JP5326121B2 - Mold for molding molten glass lump and method for producing the same - Google Patents

Description

  The present invention relates to a molten glass lump-molding mold and a method for producing the same, and in particular, is a new proposal characterized by the structure of a coating layer formed on the surface of a molding mold that contacts the molten glass lump.

Generally, a glass bottle etc. are manufactured through the following processes. For example, a raw material composed of main raw materials such as soda ash, limestone, and glass scraps, and auxiliary raw materials such as mirabilite (Na ₂ SO ₄ ), various colorants, and decolorizers is heated to a temperature of about 1500 to 1600 ° C. After melting and removing bubbles, etc., it is adjusted to a temperature of about 1100 ° C. to 1200 ° C. according to the weight and shape of the bag, and a molten glass lump (a high-temperature lump glass in a softened state) through a feeder ) Is finally supplied to a iron making machine, that is, a molding die.

  FIG. 1 shows an outline of a general glass bottle manufacturing process. Here, 1 in the figure indicates molten glass, 2 indicates a glass melting furnace, 3 indicates a work chamber, 4 indicates a feeder, 5 indicates an orifice, and 7 indicates a molten glass lump. The molten glass 1 in the melting furnace 2 is processed in the working chamber 3 and the feeder 4, and then cut into a glass lump 7 having an appropriate size by a cutting machine 6. Then, it passes through a series of rain gutter-shaped conveying members called a funnel 8, a scoop 9, a trough 10, and a deflector 11, and is fed into a mold for mold making 12 to form a required glass bottle.

By the way, the following properties are required for the surface of a cast iron substrate such as a molding die in contact with the molten glass lump.
(1) The coefficient of friction with molten glass is small and the slipperiness is good.
(2) It has excellent high temperature wear resistance and can maintain the initial performance for a long time.
(3) Dirt is difficult to adhere and does not contaminate the molten glass.
(4) Maintenance and inspection are easy and can be regenerated.
(5) Be economical.

  In particular, for a mold for molding a molten glass lump, it is important that the frictional resistance is small, the glass lump can be smoothly inserted into the mold, and the moldability of the glass bottle after molding is excellent. It is.

  Conventionally, such a requirement has been dealt with by applying a lubricant composed of graphite powder (graphite powder) and resin or drying oil to the inner surface of the molding die in contact with the molten glass lump and the conveying member. Yes. While this conventional method has advantages such as easy operation, good sliding of the molten glass lump, and no adverse effect on the quality of the glass, the consumption rate of the graphite powder is large and it is frequently applied. There is also a drawback that it is necessary. Further, the lubricant containing the graphite powder has the property of being easily scattered, and thus has a drawback of not only deteriorating the working environment but also causing the operator to feel uncomfortable.

As a countermeasure, proposals have been made to apply various surface treatment films to the surface of the molding die (member) in contact with the molten glass lump, the conveying member, the plunger, etc. Has improved considerably. For example,
(1) In Patent Documents 1 to 5, a cermet sprayed coating using a self-fluxing alloy, carbide (Cr ₃ C ₂ ), or oxide ceramic particles is coated on the surface of a molding plunger or the surface of a glass lump conveying member. Methods and Patent Documents 6 to 7 disclose a method of coating a nitride, carbide, oxide film or the like on the surface of a molten glass lump supply jig.
(2) Patent Document 8 discloses a technique for coating a thin film such as TiN, TiCN, TiB ₂ , or SiC by a CVD method or a PVD method.
(3) Patent Document 9 discloses a method of coating a sheet glass forming roll with a heat-resistant and corrosion-resistant alloy film.

  On the other hand, the inventors also proposed a film in which a metal having a low free energy of carbide generation such as Mo, Ta, W or the like is added as a metal component of a carbide cermet on the surface of a bowl-shaped conveying member of a molten glass lump (Patent Document 10). Furthermore, a thermal spray coating member was proposed (Patent Document 11) using particles obtained by coating a thin film of Ni, W, Ti, Al or the like on the surface of graphite particles having excellent lubricity.

  There is also a proposal for coating various types of surface treatment film on the inner surface of a mold for molding a molten glass lump. For example, Patent Documents 12 and 13 disclose a metallic film composed mainly of Cu, Al, and Cr, with the balance being Fe. Patent Documents 14 and 15 disperse BN and colloidal silica on the mold surface. A technique for applying a dried aqueous solution and drying it to form a film is disclosed, and Patent Documents 16 to 18 disclose a technique for coating a carbide or a carbide cermet film.

