is mixed with the aqueous chromic acid solution. In addition, chromium oxide powder may be added as an aggregate as necessary. The suspended solid adjusted by 16 201011112 is coated on the tungsten carbide-cobalt molten film covered on the surface of the steel base material by coating or spraying. Then, it is heated and fired at a temperature of 550 to 700 ° C, and the fired fine particles are coated on the molten film while being infiltrated and impregnated into minute pores in the vicinity of the surface layer. Table 3 is the use of tungsten carbide. -Cobalt porcelain gold spray film is coated with 2 5mm X 3 0 0 mm 1 carbon steel at 9〇/iin thickness. These are mixed suspension of 1 chromic acid aqueous solution and cesium nitride (SiaN4), 2 chromic acid aqueous solution and a mixed suspension of boron nitride (BN), a mixed suspension of 3 chromic acid aqueous solution and aluminum nitride (A1N), and a comparative example 4 only a chromic acid aqueous solution, each coated and impregnated after coating; at 550 C xl The material burned under the conditions of the hour is used as a test material. And these materials are installed in the end of the roller body in the zinc-0.1% aluminum 460 ° C plating solution, after 300 hours of flow impregnation, 'Comparative observation of the surface of the crystalline iron-aluminum or iron-aluminum- The extent to which zinc intermetallic compounds adhere. According to this result, when the suitable case number 1, number 2, and number 3 of the present invention are compared with the comparative case number 4 φ, the superiority of the amount of adhesion of the intermetallic compound can be considered. In addition, the test material described above was cut and cut, and the presence of the surface of the film was semi-quantitatively analyzed by SEM characteristics. As shown in Table 3, compared with Comparative Case No. 4, the number 1 of the appropriate case of the present invention was determined. Advantages of ~ f ° This part of the 'burned film of a mixture of chromium oxide and nitride impregnated on the carbonized n-gold molten film and a part of the filled layer' although a chromium oxide Some of them are also made of extremely fine metal complexes due to melting, but they can reduce the contact with mineral fluids due to the adjacent nitrides. In addition, since the nitride in the vaporization butterfly (10) 17 201011112 has a solid-slip function, it can reduce the contact and adhesion with the metal plating solution in the grain boundary field. [Table 3] Immersion liquid of the tungsten carbide-cobalt-gold alloy spray film of the difference number - adhesion state of aluminum after immersion in aluminum liquid (SEM) Suitable case 1 Mixture of aqueous solution of chromic acid and cesium nitride (Si3N4) ◎ 2 Mixture of chromic acid aqueous solution and boron nitride (BN) aqueous solution 3 Mixture of chromic acid aqueous solution and aluminum nitride (A1N) aqueous solution ◎ Comparative case 4 chromic acid aqueous solution ~~~~~ 〇: Good for practical use ◎: Excellent 0 [ Example 1] The experimental material of the first embodiment is a surface of a roller body (made of 13Cr stainless steel) having a diameter of 250 mm and a surface length of 1800 mm, and a scale of tungsten carbide - 25 wt% tungsten boride (W2B5) - 5 wt% titanium boride ( TiB2)-12wt% cobalt (Co) porcelain gold spray film thickness of 0.08~0.09mm, and coating the suspension of the following components on the carbonized town-drilled gold gold spray film, after drying, in the atmosphere, 600 °C ± 20 ° C x 2 hours of burning. This roller body is suitable for the case of supporting the roller body (3) in the plating tank containing the 0.12% molten galvanizing bath device (1) (please refer to Fig. 1). Composition of the mixed suspension for coating: The suspension was made up of a solution of a wrong aqueous solution of nitrate (concentration: 30% by weight of Zr02), and a part of stabilized zirconia (Zr02 · 8Υ2〇3) was added to have a particle size of 1 to 1 0. " m. Thus, the support roll body (3) was actually used in a hot-dip stencil for hot-dip galvanized steel sheets at 460 °C. As a result, in the 20th day after the operation, the recorded steel plate with no problem and stable surface quality can be transmitted. Then, the support body (3) was lifted from the tank to inspect the surface of the roll body, and the precipitation and adhesion of the intermetallic compound of the iron-Ming, the iron-Ming-zinc were hardly observed by visual inspection. 