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WO2018193982A1 - Revêtement par pulvérisation, tuyau stratifié et procédé de fabrication d'un revêtement par pulvérisation - Google Patents

Revêtement par pulvérisation, tuyau stratifié et procédé de fabrication d'un revêtement par pulvérisation Download PDF

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Publication number
WO2018193982A1
WO2018193982A1 PCT/JP2018/015514 JP2018015514W WO2018193982A1 WO 2018193982 A1 WO2018193982 A1 WO 2018193982A1 JP 2018015514 W JP2018015514 W JP 2018015514W WO 2018193982 A1 WO2018193982 A1 WO 2018193982A1
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Prior art keywords
spray coating
thermal spray
thermal
spraying
layer
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PCT/JP2018/015514
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English (en)
Japanese (ja)
Inventor
田代　博文
稲沢　弘志
浩郎 平田
Original Assignee
東洋鋼鈑株式会社
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Priority to JP2019513604A priority Critical patent/JPWO2018193982A1/ja
Publication of WO2018193982A1 publication Critical patent/WO2018193982A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes

Definitions

  • the present invention relates to a thermal spray coating, a laminated tube, and a method for manufacturing the thermal spray coating.
  • an apparatus (die casting machine) used in a die casting method is mainly composed of parts such as a plunger, a sleeve, and a molding die, and is in direct contact with a molten metal (for example, aluminum, zinc, magnesium, etc.). Used in state. Therefore, the properties required for such parts are as follows. Corrosion resistance to high-temperature metals such as molten metal, that is, it may be melted by the high-temperature metal or a reaction layer on the surface by contact with the high-temperature metal. The characteristic which can prevent forming is mentioned.
  • tool steel and hot tool steel such as SKD61
  • SKD61 hot tool steel
  • a method of forming a nitrided layer by nitriding the hot tool steel for the purpose of improving the corrosion resistance is also known, but the nitrided layer formed by the nitriding process has a thickness of about 20 to 30 ⁇ m. Even if this material is used, it is difficult to maintain sufficient corrosion resistance over a long period of time.
  • ceramic materials such as sialon (SiAlON), etc.
  • SiAlON sialon
  • such a ceramic material has a high manufacturing cost and a low workability, and is harder than necessary.
  • SiAlON sialon
  • it is like a plunger tip.
  • Patent Document 1 discloses that an inner layer is formed of a first layer containing tungsten, and an outer layer of the first layer is ferrite.
  • a laminated tube formed by forming a second layer made of a stainless steel material or the like and a third layer made of a martensite stainless steel material or the like is disclosed.
  • the first layer containing tungsten is excellent in corrosion resistance in a portion in direct contact with a high-temperature metal, but is in contact with the atmosphere when in contact with the atmosphere in a high-temperature environment. There was a problem in that the portion that was oxidized corroded as the oxidation progressed.
  • An object of the present invention is to provide a thermal spray coating excellent in corrosion resistance against high temperature metals and corrosion resistance against air in a high temperature environment.
  • the present inventors have found that the above object can be achieved by containing a tungsten phase and a ternary boride phase in a specific ratio in the spray coating, and have completed the present invention.
  • the thermal spray coating contains a tungsten phase and a ternary boride phase, and is derived from the tungsten phase when the surface of the thermal spray coating is measured by an X-ray diffraction method.
  • the ratio (I max / I w ) of the peak intensity I max of the peak having the highest intensity among the peaks derived from the ternary boride phase to the peak intensity I w of the (110) plane is 1/100 or more.
  • the ternary boride phase mainly contains Mo 2 NiB 2 , and the peak intensity I max is a peak intensity of the (211) plane derived from the Mo 2 NiB 2.
  • the thermal spray coating of the present invention it is preferable that the ternary boride phase mainly contains WFeB, and the peak intensity I max is a peak intensity of the (112) plane derived from the WFeB.
  • the thermal spray coating of the present invention preferably further contains a binary boride phase.
  • the binary boride phase preferably contains W 2 B.
  • the Vickers hardness (HV) measured in the range of 300 to 700 ° C. is preferably 400 or more.
  • the laminated pipe provided with either of the said thermal spray coatings on an inner surface is provided.
  • the ratio (L / D) of the length L of the laminated tube to the inner diameter D of the sprayed coating provided on the inner surface is preferably 2 or more.
  • any one of the above-described methods for producing a thermal spray coating comprising preparing a thermal spraying powder containing tungsten and a ternary boride and having an average granule strength of 10 MPa or more.
  • a method for manufacturing a thermal spray coating comprising a step and a step of spraying the thermal spraying powder on a metal base material by a high-speed flame spraying method.