JP 54-146818 A JP-A-2-111634 Japanese Patent Laid-Open No. 4-139032 JP-A-3-290326 JP-A-11-171562 Japanese Patent Laid-Open No. 2-102145 JP-A 63-297223 JP-A-1-239029 Japanese Patent Laid-Open No. 3-137032 JP 2002-20126 A JP 2002-20851 A JP-A-8-109460 JP-A-8-120435 Japanese Patent Laid-Open No. 2003-119049 Japanese Patent Laid-Open No. 2003-119047 JP-A-62-158122 JP-A-2-146133 JP 2002-178034 A

  Among the above-described conventional techniques, for example, in the case of various surface treatment films in which a lubricant containing graphite powder is applied to the mold surface, there are the following problems. The mold surface coated with graphite powder has good lubricity and has the advantage that it does not wrinkle even when it comes into contact with molten glass, but the lubricant is liable to volatilize and contaminates the work environment. It is easy. In addition, since the determination of the application method and the application time all depend on the experience of skilled workers, there is a problem that it is difficult to unmanned operations such as automation and robotization.

  In addition, conventional surface treatment techniques such as carbide cermet, oxide, nitride, heat-resistant alloy by thermal spraying method, CVD, PVD, etc. are insufficient, although some effects are recognized compared with the case of no treatment, There is a problem that it is often necessary to use in combination with a graphite powder coating technique.

  By the way, conventionally, because the conditions and characteristics required for the molten glass lump conveying member and the “glass lump forming mold” which is the subject of the present invention are clearly different, the originally required characteristics are Where appropriate surface treatment is required, in reality, sufficient consideration has not been made and these remain unsolved.

  For example, for the conveying member, since the contact pressure between the hot molten glass lump and the surface treatment film formed on the surface thereof is small and the contact time is short, generally the lubrication performance of the film is an important management target. .

  On the other hand, in the case of a molding die, since the contact time with the molten glass block is long, heat resistance and high-temperature wear resistance are required, and the surface treatment film surface has a fine roughness and slight wrinkles. Since it is easily transferred to the glass surface, it is required to use a film or a material that can be easily processed such as grinding and polishing of the film surface. Moreover, the entrance of the molding die for making iron is generally narrow, and the lubricity of the molten glass mass passing through it and the releasability of the glass product after molding are also important characteristic factors. In fact, surface treatment coatings with characteristics, particularly thermal spray coatings, have not yet been developed.

In recent years, safety awareness of the work environment and glass molded products has been improved, and measures and examinations regarding the generation of harmful substances are also necessary. In this regard, conventional thermal spray coatings are often made of Cr-containing compounds such as chromium carbide (Cr ₃ C ₂ ), Ni—Cr alloys, self-fluxing alloys, and Cr-containing alloys. Although there is a possibility that a compound of hexavalent chromium that is oxidized in the environment and partially harmful is generated, these problems remain unresolved.

  The object of the present invention is to solve the above-mentioned problems of the prior art, in particular, excellent in heat resistance and high temperature wear resistance, and excellent in releasability from molten glass lump, as well as the quality of glass products. An object of the present invention is to propose a mold for molding a molten glass lump for manufacturing a product excellent in safety and safety and a method for manufacturing the same.

In order to solve the above-mentioned problems of the prior art and achieve the above-described object, in the present invention, the inner surface of the mold that is in contact with the molten glass lump is directly or via an undercoat, and the content of W Ni—W alloy having a W content of 0.5 to 10 mass%, a W content of 0.5 to 10 mass%, a Cr content of less than 20 mass%, and a W content of 0. One selected from Ni—W—Cr— (P—B) alloys containing 5 to 10 mass%, Cr content of less than 20 mass%, and further containing at least one of P and B of 7 mass% or less. propose a Ni-base heat-resistant alloy of one or more Ni and W as essential components, the molten glass gob molding die, characterized in that it is coated formed by spray coating a metal boride cermet consisting of The

Further, in the present invention, the content of the metal boride and W having a particle size of 5 to 60 μm is directly or via an undercoat on the inner surface of the molding die in contact with the molten glass lump. A Ni—W alloy having a W content of 0.5 to 10 mass%, a Cr content of less than 20 mass%, and a W content of 0.5 to 10 mass%, Essentially, at least one of Ni and W selected from Ni—W—Cr— (P—B) alloys having a content of less than 20 mass% and containing 7 mass% or less of at least one of P and B, respectively. A metal boride cermet sprayed material composed of a Ni-base heat-resistant alloy as a component is applied to any one of a spraying method selected from an atmospheric plasma spraying method, a low pressure plasma spraying method, a high-speed flame spraying method, and an explosion spraying method. Sprayed I propose a method for producing a molten glass gob molding die, which comprises coating forming a metal boride cermet thermal spray coating having a thickness of 50 to 1000 [mu] m.

In the present invention,
(1) The metal boride cermet sprayed coating has a smooth surface with a surface roughness Ra of 2 μm or less and Rz of 4 μm or less,
(2) The metal boride may be any one or more metal borides selected from TiB ₂ , ZrB ₂ , HfB ₂ , VB, TaB, NbB, W ₂ B ₅ , CrB ₂ , NiB and MoB. be contained ~90mass%,
(3) The metal boride cermet sprayed coating in which the heat-resistant alloy component of the cermet is a Ni—W—Cr— (P—B) alloy is heat-treated at 300 to 700 ° C. for 0.5 to 5 hours. Being a thermal spray coating,
(5) The undercoat is any one selected from Ni—Al, Ni—Cr, Ni—Cr—Al, self-fluxing alloy, MCrAlX alloy (where M is Co and / or Ni, and X is a rare earth element). A spray coating of one or more alloys, the film thickness being 50-150 μm,
Provides a more preferred configuration.

