This application is the U.S. National Stage entry of International Application No. PCT/JP2020/019745 filed under the Patent Cooperation Treaty and having a filing date of May 19, 2020, which claims priority to Japanese Patent Application No. 2019-096985 having a filing date of May 23, 2019, both of which are incorporated herein by reference.
The present invention relates to a nickel-based self-fluxing alloy used in a glass manufacturing member for transporting or molding glass, and a glass manufacturing member using the Ni-based self-fluxing alloy, as well as a mold and a glass gob transporting member each using the glass manufacturing member.
In glass product molding processes, when a glass manufacturing member and glass heated to a high temperature tend to adhere to each other, molding defects such as inaccurate shaping of a product or formation of scratches on the surface of a glass product are likely to occur. For this reason, in the molding of glass bottles, for example, a mold release agent is frequently applied (“swabbing”) to ensure mold release (See Patent Document 1, for example). As used herein, the term “molten glass” or “molten glass gob” refers to glass at a high temperature which allows molding and processing of the glass; that is glass (or glass gob) with a viscosity of log η=3 to 14.6 (=103 to 1014.6 poise), where log η represents the natural logarithm.
In addition, alloys containing a small amount of B (boron) have been proposed as a material used in a glass manufacturing member with excellent heat resistance and wear resistance (See Patent Document 2, for example).
Known technologies in the technical fields other than glass molding include forming a thermal-sprayed coating on the surface of a plunger, a hearth roll or other members to improve the wear resistance of the surface of the member. It has been proposed to use self-fluxing alloys that can create coatings which would not peel off even when subjected to rapid thermal changes, and that can be thermal splayed and then subjected to a fusing (re-melting) treatment to form a more homogeneous coating without pores. Known such self-fluxing alloys include one containing: Ni (nickel) in an amount of 40% to 70% m/m; Cr (chromium) in an amount of 5% to 40% m/m; B (boron) in an amount of 1% to 6% m/m; Si (silicon) in an amount of 1% to 6% m/m; C (carbon) in an amount of 0.1% to 2.0% m/m; F (iron) in an amount of 1% to 10% m/m; W (tungsten) in an amount of 1% to 20% m/m; and Cu (copper) in an amount of 0.8% to 5% m/m (See Patent Document 3, for example).
The properties required for glass manufacturing members that come into contact with a molten glass gob in glass product molding processes include: adequate non-adherence to a molten glass gob; absence of unintended holes (such as pinholes) on their surfaces; good wear resistance; and longer life. However, glass manufacturing members of the prior art still do not adequately satisfy these requirements for the properties.
The present invention has been made in view of this problem of the prior art, and a primary object of the present invention is to provide a nickel-based self-fluxing alloy with high wear resistance and low adhesion to molten glass, and a glass manufacturing member using the nickel-based self-fluxing alloy, as well as a mold and a glass gob transporting member each using the glass manufacturing member.
An aspect of the present invention provides a nickel-based self-fluxing alloy comprising: B (boron) in an amount of ranging from 0 percent to 1.5 percent by mass; hard particles; and Si (silicon), and a glass manufacturing member using the nickel-based self-fluxing alloy. Another aspect of the present invention provides a mold and a glass gob transporting member each using a glass manufacturing member, the glass manufacturing member having a contact part to be in contact with molten glass in a glass molding process, wherein the contact part is made of the nickel-based self-fluxing alloy.
A nickel-based self-fluxing alloy according to the present invention is hard to adhere to molten glass even at high temperatures. Thus, when a glass manufacturing member in which the alloy is entirely or partly used comes into contact with molten glass, the alloy reduces friction between the glass manufacturing member and molten glass, thereby reducing the necessity of swabbing treatment and minimizing the defects in resulting products, which improves the production yield.
The present invention is based primarily on the inventors' discovery that a certain alloy composition including a predetermined amount of B (boron) or not including B, does not adhere to molten glass even at a high temperature. The present invention can improve the slipperiness of a molten glass gob on the surface of the nickel-based self-fluxing alloy.