18 201011112 Thereafter, in order to remove metallic zinc adhering to the surface of the roll body, the support roll body (3) was immersed in a μ sulfuric acid (myocardium) aqueous solution for 15 minutes to remove the metal word. Next, it was reinstalled into the molten, and used on the moth/degree device (I), and the operational life was almost the same as the initial use. According to the implementation of the case, the support roller body (3) has a durability life of 5 to 15 days, and the support roller body (3) uses a total of about 8 mouths to prolong the life of 2. 5 times, and obviously Improve the surface quality of the steel plate. [Embodiment 2] The experimental material of the case 2 is a roller body having a diameter of 7 mm and a face length of 8 mm (13Cr stainless steel, but the surface of the roller body is previously constructed to have a depth of 0.25 to 0.35 mm, pitch (Pitch) 2.5 mm threaded foreign matter discharge groove). The surface is covered with a carbonized town (wc)-30wt% chrome (CrB2)-12wt% cobalt porcelain gold spray film having a thickness of about 0.08~〇.〇9mm, and tungsten carbide-cobalt spray on the surface of the roller body. Apply the following suspension on the film, dry and then in the atmosphere at 60 (TC ± 2 (rc X 2 hour calendered body. 0 mixed suspension composition; this suspension is using a commercial nitric acid aqueous solution ( Concentration··Y2〇3 conversion 30% by weight) 'Additional weight of boron nitride (bn) is used as the aggregate. The roll body according to the above treatment is regarded as the support roll of the same hot-dip galvanizing apparatus (1) as in the first embodiment. The actual use of the body (3), as a result, almost the same as the implementation case, although it was once pulled up by the plating tank for pickling, but it can be extended to about 45 days of use. [Embodiment 3] The experimental material of Case 3 is the surface of a roll body (made of 13Cr stainless steel) with a diameter of 250 mm and a face length of l8〇〇mm 19 201011112, coated with tungsten carbide _12% cobalt porcelain gold melting. Film thickness of 0.08~0.09mm, and on this tungsten carbide_cobalt porcelain gold spray film After the suspension of the following components is dried, it is 60 (TC ± 2 (rCx 2 hours) in an atmosphere. Example 3 is a support roller for a molten galvanizing bath containing 0.12% aluminum. Case (refer to the first figure) 〇L float composition. Specific gravity 1. 6 〇 chromic acid aqueous solution and particle size range 5~1 〇❹

The tantalum nitride was added to the water solution adjusted to a specific gravity of 19 to 21 by the purified water, and the mixing ratio (volume ratio) was 1:1. The above support roller body is obtained at 46 〇. It is actually used in the hot-dip galvanizing tank of bismuth. As a result, after the operation, %2〇曰 was obtained, and a metal plated steel plate with no problem and stable surface quality was obtained. Thereafter, the support roller body was lifted from the groove to inspect the surface of the parent body, and visual inspection revealed that the precipitation of the intermetallic compound of the iron or the metal was hardly observed. Thereafter, in order to remove the metal adhered to the surface of the roll body, the support roll body was dipped for 15 minutes to remove the metal zinc. The use of the above-mentioned, and the previous support, the above-mentioned support roller body can significantly improve the operating life of the steel sheet and then re-installed to the molten zinc for almost the same period of use. The support roller body has a durable life of 5 to 15 and can be used twice to extend the life by 2.5 times, while the surface quality. [Example 4] The experimental material of the implementation case 4 is a diameter 亀m, a surface roller body...not made of steel, but the surface of the clock is pre-constructed to be 20:201011112 degrees 0.25~〇.35mm, pitch (Pitch) 2 5mm thread processing foreign matter discharge groove). The surface is covered with a carbonized crane (wc)_i2% diamond-gold-solubilized film with a thickness of about 0.08~〇.