  According to the present invention configured as described above, in addition to being excellent in heat resistance and high-temperature wear resistance, it is excellent in releasability from a molten glass lump, and in addition to maintaining initial mold dimensional accuracy over a long period of time, It can greatly contribute to the production of high quality glass molded products.

  Further, according to the method of the present invention, no harmful hexavalent chromium compound is generated from the spray coating component, and a safe and hygienic working environment can be provided, and a glass product can be produced safely. . In particular, since the regular graphite powder coating operation on the mold member surface, which has been conventionally employed, can be omitted or the frequency of coating can be significantly reduced, the generation of the hexavalent chromium compound can be prevented and the working environment can be greatly improved. Contribute.

It is a basic diagram of the glass bottle manufacturing process which shows the outline of the conveyance process of a molten glass lump, and the supply process to the metal mold | die for shaping | molding. It is an electron micrograph which shows the cross-sectional condition of the Ni-20mass% Cr alloy particle which coat-formed the Ni-WP alloy by the electroless-plating method. (A) is a cross section of the entire particle, and (B) is an enlarged photograph of the coated Ni—WP alloy film.

  In order to solve the above-mentioned problems of the prior art, as a result of intensive experiments and researches, the inventors have developed the present invention according to the following solution means, and the details of the configuration will be described.

(1) Metal boride cermet thermal spray coating, especially composition and characteristics of thermal spray powder material composed of metal boride cermet The metal boride cermet thermal spray powder material used in the present invention is composed of the following metal boride and refractory metal / alloy. It is composed.
(A) Boride: TiB ₂ , ZrB ₂ , HfB ₂ , VB, TaB, NbB, W ₂ B ₅ , CrB ₂ , NiB, MoB (Note that the molecular formula of boride varies depending on the manufacturing conditions, so it is absolute Not listed here, according to the indication of the commercial product
(B) Ni-based heat-resistant alloy;
(A) Ni-W alloy containing 0.5 to 10 mass% of W,
(B) Ni—W—Cr alloy containing 0.5 to 10 mass% of W and containing less than 20 mass% of Cr,
(C) Ni—W—Cr— (P—B) alloy containing 0.5 to 10 mass% of W and less than 20 mass% of Cr and containing at least one of P and B at a ratio of 7 mass% or less. ,

  The mixing ratio of the metal boride and the Ni-base heat-resistant alloy is in the range of boride: 20 to 90 mass%, Ni-base heat-resistant alloy: 80 to 10 mass%. These preferable mixing ratios are boride 40-60 mass% and the balance Ni-base heat-resistant alloy. In the present invention, the reason for limiting to the above range by focusing on the metal boride is that the boride is hard and excellent in high temperature wear resistance, and has a low reactivity with a glass block in a high temperature state, so that the fusion phenomenon is suppressed. It is because there is little possibility of inviting, and also, it is excellent in releasability (mold releasability) from the molded glass product. On the other hand, the above-mentioned refractory metal / alloy components are mixed with metal boride particles, thereby improving the mutual bonding force between the particles when forming a thermal spray coating, and a laminated structure of only metal boride particles. It is effective in preventing the formation of gaps seen at the time of forming a dense sprayed coating.

  In the metal boride cermet, if the content of the heat-resistant alloy is less than 10 mass%, the effect of adding the heat-resistant metal / alloy is not sufficient, while if the content of the metal boride is less than 20 mass%, Various properties such as excellent heat resistance, high-temperature stability, and high-temperature wear resistance of the chemical compound cannot be obtained. The thermal spray coating is cermetized to improve the adhesion between the substrate and the coating.

a. First, among the heat-resistant alloys, the Ni—W alloy contains W: 0.5 to 10 mass%, and the balance is Ni. Ni-based heat-resistant alloys composed of Ni and W are generally manufactured by a method of melting Ni and W in a vacuum melting furnace, and in this treatment, the amount of W added is 0.5 to 10 mass%. It is. When the W component is made into an alloy and a film thereof, the W component is excellent in releasability from molten glass, and since it is hard, it exhibits an effect of excellent high temperature wear resistance. In this regard, if the W content is less than 0.5 mass%, the effect of adding W is not manifested. On the other hand, if it is added in an amount of 10 mass% or more, the film is easily cracked. The Ni—W alloy used is a spherical particle having a particle size of about 5 to 60 μm by a pulverization method or a spray method from a small nozzle in a molten state.