The mechanism behind the findings of the inventors is inferred as follows:
Generally, Ni is known to have lower adhesion to glass than other metal materials. It is also known that a nickel-based alloy which contains B (boron) may have high adhesion to a molten glass gob; that is, a level of slipperiness of a molten glass gob is decreased on the surface of the metal material including B (boron). While not being held to any specific theory, it is presumed that B in the Ni-based alloy or B2O3 occurring on the surface of the Ni-based alloy at high temperatures improves the adhesion of the Ni alloy oxide to the base metal, or the mixed oxide of B and Ni alloy is hardly peeled off from the base metal, which is thought to prevent the above-described phenomenon of peeling of the oxide film, resulting in that the oxide film firmly adheres to the surface of the Ni alloy firmly adheres, decreasing the slipperiness of a molten glass gob on the Ni-based alloy.
According to the present embodiment, the Ni-based self-fluxing alloy used in a glass manufacturing member for molding glass with a viscosity of log η=3 to 14.6, comprises B (boron) in an amount of ranging from 0 percent to 1.5 percent by mass; hard particles; and Si (silicon). The glass manufacturing member comprises a glass molding member, and a glass transporting member. The expression “log η” represents the natural logarithm. The amount of each of the components contained in the Ni-based self-fluxing alloy according to the present embodiment is preferably in the range described later. Examples of the type of glass include soda-lime glass, and borosilicate glass, lead glass. The glass manufacturing member may be a member for transporting or molding glass at temperatures of ranging from 400 to 1400° C.
According to the present embodiment, the Ni-based self-fluxing alloy contains B (boron) in an amount of ranging from 0 percent to less than 1.5 percent by mass. The Ni-based self-fluxing alloy may contain B (boron) in an amount of ranging from 0 percent to 1.1 percent by mass, preferably in an amount of ranging from 0 percent to less than 1.0 percent by mass, more preferably in an amount of ranging from 0 percent to less than 0.75 percent by mass, most preferably in an amount of ranging from 0 percent to less than 0.5 percent by mass. Furthermore, the Ni-based self-fluxing alloy may contain B (boron) in an amount of ranging from more than 0 percent to less than 1.0 percent by mass, preferably in an amount of ranging from more than 0 percent to less than 0.75 percent by mass, most preferably in an amount of more than 0 percent to less than 0.5 percent by mass. In other embodiment the Ni-based self-fluxing alloy does not contain B (boron).
The Ni-based self-fluxing alloy may contain Si (silicon) preferably in an amount of ranging from 0 percent to 10 percent by mass, more preferably in an amount of ranging from 1.0 percent to 7.5 percent by mass.
B and Si are flux components, and the self-fluxing property of the Ni-based self-fluxing alloy increases with an increasing amount of these components. B and Si form B2O; and SiO2 oxide films on the surface of the Ni-based self-fluxing alloy. As described above, B2O3 can be one of the factors for increasing the adhesiveness to molten glass. Thus, in the present embodiment, the Ni-based self-fluxing alloy containing a smaller amount of B is more preferable.
The Ni-based self-fluxing alloy according to the present embodiment contains hard particles in order to improve wear resistance. Examples of the hard particles include carbides, nitrides, oxides and cermet materials (i.e., composite materials composed of carbides, nitrides, or oxides in combination with metal materials). The Ni-based self-fluxing alloy according to the present embodiment contains at least one of a carbide, a nitride, an oxide and a cermet. The Ni-based self-fluxing alloy comprises hard particles in an amount of 0 percent to 50 percent by mass, preferably in an amount of 5 percent to 50 percent by mass, more preferably in an amount of 5 percent to 30 percent by mass. When containing too small an amount of hard particles, the Ni-based self-fluxing alloy does not have sufficient wear resistance and goes unusable in a short time period. When containing too large an amount of hard particles, the Ni-based self-fluxing alloy becomes difficult to be processed into a member(s).
Carbides as hard particles comprise any one of the elements of Groups 4, 5 and 6 (of the Periodic Table). Examples of such carbides include: TiC (titanium carbides); ZrC (zirconium carbides); HfC (hafnium carbides); VC or V2C (vanadium carbides); NbC (niobium carbides); TaC (tantalum carbides); Cr3C2, Cr7C3 or Cr23C6 (chromium carbides); Mo2C (molybdenum carbides); and WC or W2C (tungsten carbides).