〇9mm, and the following suspended matter is coated on the surface of the carbonized heparin on the surface of the parental body. After drying, the roll body was fired at 600 ° C ± 20 ° C x 2 hours in an atmospheric environment. Suspension composition: specific gravity 1.60 chromic acid aqueous solution and particle size 5 to 1 〇um boron nitride (BN) particles were added to purified water to adjust the specific gravity to 13 〇, and the mixing ratio (volume ratio) was 1:2. The roll body according to the above treatment was actually used as the in-slot roll body in the same melt galvanizing apparatus (refer to the first figure) as in the embodiment. As a result, in the past technology, fine surface defects adhering to the surface of the roller body in the groove gradually increase the surface defects on the plated steel sheet, and the roller body is replaced almost every 5 days in order to increase the allowable limit of the galvanized surface. However, in the above-described example, the in-slot roll body can obtain a zinc-zinc steel plate having a stable surface quality within two weeks from the start of the operation. Moreover, in the tank, the surface of the tank is taken out from the surface of the mine to detect the adhesion of the iron-Ming, the iron-Ming-Zinc metal compound which causes crushing of the steel sheet. The surface quality of the galvanized steel sheet has a stable effect. According to the above description, according to the present invention, the surface of the steel plate for guiding the parent body of the molten iron metal groove coated with the tungsten carbide-metal shed compound-cobalt-gold alloy spray coating is coated or sprayed or impregnated. After the method is coated with a thermodynamically stable oxide and/or a nitrogen-containing aqueous solution, a thermostatically stable protective layer for the metal ore can be formed by the firing method, and the iron-Ming and iron present in the key solution are formed. -Ming-zinc intermetallic compound particles are also not easy to grow, and have a good durability of 21.201011112 and can produce high quality steel sheets with less metallized surface defects. On the other hand, according to the present invention, the surface of the steel sheet guiding roll body for the molten metal plating bath coated with the tungsten carbide-cobalt-based porcelain gold powder is coated or sprayed or immersed in a manner such as impregnation to coat the nitride. The w-float composed of the chromic acid aqueous solution can also form a thermostatically stable protective layer for the metal plating solution by the firing method, and the iron-aluminum and iron-aluminum-zinc-gold intermetallic compound particles present in the plating solution are also It is not easy to grow, it also has good durability, and it can produce high-quality steel sheets with few key metal surface defects. [Simple description of the drawings] The first figure is a schematic diagram of a molten metallization equipment. The second A is a schematic view of the groove on the surface of the roller body in the groove. The second B is a representation of another groove in the surface of the roller body in the groove. The third figure is an illustration of the aforementioned metal oxide used in the present invention. Standard generation free energy temperature line diagram. Table [Description of main parts symbols] (1) Metal plating equipment (2) In-tank roller body (3) Supporting roller body (4) (4') spiral groove 22

Claims (1)

-201011112 X. Patent application scope: 1. A roller body part for molten metal plating solution, the surface of which is coated with a tungsten carbide-metal boride-cobalt-based porcelain gold-plated film on the surface of the steel substrate, in the above-mentioned carbonization The surface of the tungsten-metal boride-cobalt-based porcelain gold-soldered film is formed while the metal oxide of the metal oxide having a greater chemical affinity with oxygen or a mixture of the oxide and the nitride is formed. The micropores present in the vicinity of the surface layer of the aforementioned molten film are also filled with the above-mentioned oxide or a mixture of an oxide and a salt thereof to be fired into fine particles. The roller body part according to claim 1, wherein the aforementioned tungsten carbide-metal boride-cobalt-based porcelain gold spray film is made of titanium oxide (TiB2) and boride. Error (ZrB2), boronation (HfB2), boronic hydride (VB2), boronized button (TaB2), lanthanum boride (NbB2), nickel boride (NiB2), tungsten boride (WZB5 or WB), and The group consisting of chromium boride (CrB2) is selected from the group consisting of more than 5 to 60 wt% of metal-containing boride, 5 to 20 wt% of cobalt (c〇), and the remainder is tungsten carbide. β ❹ 3 . The roller body member according to Item 1, wherein the oxide is a sharp (Nb), a violent (Μη), a dream (Si), a wrong (Zr), a magnesium (Mg), a (Ca), or a titanium ( One or more oxides are selected from the group consisting of Ti), aluminum (A1), and yttrium (γ). 