b. Next, in a Ni—W—Cr-based Ni-based heat-resistant alloy, when Cr is contained, there is no practical problem in the peelability from the molten glass, and the heat resistance is good. However, when containing 20 mass% or more of Cr, the heat resistance and oxidation resistance are improved, but on the other hand, the adhesion between Cr or a trivalent Cr oxide (Cr ₂ O ₃ ) and molten glass is strong. (Deterioration of releasability) reduces productivity as a molding die, and depending on use conditions such as a high temperature environment, harmful hexavalent chromium compounds (mainly oxides CrO ₃ and Na ₂ Cr ₂ O ₇ ) Is expected and is not preferred. In addition, although commercially available Ni-Cr alloy contains Si, P, S, Fe, C, etc., these component elements have a small content and do not affect the object of the present invention. Therefore, there is no particular restriction.

c. Next, a Ni-W-Cr- (P-B) alloy, which is one of Ni-base heat-resistant alloys, uses a Ni-Cr alloy with a Cr content of 20 mass% as a matrix, and W is 0.5 to 10 mass. %, P and B are heat resistant alloys having a composition containing 7 mass% or less.

In addition to P and B, the Ni—W—Cr— (P—B) alloy containing Ni, W and Cr contains Ni—Cr alloy particles (particle size 5 to 50 μm) with a Cr content of 20 mass%. The surface of the alloy particles is manufactured by coating an alloy of Ni and W by an electroless plating method. P and B are components that are eutectoid during the plating process. Specifically, when sodium hypophosphite (NaH ₂ PO ₂ ) is used as a reducing agent for precipitating Ni ions and W ions on the surface of Ni—Cr alloy particles, Ni and W are precipitated together with 1 When about 7 mass% of P is co-deposited and a dimethylamine borane compound ((CH ₃ ) NHBH ₂ ) or a hydrogenated terraced compound (NaHB ₄ ) is used, B in the range of 1-7 mass% is Ni, Precipitates with W. When hydrazine (NH ₂ · NH ₂ ) is used as the reducing agent, only Ni—W is precipitated, and P and B are not included. According to the research of the inventors, if the content of P or B is in the range of 1-7 mass%, more preferably P: 2-7 mass%, B: 2-4 mass%, the thermal spray coating of the object of the present invention Since there was no problem in the performance of each, including the case of (NH ₂ · NH ₂ ) reducing agent, the allowable content thereof is preferably in the range of 1 to 7 mass%.

  Table 1 exemplifies the composition and temperature conditions of an electroless plating solution for forming Ni—WP and Ni—WB heat resistant alloy plating films. After the Ni—WP alloy is coated, a Ni—WB alloy film is subsequently formed, resulting in a thermal spray powder material containing P and B.

  FIG. 2 is an electron micrograph obtained by observing the cross-sectional state of a Ni-20 mass% Cr alloy particle after the Ni-WP alloy film was coated on the outer peripheral surface of the Ni-20 mass% Cr alloy particle by an electroless plating method. It can be observed that the Ni—WP alloy film is densely and evenly formed on the surface of the particles.

  Next, the metal boride particles and the Ni-base heat-resistant alloy particles containing Ni and W as essential components are granulated using a binder such as a vinyl chloride solution, and the metal boride having a particle size in the range of 5 to 60 μm. A thermal spray powder material made of cermet is used. If the particle size of the thermal spray powder material is less than 5 μm, continuous supply to the thermal spray gun may be difficult. On the other hand, if the particle size is larger than 60 μm, the melting and softening phenomenon is insufficient in relation to the thermal spray heat source. There is a case. In particular, since the melting point of borides is 2000 ° C. or higher, it is not preferable to use an excessively large particle size.

  The Ni-based heat-resistant alloy is obtained by coating WP and B by electroless plating on the surfaces of Ni and Ni—Cr alloy particles (hereinafter referred to as “matrix metal particles”). A metal film (hereinafter referred to as “alloy plating film”) made of alloys Ni—W, Ni—WP, Ni—WB, and Ni—WP—B has the following mechanism of action.

(B) The matrix metal particles coated with the alloy plating film reach the melting point within a short time when put in the thermal spray heat source, but the heating time is very short, so the alloy plating film and the matrix metal particles are It does not fuse with each other and average the chemical components. Incidentally, the velocity of the particles flying in the thermal spray heat source is 1/100 to 3/100 seconds in the atmospheric plasma spraying method and 1/500 to 1/1000 seconds in the high-speed flame spraying method.

  According to the experimental findings of the inventors, most of the thermal spray coating formed by the matrix metal particles coated with the alloy plating film is deposited in a state where the alloy plating film is coated, and the matrix metal particles are deposited on the surface. It has been confirmed that there is little exposure. For this reason, the Ni-base heat-resistant alloy used in the present invention is composed of an alloy plating film whose main component is Ni-W or the like whose surface of the particles is superior to the molten glass lump than the matrix metal. The characteristics of these components can be used preferentially.

  The thickness of the alloy plating film for exerting such characteristics is also affected by the size of the matrix metal particles. For example, when the matrix metal particles have a particle size of 5 to 50 μm, the thickness is 0.5 to A coating thickness of 10 μm is desirable, and a thickness of 1 to 5 μm is particularly preferable.