Carbides as hard particles may include silicon carbide.
Oxides as hard particles may include at least one selected from lanthanide metal oxides. The at least one selected from lanthanide metal oxides is preferably cerium oxide.
The cermet may comprise a carbide of any one of the Group 4, 5 and 6 elements. The cermet which is a composite material composed of the carbide and a metal material, is preferably, but is not limited to, WC (WC-12% Co) containing 12% m/m Co (cobalt) as a binder.
The hard particles disperse in the base material, the Ni-based self-fluxing alloy, improving the wear resistance of the alloy, which means that a glass manufacturing member using the Ni-based self-fluxing alloy exhibits long-term durability.
The Ni-based self-fluxing alloy may comprise the at least one metal selected from Group 15 elements, preferably in an amount of ranging from 0 percent to 15 percent by mass. The at least one metal selected from Group 15 elements is preferably P (phosphorus).
The Ni-based self-fluxing alloy according to the present embodiment may contain P (phosphorus) in an amount of ranging from 0 percent to 5 percent by mass, preferably in an amount of ranging from 0.5 percent to 4 percent by mass.
The Ni-based self-fluxing alloy according to the present embodiment may contain at least one metal selected from Group 4, 5 and 6 elements in an amount of ranging from 0 percent to 30 percent by mass, preferably in an amount of ranging from 2.5 percent to 30 percent by mass. The at least one metal selected from Group 4, 5 and 6 elements is preferably Cr (chromium), and the amount of Cr (chromium) preferably ranges from 2.5 percent to 30 percent by mass.
The Ni-based self-fluxing alloy according to the present embodiment may contain at least one metal selected from Group 3 elements, preferably in an amount of ranging from 0 percent to 10 percent by mass. The at least one metal selected from Group 3 elements is preferably Y (yttrium).
The Ni-based self-fluxing alloy according to the present embodiment may contain at least one metal selected from Group 7 elements, preferably in an amount of ranging from 0 percent to 10 percent by mass. The at least one metal selected from Group 7 elements is preferably Mn (manganese) or Re (rhenium).
The Ni-based self-fluxing alloy according to the present embodiment may contain at least one metal selected from Group 8 elements, preferably in an amount of ranging from 0 percent to 30 percent by mass. The at least one metal selected from Group 8 elements is preferably Fe (iron).
The Ni-based self-fluxing alloy according to the present embodiment may contain at least one metal selected from Group 11 elements, preferably in an amount of ranging from 0 percent to 10 percent by mass. The at least one metal selected from Group 11 elements is preferably Cu (copper) or Ag (silver).
The Ni-based self-fluxing alloy according to the present embodiment may contain the balance nickel in an amount ranging from 3.5 percent to 97.5 percent by mass, and other incidental process impurities in a small amount.
The metal components other than hard particles of the Ni-based self-fluxing alloy according to the present embodiment may be prepared by using any preparation scheme as long as the resulting alloy has a composition within the prescribed scope. For example, the Ni-based self-fluxing alloy may be prepared by melting and mixing metals comprising essential components and an inorganic compound(s) and then solidifying them to produce alloy, or only by mixing fine particles of metals comprising essential components with those of an inorganic compound(s).
Examples of methods for producing glass manufacturing members using the Ni-based self-fluxing alloy of the present invention include, but are not limited to, sintering or casting.
One example of a method of applying the Ni-based self-fluxing alloy only to a contact part, which is to be in contact with molten glass, of a mold and/or a molten glass gob transporting member both made of a metal such as iron, involves coating the contact part with a film made of Ni-based self-fluxing alloy by thermal spraying, plating, cladding, laminated molding, welding, or any other suitable method. Moreover, the method may further comprise, subsequent to forming the film, subjecting the film to a fusing (re-melting) treatment to thereby close the pores in the film and improve the adhesion between the film and the base material.