  • thermo spray coating excellent in corrosion resistance against high temperature metals and corrosion resistance against air in a high temperature environment.
  • FIG. 1 It is sectional drawing which shows one Embodiment of the die-casting apparatus using the sleeve to which the laminated tube which concerns on this invention is applied. It is a perspective view which shows one Embodiment of the laminated tube which concerns on this invention. It is sectional drawing which shows the layer structure of the laminated tube shown in FIG. It is a figure for demonstrating an example of the method of producing the laminated tube which concerns on this invention. It is the photograph obtained by measuring the cross section of the sprayed coating of a comparative example by SEM. It is a graph which shows the result obtained by carrying out X-ray diffraction measurement of the surface of the thermal spray coating of an Example and a comparative example.
  • the thermal spray coating according to the present invention can be formed on a component that requires corrosion resistance in a high temperature environment and high hardness.
  • it can be formed on the inner surface of the sleeve 11 of the die casting apparatus 1 as shown in FIG.
  • the present invention will be described in an embodiment using a laminated tube in which a thermal spray coating according to the present invention is formed on the inner surface as the sleeve 11 of the die casting apparatus 1.
  • FIG. 1 is a cross-sectional view showing an embodiment of a die casting apparatus 1 using a sleeve 11 to which a laminated tube in which a thermal spray coating according to the present invention is formed is applied.
  • the die casting apparatus 1 in this example is a die casting apparatus for forming a molten metal such as aluminum.
  • the die casting apparatus 1 includes a sleeve 11, a plunger 12, a flow path 13, a die cavity 14, a first mold 15, and a second mold 16.
  • the die casting apparatus 1 shown in FIG. The sleeve 11 forms a passage for the plunger 12 to move, and the passage formed by the sleeve 11 is connected to the flow path 13 and the die cavity 14.
  • the plunger 12 reciprocates back and forth in the passage formed by the sleeve 11, and injects the molten metal poured into the sleeve 11 from the sleeve 11 into the die cavity 14 through the flow path 13.
  • the sleeve 11 of the present embodiment is formed using the laminated tube 2 shown in FIG.
  • FIG. 2 is a perspective view showing an embodiment of a laminated tube in which a thermal spray coating according to the present invention is formed on the inner surface.
  • the inner diameter of the laminated tube 2 is indicated by D and the length is indicated by L.
  • the laminated tube 2 of the present embodiment includes a thermal spray coating 21 constituting an inner layer, a second layer 22 formed on the outer peripheral surface of the thermal spray coating 21, and a second layer 22. It has a three-layer structure including a third layer 23 formed on the outer peripheral surface.
  • the laminated tube 2 of the present embodiment is formed by spraying a core material 3 made of an inexpensive and easy-to-process material such as iron, copper, and aluminum by thermal spraying. After the 22 and the third layer 23 are formed in this order, the core material can be removed by machining.
  • the thermal spray coating 21 constituting the inner layer contains a tungsten phase mainly made of tungsten and a ternary boride phase mainly made of ternary boride.
  • the thermal spray coating 21 can be formed by spraying a specific thermal spraying powder containing tungsten and a ternary boride.
  • the tungsten phase constitutes the main phase
  • the ternary boride phase constitutes the binder phase.
  • Thermal spray coating 21 of the present embodiment in the case of measuring the surface by X-ray diffraction method, to the peak intensity I w of from tungsten phase (110) plane, in the peak derived from the ternary boride
  • the ratio (I max / I w ) of the peak intensity I max of the peak with the highest intensity is 1/100 or more.
  • the thermal spray coating 21 by controlling the peak intensity ratio I max / I w derived from the tungsten phase and the ternary boride phase to the above range, the thermal spray coating 21 has corrosion resistance to high-temperature metals. And the corrosion resistance with respect to the air
  • this ternary boride phase acts as a bonding phase for bonding the tungsten phases and the thermal spray coating 21 is densified
  • the thermal spray coating 21 is brought into direct contact with a high-temperature metal such as a molten metal. Corrosion resistance can be significantly improved.
  • the fact that the ternary boride itself is excellent in corrosion resistance can also improve the corrosion resistance in direct contact with the high-temperature metal in the thermal spray coating 21.
  • the thermal spray coating 21 is densified by the ternary boride phase, so that the gas permeability of the thermal spray coating 21 can be lowered. Even in contact with the atmosphere, the corrosion resistance of the thermal spray coating 21 to the atmosphere can be significantly improved.
  • the thermal spray coating of Comparative Example 1 described later (a thermal spray coating formed by spraying a thermal spraying powder containing B, Mo, Ni, Ti, and W by a plasma spraying method) was measured by SEM. The photograph obtained in this way is shown. Similarly, even when the thermal spray coating formed by such a plasma spraying method was measured by the X-ray diffraction method, no peak derived from the ternary boride was observed as shown in FIG.