  That is, if this alloy plating film is thinner than 0.5 μm, the surface of the matrix metal particles cannot be sufficiently covered when heated in a thermal spraying heat source, and the releasability from the molten glass lump is improved. It becomes difficult. On the other hand, when the thickness is thicker than 10 μm, the coating effect is saturated, and the plating cost increases, resulting in an increase in film formation cost.

(B) Although Cr contained in the matrix metal particles is excellent as a heat-resistant and oxidation-resistant metal component, it may generate a harmful hexavalent chromium compound in a high-temperature environment containing oxygen. In this regard, the Ni—Cr alloy matrix formed by coating the alloy plating film as in the present invention is harmful because the matrix metal is not exposed not only in the thermal spraying heat source but also in the film formation. Formation of the valent chromium compound can be suppressed.

  In addition, when heated in a thermal spraying heat source, even when the alloy plating film and the matrix metal particles are completely fused, the Cr content in the matrix particles is diluted by the presence of the alloy plating film. The risk of the generation of can also be expected to shift to the safe side. For this reason, the Cr content in the Ni—Cr alloy used in the present invention may not necessarily be limited to less than 20 mass%. According to the findings from the experimental results, even with a Ni-22 mass% Cr alloy, It is possible to suppress the generation of the valent chromium compound.

(2) Forming method of sprayed coating To form a sprayed coating using a sprayed powder material of metal boride cermet, apply atmospheric plasma spraying method, low pressure plasma spraying method, high-speed flame spraying method, explosion spraying method, etc. The film can also be formed by worm spray or cold spray in which the temperature of the spraying atmosphere gas is kept low. The metal boride cermet sprayed coating by these thermal spraying methods may be directly formed on the inner surface of the mold (base material). First, an undercoat is applied to the surface of the base material, and a so-called top coat is formed thereon. Alternatively, a thermal spray coating of the metal boride cermet may be coated and laminated.

  The thickness of the metal boride cermet sprayed coating is preferably in the range of 50 to 1000 μm, particularly preferably 100 to 300 μm. The reason is that when the thickness is less than 50 μm, it is impossible to form a film with a uniform thickness on the surface of the base material. On the other hand, the thermal spray coating having a thickness of more than 1000 μm has more pores, resulting in a glass molding surface. This is because it has an adverse effect.

  In addition, since the metal boride cermet sprayed coating of the present invention contains a heat-resistant alloy component at a ratio of 10 to 80 mass%, the undercoat is not essential, but a thick film, for example, a coating of 300 μm or more In order to improve the adhesion to the top coat, it is desirable to apply this undercoat.

  As an undercoat, Ni-Al, Ni-Cr, Ni-Cr-Al, a self-fluxing alloy (JIS H8303), M (Ni or Co) is given priority to the function of improving the adhesion and heat resistance with the substrate. ) -Cr-Al-X alloy (where X is a rare earth element such as Y, Ce or La) is preferred. The thickness is preferably in the range of 50 to 150 [mu] m, and particularly preferably 50 to 100 [mu] m. The reason is that when the film thickness is thinner than 50 μm or more than 150 μm, the function as an undercoat is not sufficient.

(3) Surface properties of metal boride cermet sprayed coating The surface of the metal boride cermet sprayed coating after film formation is affected by the spraying process and the particle size of the sprayed material, but is generally rough (Ra ≧ 3 to 8 μm, Rz ≧ 10 to 22 μm), there is a disadvantage as described above. Therefore, in the present invention, it is effective to finish the sprayed coating surface to a smoother surface with Ra: 2 μm or less and Rz: 4 μm or less by mechanical or electrical means such as grinding or polishing. In the case of a glass molding die, the properties of the surface of the sprayed coating formed on the surface thereof are directly transferred to the glass molding surface, so that not only the Ra value but also the Rz value is a predetermined value or less. It is preferable to perform sufficient finishing management.

  The reason why the surface roughness Ra ≦ 2 μm of the metal boride cermet sprayed coating is to reduce the contact resistance with the molten glass lump and to ensure a smooth glass molding surface, while Rz ≦ 4 μm. This is because the roughness of the thermal spray coating is transferred to the glass molding surface, which may cause defective products.

  In addition, when the metal boride cermet sprayed coating formed in the present invention includes a Ni—W—Cr— (P—B) alloy, it is more effective to perform heat treatment. That is, since the coating is obtained by spraying a thermal spray material mixed with a refractory metal / alloy on a boride, it is beneficial to heat-treat this coating. The heat treatment conditions are preferably 300 to 700 ° C. and 0.5 to 5 hours in air, vacuum or inert gas. If the temperature is out of the specified range or the time is out of the predetermined range, the hardening is insufficient, the increase in hardness is saturated and the production cost increases, and sometimes the crystal is coarsened and the hardness is reduced. The effects and effects of this are diminished. In particular, this heat treatment is effective in the case of an alloy containing P or B.