Examples of glass manufacturing members will be described. As shown in
In the above-described embodiments, the Ni-based self-fluxing alloy has characteristics such that, when the Ni-based self-fluxing alloy is formed into a plate, heated to 480° C. and placed to be inclined at 70 degrees with respect to the horizontal, and 0.3 g of molten glass heated to 1,000° C. is dropped onto the heated plate of the Ni-based self-fluxing alloy, the molten glass slides down without adhering to the plate of the Ni-based self-fluxing alloy.
Thus, according to the above-described embodiments, a Ni-based self-fluxing alloy which does not adhere to a molten glass gob even at a high temperature can be provided. Furthermore, provided by applying the Ni-based self-fluxing alloy to various glass molding members are various glass manufacturing members which have an improved slipperiness against a glass gob and do not adhere to a molten glass gob or flat glass. Examples of such glass manufacturing members include molds for press molding, molding rolls, transfer rolls, and transfer molds, and jigs which come into contact with glass.
(Molten Glass Adhesion Testing Device)
A molten glass adhesion testing device 21 (
The sample 20 was placed to be inclined at 70 degrees with respect to the horizontal, such that the central portion of the sample was located below the center point A of a rectangular burner support frame 28 at a distance of 100 mm. Furthermore, the sample heating device 27 was a metal plate provided with a heater 30 and a thermocouple 31 both connected to a temperature controller 32.
The glass rod heating device 24 was provided with the rectangular frame 28 and four burners 29 supported by the frame 28. The burners 29 were supported by the frame 28 so that their injection holes face the inside of the frame 28 and the respective injection axes intersect at the center point A of the frame 28. The burners 29 were adjusted so that the tips of the respective flames ejected from the burners 29 intersected at the center point A of the frame 28.
(Glass Bar)
The glass rod 22 was made of glass having the composition comprising: SiO2 in an amount of 69% m/m; Al2O3 in an amount of 1.7% m/m; Fe2O3 in an amount of 0.06% m/m; Na2O in an amount of 8.5% m/m; K2O in an amount of 4.9% m/m; MgO in an amount of 2.2% m/m; CaO in an amount of 4.0% m/m; SrO in an amount of 6.0% m/m; BaO in an amount of 3.2% mm; Sb2O3 in an amount of 0.3% mm; P2O5 in an amount of 0.2% m/m; TiO2 in an amount of 0.03% m/m; Cl in an amount of 0.03% m/m; SO3 in an amount of 0.03% m/m; and ZrO2 in an amount of 0.1% by m/m. The diameter of the glass rod was 4 mm.
(Test Method)
After a surface temperature of a sample 20 was confirmed to be at a predetermined temperature by measuring the sample with a temperature sensor (Anritsu Meter Co., Ltd., Static surface temperature sensor, Model A series), the lower end of the glass rod 22 was disposed at the center point A of the frame 28, and heated by the flames ejected from the burners 29. The lower end of the heated glass rod melted into a spherical shape and naturally dropped onto the sample 20. The temperature of the glass gob at the time of dropping onto the sample was measured by thermography (Shinano Kenshi Co., Ltd., PLEXLOGGER PL3).
(Method for Measuring Adhesion Rate)
In the test, a glass gob dropped onto the sample 20 adheres to the sample 20 or falls downward without adhering thereto. When the temperature of a glass gob at the time of dropping onto the sample 20 was within the range of 1000 (±20)° C., it was determined whether the glass gob adhered to the surface of the sample 20 or fell downward without adhering thereto; that is, it was determined whether the test result was “adhesion” or “non-adhesion.” This test was carried out 10 times at a certain temperature of the surface of the sample 20, and an adhesion rate (%) was calculated as the ratio of the number of the “adhesion” results to all the 10 test results. When the temperature of a glass gob dropped onto the sample did not fall within the prescribed range, the determination result was not counted as a test result for adhesion rate.
Samples of Examples 1 to 48 and Comparative Examples 1 to 5 were prepared by the methods shown below and their adhesion properties were evaluated. Tables 1 to 15 show compositions (ratios of components), production methods, and adhesion test results of Examples 1 to 48 and Comparative Examples 1 to 5.