4 The roller body member according to the above-mentioned patent application, wherein the nitride system is made of titanium nitride (TiN), nitrided (ZrN), nitrided (VN), nitrided (TaN), One of a group consisting of aluminum nitride (A1N), boron nitride (BN), niobium nitride (NbN), niobium nitride (SisN4), and ceria-aluminum nitride (si〇2-AlN) The above. 23 201011112 '5, a method for producing a roll body part for a molten metal plating solution, characterized in that a tungsten carbide-metal boride-cobalt-based gold powder is coated on a surface of a steel substrate to form a tungsten carbide-metal a boride-cobalt-sprayed film, followed by coating a metal oxide having a greater chemical affinity than chromium's and antimony on the surface of the tungsten carbide-metal boride-cobalt-based porcelain gold-plated film or oxidizing it After the mixture of the substance and the nitride and the suspension of the aqueous metal salt solution, the mixture is heated and fired to form a fine pore in the vicinity of the surface of the tungsten carbide-metal boride-cobalt-based porcelain gold-plated film and the film layer. And filling the fired oxide or a fired mixture of the oxide and the nitride. 6. The method of manufacturing a roller body member according to claim 5, wherein the powder of the tungsten carbide-metal boride-cobalt-based porcelain gold-solder film is first fired into tungsten carbide and cobalt (Co). The mixed powder is used to form the intermetallic compound or the carbonized town composite compound, and then the mixed metal compound is added to the carbonized town-junction intermetallic compound or the tungsten carbide composite compound by the binder (5). Particles of ~50/zm size ^ as a use. The method for manufacturing a roller body member according to claim 5, wherein the tungsten carbide-metal boride_cobalt-based porcelain gold is self-contained titanium boride (TiB2) or lanthanum boride ( ZrB2), lanthanum boride (HfB2), vanadium boride (VB0, TaB2, NbB2, NiB2, tungsten boride or WB), and chromium boride (crB2) Among the group formed, one or more metal borides are selected in an amount of 5 to 60% by weight, a material containing cobalt (Co) 5 to 20% by weight, and the remainder of which is a composition of tungsten carbide is sprayed. 8. The method of manufacturing a roller body member according to claim 5, wherein the oxide is derived from niobium (Nb), manganese (Mn), niobium (Si), and (Zr). One or more oxides selected from the group consisting of magnesium (Mg), calcium (Ca), titanium (Ti), aluminum (A1), and (Y). 9. The method of manufacturing a roller body member according to claim 5, wherein the nitride is made of titanium nitride (TiN), zirconium nitride (ZrN), vanadium nitride (VN), Nitride button (TaN), aluminum nitride (A1N), boron nitride (BN), tantalum nitride (NbN), tantalum nitride (3^, and cerium oxide-nitrogen hydride) (81〇2_ One or more selected from the group consisting of humans and sputums. 10· A roller body member for molten metal plating solution, which is a roller body coated with a tungsten carbide-cobalt-gold alloy molten film on the surface of a steel substrate. a mixture of a chromium oxide and a nitride is formed on the surface of the tungsten carbide-cobalt-gold alloy molten film, and the micropores in the vicinity of the surface layer of the molten film are filled with the foregoing chromic acid and nitride. The roll body member according to claim 10, wherein the nitride system is made of titanium nitride (TiN), nitriding hammer (zrN), arsenic nitrogen. Vanadium (VN), nitride button (TaN), aluminum nitride (Α1Ν), boron nitride (ΒΝ), tantalum nitride (ΝΜ), tantalum nitride (si, 4), And one or more selected from the group consisting of cerium oxide-aluminum nitride (Si〇2_AlN). 12) A method for producing a rolled body part for a molten metal plating solution, characterized in that carbonized surface is coated on a steel substrate a tungsten-cobalt-gold alloy spray, followed by coating a suspension of a mixture of an aqueous solution of chromium oxide and a nitride on the surface of the tungsten carbide-cobalt-gold alloy spray film, followed by heating and firing, in the foregoing tungsten carbide - The surface of the cobalt-gold-gold fused film and the tiny pores existing near the surface layer of the film are characterized by the coating and filling of the firing mixture. 25 .201011112 13 · Manufacture of the roller body parts as described in the scope of claim 1 The method 'is characterized by 'the aforementioned nitride system is titanium nitride (TiN), zirconium nitride (ZrN), vanadium nitride (VN), nitride nitride (TaN), aluminum nitride (A1N), nitride One or more selected from the group consisting of boron (BN), niobium nitride (NbN), tantalum nitride, and SiOfAlN. page 26