(4) Substrate As the base material of the molding die for forming the boride cermet film of the present invention, those made of steel such as cast iron, cast steel, carbon steel, tool steel, low alloy steel are suitable. . In addition, non-ferrous metals such as Al and alloys thereof, Ti and alloys thereof, and Mg alloys, ceramic sintered bodies, sintered carbon, and the like can also be used.

Example 1
In this example, the adhesion of a metal boride cermet sprayed coating made of a heat-resistant alloy containing metal boride and Ni and W as essential components to a steel substrate was examined by a thermal shock test.

(1) Test base material: As a test base material, a test piece of SUS410 steel (dimensions: width 50 mm × length 50 mm × thickness 3.2 mm) was used.
(2) Film-forming material: MoB and W ₂ B ₅ are used as borides. Ni is 80 to 99 mass%, W is 0.5 to 10 mass%, and P is 5 to 7 mass for each metal boride particle. A cermet powder prepared by blending 50 mass% of heat-resistant alloy particles in which% and B were changed to 2 mass% was prepared, and a film having a thickness of 150 μm was directly formed on one surface of the test piece by an atmospheric plasma spraying method.
Further, as a comparative example, a film having a thickness of 150 μm was directly formed on a substrate by an atmospheric plasma spraying method using only a film of metal boride particles (W ₂ B ₅ , MoB, TaB, CrB ₂ ).
(3) Thermal shock test: After heating the above-mentioned sprayed coating specimen in an electric furnace at 650 ° C. for 15 minutes, taking it out of the furnace and cooling it to a temperature of 80 ° C. or less while flowing air from the blower. The test was repeated for a total of 10 cycles. In each cycle test, the surface of the sprayed coating was observed with a magnifying glass (× 8) to investigate the presence or absence of “cracking” and local peeling.
(4) Test results: The test results are shown in Table 2. As is apparent from the results shown in Table 2, the boric acid-only comparative film (Nos. 9 to 12) was cracked or locally peeled by repeating the thermal shock cycle 5 to 8 times. There has occurred. On the other hand, the metal boride cermet sprayed coating (Nos. 1 to 8) conforming to the present invention showed good thermal shock resistance without cracking or peeling even in a 10-cycle thermal shock test. . From this result, it was found that the adhesion to the substrate can be improved by adding Ni—W-containing heat-resistant alloy particles to the boride particles.

(Example 2)
In this example, the releasability and thermal shock resistance were qualitatively determined by clarifying the relationship between the type of alloy component added to the metal boride and the adhesion of the molten glass lump.

(1) Test base material: As a test base material, a test piece of FC200 (dimensions: width 50 mm × length 70 mm × thickness 7 mm) was used.
(2) Test coating: As a test coating, a metal boride cermet material in which the following metal borides and alloy components are mixed at a weight ratio of 50:50 is air plasma sprayed to form a sprayed coating having a thickness of 100 μm. did.
a. Boride: CrB ₂ , ZrB ₂ , MoB, TaB, W ₂ B ₅
b. Alloy component: Ni-based heat-resistant alloy in which Ni is changed to 20 to 99 mass%, W is changed to 0.5 to 15 mass%, P is changed to 2 to 7 mass%, and B is changed to 2 to 4 mass%. In addition to cermet materials containing 50% by mass of Cr and Ni-50 to 75 mass% Cr alloy, self-fluxing alloy (SFNi4 of JIS H8303), and currently used graphite coating film, tested under the same conditions. did.
(3) Adhesion test with molten glass: After a 1200 ° C molten glass lump was pressure-bonded to the surface of the test film, it was allowed to cool to room temperature, and the glass lump fixed to the film surface was struck down with a wooden hammer. Then, the adhesion (release property) of the glass lump was qualitatively investigated.
(4) Thermal shock test: evaluated in the same manner as in Example 1.
(5) Test results: The test results are shown in Table 3. As is apparent from the results shown in Table 3, even when the metal boride cermet sprayed coating is used, the metal (alloy) to be added is Cr or an alloy coating having a high Cr content (No. 2, 5, 9, 11). However, it has been found that although it has excellent thermal shock resistance, it has high adhesion to molten glass and is not suitable as a coating for a mold for molding a molten glass lump. Further, the self-fluxing alloy film (No. 14) also exhibited good thermal shock properties, but the peelability from the molten glass lump was not good.

  On the other hand, the coating film of graphite powder was extremely good in peelability from the molten glass lump, but even during the test, it was easily scattered around and contaminated the laboratory environment. The application of was found to be difficult.

  On the other hand, the film (No. 1, 3, 4, 6, 7, 8, 10) suitable for the present invention has a good releasability from the molten glass lump. No exfoliation was observed and excellent performance was demonstrated.

(Example 3)
In this example, the surface of the mold for making iron was coated with various sprayed coatings including a metal boride cermet sprayed coating conforming to the present invention, and then the workability under actual working conditions was tested.