Raw materials of Ni-based allow comprised of Si with a particle size (particle diameter) of 105 μm or less, Ni2P with a particle size of 150 μm or less. Cr with a particle size of 63 μm or less, the balance Ni with a particle size of 2 to 3 μm, and Mo powder with a particle size of about 1.5 μm or less (both available from Kojundo Chemical Lab. Co., Ltd.), and WC-12% Co with a particle size of 15-45 μm (Eutectic Japan Ltd.) as hard particles were mixed at the ratios shown in Table 1, to thereby produce the alloy. After a plate of the alloy was produced by a pulse energization sintering method, the plate was further processed into a plate having a width of 3 cm, a depth of 4 cm, and a thickness of 3 mm and with a surface roughness (arithmetic mean roughness Ra) of about 1 m or less. Then, the molten glass adhesion evaluation test was performed by using the resulting plate as a sample 20.
The evaluation test was performed in the same manner as Example 1 except that B (boron) with a particle size of 45 μm or less was further mixed in an amount of 0.1% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 2 except that the amount of B (boron) was 0.5% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 2 except that the amount of B (boron) was 1.1% m/m and the amount of Si (silicon) was 2.5% mm in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that the amount of Si (silicon) was 1.0% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that the amount of Si (silicon) was 2.5% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Cr was not mixed as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Cr was mixed in an amount of 20% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Mo was not mixed as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 9 except that V (vanadium) with a particle size of 150 μm or less (Kojundo Chemical Lab. Co., Ltd.) was further mixed in an amount of 0.4% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that WC-12% Co was not mixed as a raw material of the Ni-based alloy, but WC with a particle size of about 5 μm and Co with a particle size of about 5 μm (both available from Kojundo Chemical Lab. Co., Ltd.) were mixed at the ratios shown in Table 1 in the preparation of a sample.
The evaluation test was performed in the same manner as Example 11 except that Co was not mixed as a raw material of the Ni-based alloy in the preparation of a sample.
After the raw materials of the alloy were mixed at the same ratios as Example 1 and a metal plate was produced by casting, the metal plate was additionally processed into a plate having a width of 3 cm, a depth of 4 cm, and a thickness of 3 mm, and having a surface roughness (arithmetic mean roughness Ra) of about 1 μm or less. The evaluation test was performed on the resulting plate.
The evaluation test was performed in the same manner as Example 12 except that WC fine carbide particles were not mixed, but CrC (chromium carbide) with a particle size of 45 μm or less (Kojundo Chemical Lab. Co., Ltd.) was mixed in an amount of 15.7% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 12 except that WC fine carbide particles were not mixed, but VC (vanadium carbide) with a particle size of 10 μm or less (Kojundo Chemical Lab. Co., Ltd.) was mixed in an amount of 15.7% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 12 except that WC-12% Co was not mixed, but ZrC (zirconium carbide) with a particle size of 10 μm or less (Kojundo Chemical Lab. Co., Ltd.) was mixed in an amount of 15.7% mm as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 12 except that WC-12% Co was not mixed, but ZrC (zirconium carbide) with a particle size of 10 μm or less (Kojundo Chemical Lab. Co., Ltd.) was mixed in an amount of 15.7% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that WC-12% Co was not mixed, but WC-10% Ni with a particle size of 45 μm or less (Eutectic Japan Ltd.) was mixed in an amount of 15.7% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that WC-12% Co was not mixed, but WC-10% Co with a particle size of 45 μm or less (Eutectic Japan Ltd.) was mixed in an amount of 15.7% mm as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that WC-12% Co was not mixed, but WC-20% Cr7% Ni with a particle size of 45 μm or less (Eutectic Japan Ltd.) was mixed in an amount of 15.7% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that WC-12% Co was not mixed, but CrC-20% Ni5% Cr with a particle size of 45 μm or less (Eutectic Japan Ltd.) was mixed in an amount of 6.7% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 21 except that the amount of CrC-20% Ni5% Cr was 15.7% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that WC-12% Co was not mixed, but CrC-20% Ni5% Cr with a particle size of 45 μm or less was mixed in an amount of 15.7% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Cr and Mo were not mixed, but Ti (titanium) with a particle size of 45 μm or less (Kojundo Chemical Lab. Co., Ltd.) was mixed in an amount of 5% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Cr and Mo were not mixed, but Zr (zirconium) with a particle size of 45 μm or less (Kojundo Chemical Lab. Co., Ltd.) was mixed in an amount of 10% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 7 except that the amount of Mo was 5% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 7 except that the amount of Mo was 10% mm in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Cr and Mo were not mixed, but Ta (tantalum) with a particle size of 45 μm or less (Kojundo Chemical Lab. Co., Ltd.) was mixed in an amount of 10% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that V (vanadium) was further mixed in an amount of 5% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 10 except that the amount of V was 5% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that V and Zn were further mixed in amounts of 3% m/m and 10% m/m, respectively, as raw materials of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Cr and Mo were not mixed, but W (tungsten) (Kojundo Chemical Lab. Co., Ltd.) was mixed in an amount of 10% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that the amount of WC-12% Co was 5% mm in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that the amount of WC-12% Co was 20% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that P was not mixed as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that the amount of P was 3% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that the amount of P was 5% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Sb (antimony) with a particle size of 150 μm or less (Kojundo Chemical Lab. Co., Ltd.) was further mixed in an amount of 10% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that P was not mixed, but Bi (bismuth) with a particle size of 150 μm or less (Kojundo Chemical Lab. Co., Ltd.) was further mixed in an amount of 5% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that cerium oxide was further mixed in an amount of 10% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Y (yttrium) with a particle size of 150 μm or less (Kojundo Chemical Lab. Co., Ltd.) was further mixed in an amount of 1.11% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Y (yttrium) was further mixed in an amount of 10% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Mn (manganese) with an average particle size of 50 μm or less (Kojundo Chemical Lab. Co., Ltd.) was further mixed in an amount of 5% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Re (rhenium) with a particle size of 45 μm or less (Kojundo Chemical Lab. Co., Ltd.) was further mixed in an amount of 10% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 1 except that raw materials of Ni-based allow comprised of Si, Ni2P, Cr, the balance Ni, Mo, and Fe (iron) powder (all available from Kojundo Chemical Lab. Co., Ltd.), as well as WC-12% Co with a particle size of 15-45 μm (Eutectic Japan Ltd.) as hard particles, were mixed at the ratios shown in Table 11, to thereby produce the alloy.
The evaluation test was performed in the same manner as Example 4 except that Cu (copper) with an average particle size of 50 μm or less (Kojundo Chemical Lab. Co., Ltd.) was further mixed in an amount of 5% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Example 4 except that Ag (silver) with an average particle size of 50 μm or less (Kojundo Chemical Lab. Co., Ltd.) was further mixed in an amount of 1.34% m/m as a raw material of the Ni-based alloy in the preparation of a sample.
A metal powder as a raw material of the alloy was prepared by using a gas atomization method such that the resulting metal powder had a composition and a particle size (median diameter) shown in Table 16, where the composition was analyzed by ICP emission spectroscopy and the particle sizes were measured by laser diffraction spectrometry. After the metal powder was mixed with WC-12% Co, the mixed powder was thermal-sprayed on the surface of a gray cast iron plate by using a high-speed frame thermal spraying method (HVOF (High Velocity Oxygen Fuel) method), to form a nickel-based alloy film having a thickness of about 0.8 mm, which was used as a test piece. Table 14 shows the composition of the thermal-sprayed coating measured with a fluorescent X-ray analyzer. The test piece was additionally processed into a plate having a width of 3 cm, a depth of 4 cm, and a thickness of 3 mm, and having a surface roughness (arithmetic mean roughness Ra) of about 1 μm or less. The resulting plate was used as Example 48, and the molten glass adhesion evaluation test was performed on the alloy film of the plate as a sample surface.
The evaluation test was performed in the same manner as Example 2 except that B was mixed in an amount of 5.0% m/m in the preparation of a sample.
The evaluation test was performed in the same manner as Comparative Example 1 except that Si was not mixed as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Comparative Example 2 except that B and P were not mixed as raw materials of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Comparative Example 2 except that P was not mixed as a raw material of the Ni-based alloy in the preparation of a sample.
The evaluation test was performed in the same manner as Comparative Example 2 except that P was mixed in an amount of 3% m/m in the preparation of a sample.