(1) Test mold: The following sprayed coating was formed on the inner surface of a cracked mold made of cast iron.
(2) Test film: As a film according to the present invention, a metal boride cermet in which a heat-resistant alloy containing Ni and W as essential components is mixed with MoB at a ratio of 50 mass% is 200 μm by atmospheric plasma spraying. The thickness was formed. In addition, as a comparative example, a MoB cermet sprayed coating to which a heat-resistant metal (alloy) not containing Ni and W was added at a ratio of 50 mass% was applied with a thickness of 200 μm by a thermal spraying method, and Cr ₃ C ₂ -20 mass. % Ni-8mass% Cr cermet material formed by high-speed flame spraying to a thickness of 120 μm was prepared. The surfaces of the test sprayed coatings were all finished to a smooth surface with a surface roughness Ra: 2.0 μm or less and Rz: 4 μm or less by a mechanical polishing method.
(3) Test items: The test items of the test film in the actual iron making plant are observation of the state of insertion of the molten glass lump into the mold and observation of the surface of the film after the test (presence of cracks and peeling). .
(4) Test results: Table 4 shows the test results. As is apparent from the results shown in Table 4, the metal boride cermet sprayed coating (Nos. 6 to 8) made of a heat-resistant alloy containing a large amount of Cr as the metal component of the comparative example is placed inside the mold of the molten glass lump. During the feeding, a phenomenon of temporarily staying near the entrance was observed, and it was found that the frictional resistance with the glass block was large. Moreover, since the production | generation of the hexavalent chromium compound was recognized on the film | membrane surface after a test in small quantities, the possibility of contaminating a work environment is apparent. In addition, although the carbide cermet sprayed coating (No. 9) has little contact resistance with the molten glass lump, the production | generation of the hexavalent chromium compound was recognized also on the surface of this membrane | film | coat. The hexavalent chromium compound on the surface of the film is highly likely to be oxidized by the Cr ₃ C ₂ component.

  In contrast to the above results, the metal boride cermet sprayed coatings (Nos. 1 to 5) containing Ni and W conforming to the present invention as essential components and having an Cr content of 18 mass% or less are melted. The glass lump was smoothly supplied to the inside of the mold, and the film surface after 150 hours of use was free from cracks and peeling and maintained a healthy state.

Example 4
In this example, the adhesion of a cermet sprayed coating in which the mixing ratio of a metal boride and a matrix metal and an alloy component coated with an electroless plating film on the surface thereof to the base material and peeling of the molten glass lump are separated. The sex (releasability) was investigated.

(1) Test base material: As a test base material, SUS410 steel (dimensions: width 50 mm × length 70 mm × thickness 3.2 mm) was used as a test piece.
(2) subjected試皮film: a metal boride, using MoB and ZrB _2, each of the metal boride, the electroless plating film (Ni-W-B alloy 1 [mu] m) matrix metal coated with (Ni or Ni- After preparing a cermet powder in which the powder of the Cr alloy was changed in the range of 10 to 90 mass%, a coating film was directly formed on one side of the substrate to a thickness of 150 μm by using these powders by the atmospheric plasma spraying method.
Moreover, as a film of the comparative example, a material having a metal boride component of 100 mass% and a metal component of 100 mass% formed to a thickness of 150 μm by an atmospheric plasma spraying method was prepared. (3) Test method: The thermal spray test method disclosed in Example 1 was used for the adhesion of the sprayed coating, and the peelability from the molten glass lump was measured using the test method employed in Example 2.

(4) Test results: Table 5 shows the test results. As is apparent from the results shown in Table 5, the adhesion of the thermal spray coating is good for the thermal spray coating (No. 8, 16) consisting only of Ni and Ni—Cr alloy coated with the electroless plating film, The cermet sprayed coating (Nos. 2 to 7 and 10 to 15) containing 10 to 90 mass% of the metal component also exhibited good adhesion under these experimental conditions, with no peeling of the coating observed.
On the other hand, in the thermal spray coating (Nos. 1 and 9) made of only the metal boride, after the test of 5 to 6 cycles, the occurrence of cracks as observed in appearance was recognized. Compared to the above, it can be seen that the adhesiveness and the resistance to thermal change are poor.

On the other hand, in a peelability test with a molten glass lump, a coating of only Ni or Ni—Cr alloy coated with an electroless plating film (No. 8, 16) and a cermet coating containing 90 mass% of metal (alloy) (No. 7). 15) shows a relatively good peelability, but when the surface of the glass lump after the test was observed with a magnifying glass, the adhesion of the metal oxide pieces was confirmed although the amount was very small. That is, in the Ni or Ni—Cr alloy film coated with the plating film, when the time of contact with the high temperature molten glass becomes long, the metal is oxidized and oxides such as NiO, W ₂ O ₅ , Cr ₂ O ₃ are formed. It can be seen that some of them may be transferred to the surface of the glass block. In addition, in the thermal spray coating (No. 1, 9) of only metal boride, while being excellent in releasability, generation of metal oxides and the like is not recognized, but when observing the joint surface with the glass lump with a magnifier, Although it is very small, it appears that the ceramic particles have fallen off, indicating that the mutual bonding force of the ceramic particles is smaller than that of the metal particles. On the other hand, a cermet sprayed coating containing 10 mass% of a metal (alloy) component is excellent in the mutual bonding force of particles, so that no particle dropout phenomenon is observed, and the transfer of metal oxide to the glass lump surface is also possible. I was not able to admit.