(Effects of B and Si)
The Ni-based self-fluxing alloy according to the above-described embodiment can achieve an improved slipperiness against a molten glass gob. Furthermore, at least one of the flux components, B and Si, contained in the alloy enables the alloy to be subjected to a fusing treatment.
(Effects of Cr)
(Effects of Carbides)
(Effects of Cermets)
(Effects of Group 4, 5 and 6 Elements)
(Effects of Hard Particles)
(Effects of Group 15 Elements)
(Effects of the Type of Hard Particles)
(Effects of Group 3 Elements)
(Effects of Group 7 Elements)
(Effects of Group 8 Elements)
(Effects of Group 11 Elements)
(Effects of Dispersion State of Hard Particles)
(Effects of the Sample Preparation Method)
The Ni-based self-fluxing alloy of the present invention has characteristics such that, when the Ni-based self-fluxing alloy is formed into a plate, heated to 480° C. and placed to be inclined at 70 degrees with respect to the horizontal, and 0.3 g of molten glass heated to 1,000° C. is dropped onto the heated plate of the Ni-based self-fluxing alloy, the molten glass slides down without adhering to the plate of the Ni-based self-fluxing alloy. Due to the characteristics of the alloy, the alloy used in a glass molding process can exhibit low friction against a molten glass gob and excellent moldability.
The present invention has been described in terms of a specific embodiment, but is not limited by such an embodiment, and can be modified in various ways without departing from the scope of the present invention.
A nickel-based self-fluxing alloy of the present invention can be used in glass manufacturing members, examples of which include metal parts such as a mold, a plunger, and a roller, and transporting members such as a shooter for transporting a molten glass gob in a glass bottle molding process.
Number | Date | Country | Kind |
---|---|---|---|
JP2019-096985 | May 2019 | JP | national |
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/JP2020/019745 | 5/19/2020 | WO |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2020/235547 | 11/26/2020 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
4040049 | Messerschmitt | Aug 1977 | A |
5006321 | Dorfman | Apr 1991 | A |
Number | Date | Country |
---|---|---|
103998164 | Aug 2014 | CN |
105779997 | Jul 2016 | CN |
2551368 | Jan 2013 | EP |
S33-4952 | Jun 1955 | JP |
47-39208 | Dec 1972 | JP |
47039208 | Dec 1972 | JP |
S61-49376 | Oct 1986 | JP |
H02229728 | Sep 1990 | JP |
H 08-311630 | Nov 1996 | JP |
2005-146409 | Jun 2005 | JP |
2008-201080 | Sep 2008 | JP |
WO 0128942 | Apr 2001 | WO |
WO 2011118576 | Jul 2013 | WO |
Entry |
---|
PCT International Search Report (w/ English translation) for corresponding PCT Application No. PCT/JP2020/019745, dated Aug. 18, 2020, 4 pages. |
Chinese Office Action for corresponding Chinese Application No. CN202080036667.0, dated Aug. 26, 2022, 30 pages. |
Guo, “Technical Manual of Mechanical Manufacturing Process Materials”, vol. 1, retrieved from https://img.duxiu.com on Aug. 10, 2022, 4 pages. |
Ma et al., “Oxyacetylene flame powder spray welding technology”, Sichuan Provincial Economic Commission and Sichuan Provincial Heat Harvest Association, 1983, retrieved from https://img.duxiu.com on Aug. 10, 2022, 3 pages. |
Qian, et al., “Welding Technical Manual”, Shanxi Science & Technology Press, retrieved from https://img.duxiu.com on Aug. 10, 2022, 3 pages. |
Wang, “Oxy-acetylene metal powder spray welding”, Dec. 1986, retrieved from sslibrary.com, on Aug. 11, 2022, 3 pages. |
Zhang, “Technical Manual of Railway Rolling Stock”, Manufacturing Technology, vol. 3, 2002, 3 pages. |
PCT international Search Report and Written Opinion (w/ English translation) for corresponding PCT Application No. PCT/JP2020/019745, dated Aug. 18, 2020, 12 pages. |
Number | Date | Country | |
---|---|---|---|
20220251684 A1 | Aug 2022 | US |