  The technology of the present invention is a heat treatment of a molten glass lump forming member as described above, a member for conveying a molten glass lump in a glass bottle manufacturing process, a large glass molded article, a glass plate material, and an automotive window glass molded article. It is also useful as a surface treatment technique for rolls and other high-temperature transport rolls.

DESCRIPTION OF SYMBOLS 1 Molten glass 2 Glass melting furnace 3 Work room 4 Feeder 5 Orifice 6 Glass cutting machine 7 Glass lump 8 Funnel 9 Scoop 10 Trough 11 Deflector 12 Mold for mold making 13 Molded bowl 14 Thermal spray coating

Claims (10)

The inner surface of the mold that comes into contact with the molten glass block is directly or through an undercoat,
Metal borides,
Ni-W alloy having W content of 0.5 to 10 mass%, Ni-W-Cr alloy having W content of 0.5 to 10 mass%, Cr content of less than 20 mass%, and W content Among the Ni—W—Cr— (P—B) alloys containing 0.5 to 10 mass%, Cr content of less than 20 mass%, and further containing at least one of P and B of 7 mass% or less, respectively. A Ni-based heat-resistant alloy containing one or more selected Ni and W as essential components;
A mold for forming a molten glass lump, which is coated with a sprayed coating of a metal boride cermet comprising: 2. The molten glass ingot molding die according to claim 1, wherein the metal boride cermet sprayed coating has a smooth surface having a surface roughness Ra of 2 μm or less and Rz of 4 μm or less. The metal _{borides, TiB 2, ZrB 2, HfB} 2, VB, TaB, NbB, 20~90mass% containing _{W 2 B 5, CrB 2,} NiB and any one or more metal boride selected from MoB The molten glass lump-molding mold according to claim 1 or 2, characterized in that: The metal boride cermet sprayed coating in which the heat-resistant alloy component of the cermet is a Ni—W—Cr— (P—B) alloy is a sprayed coating that has been heat-treated at 300 to 700 ° C. for 0.5 to 5 hours. molten glass gob molding die according to claim 1, characterized in that. The undercoat formed between the inner surface of the mold and the metal boride cermet sprayed coating is made of Ni—Al, Ni—Cr, Ni—Cr—Al, self-fluxing alloy, MCrAlX alloy (where M is Co And / or Ni, X is a sprayed coating of at least one alloy selected from the group consisting of rare earth elements). . Ni-W alloy having a metal boride and W content of 0.5 to 10 mass%, having a particle size of 5 to 60 μm, directly or through an undercoat on the inner surface of the molding die in contact with the molten glass lump Ni-W-Cr alloy with W content of 0.5-10 mass%, Cr content of less than 20 mass%, and W content of 0.5-10 mass%, Cr content of less than 20 mass% And a Ni-base heat-resisting material having at least one of Ni and W as essential components selected from Ni—W—Cr— (P—B) alloys containing 7 mass% or less of at least one of P and B. A metal boride cermet sprayed material made of an alloy is sprayed by a thermal spraying method selected from an atmospheric plasma spraying method, a low pressure plasma spraying method, a high-speed flame spraying method, and an explosive spraying method. Method for producing a molten glass gob molding die, which comprises coating forming a metal boride cermet sprayed coating of 50 to 1000 [mu] m. 7. The metal boride is any one or more selected from TiB ₂ , ZrB ₂ , HfB ₂ , VB, TaB, NbB, W ₂ B ₅ , CrB ₂ , NiB and MoB. The manufacturing method of the metal mold | die for molten-glass lump shaping | molding of description. When the Ni-base heat-resistant alloy is a Ni—W—Cr— (P—B) alloy, the metal boride cermet sprayed coating is 300 to 700 ° C. in air, vacuum or inert gas after forming the sprayed coating. The method for producing a mold for forming a molten glass lump according to claim 7, wherein the heat treatment is performed for 0.5 to 5 hours. 9. The molten glass according to claim 6, wherein the coating surface of the metal boride cermet sprayed coating is finished to a smooth surface with Ra: 2 μm or less and Rz: 4 μm or less. A manufacturing method of a block mold. The undercoat is any one selected from Ni—Al, Ni—Cr, Ni—Cr—Al, self-fluxing alloy, MCrAlX alloy (where M is Co and / or Ni, and X is a rare earth element). The method for producing a molten glass gob molding mold according to any one of claims 6 to 9, wherein said alloy is a sprayed coating and has a film thickness of 50 to 150 µm.

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