  • FIG. 6 shows a thermal spray coating of Example 1 described later (a thermal spray coating formed by thermal spraying a thermal spraying powder containing B, Mo, Ni, Ti, and W by a high-speed flame spraying method), and the above-described example.
  • the result of measuring the thermal spray coating of Comparative Example 1 by the X-ray diffraction method shows a ternary boride (in the example shown in FIG. 6, Mo 2 FeB 2 , Mo 2 NiB 2 , or W 2).
  • a black circle represents a peak derived from tungsten (W)
  • a black triangle represents a peak derived from a binary boride (in the example shown in FIG. 6, W 2 B).
  • a ternary system by spraying is used.
  • the thermal spray is applied to the metal base material during the thermal spraying. The powder is scattered, the adhesion efficiency of the thermal spraying powder to the metal base material is reduced, and the thickness of the thermal spray coating formed varies, and the total thickness of the thermal spray coating is reduced. There was a problem.
  • the present inventors have employed a high-speed flame spraying method by using a powder for spraying containing tungsten and a ternary boride having an average granule strength of a predetermined value or more as described later. It has been found that a thermal spray coating can be formed with high adhesion efficiency even when thermal spraying is carried out using a coating. And based on such knowledge, the present inventors can enable thermal spraying of a powder for thermal spraying containing tungsten and a ternary boride by a high-speed flame spraying method. It has been found that the thermal spray coating to be formed can contain a tungsten phase and a ternary boride phase.
  • a thermal spray coating formed by thermal spraying a thermal spraying powder containing tungsten and a ternary boride by a high-speed flame spraying method is shown in the figure when a cross section is observed with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • a ternary boride Mo 2 FeB 2 , Mo 2 NiB 2 , or W 2 FeB 2 in the example shown in FIG. 7
  • W tungsten
  • FIG. 7 shows a thermal spray coating of Example 1 described later (a thermal spray coating formed by spraying a thermal spraying powder containing B, Mo, Ni, Ti, and W by a high-speed flame spraying method) using an SEM. The photograph obtained by doing is shown.
  • the thermal spray coating formed by such a high-speed flame spraying method even when measured by the X-ray diffraction method, a peak derived from the ternary boride is observed as shown in FIG. .
  • the thermal spray coating is remarkably improved in corrosion resistance to high-temperature metals and to air in a high-temperature environment. It can be improved.
  • the above-described peak intensity ratio I max / I w when the surface of the sprayed coating 21 is measured by the X-ray diffraction method may be 1/100 or more, preferably 1/100 50 or more, more preferably 1/25 or more, still more preferably 1/20 or more, and particularly preferably 1/18 or more. If the intensity ratio I max / I w is too low, the effect of including a ternary boride phase in the sprayed coating 21, that is, the effect of improving the corrosion resistance to high-temperature metals and the corrosion resistance to the atmosphere in a high-temperature environment. It can no longer be obtained.
  • the upper limit of the peak intensity ratio I max / I w is not particularly limited, but is usually 1 (1/1) or less.
  • the ternary boride constituting the ternary boride phase are not limited to, Mo 2 FeB 2, Mo 2 CoB 2, Mo 2 NiB 2, W 2 FeB 2, W 2 CoB 2, W 2 NiB 2 , MoCoB, WFeB, WCoB and the like.
  • Mo 2 NiB 2 and WFeB are preferable from the viewpoint of further improving the corrosion resistance against high-temperature metals and the corrosion resistance against the atmosphere in a high-temperature environment.
  • These ternary borides can be used singly or as a mixture of two or more.
  • the peak having the highest intensity among the peaks derived from the ternary boride phase is usually (211) plane peak derived from Mo 2 NiB 2 . Therefore, in this case, as the peak intensity I max described above, the peak intensity of the (211) plane derived from Mo 2 NiB 2 can be used, and this can be set as the peak intensity I max .
  • the ternary boride constituting the ternary boride phase mainly contains any of Mo 2 FeB 2 , W 2 FeB 2 , W 2 NiB 2 , Mo 2 CoB 2 , and W 2 CoB 2
  • the peak having the highest intensity among the peaks derived from the ternary boride phase is usually Mo 2 FeB 2 , W 2 FeB 2 , W 2 NiB 2 , Mo 2 CoB 2 , or W 2 CoB 2 . It becomes a peak of (211) plane derived from either.
  • the above-described peak intensity I max is derived from any one of Mo 2 FeB 2 , W 2 FeB 2 , W 2 NiB 2 , Mo 2 CoB 2 , and W 2 CoB 2 (211) plane.
  • This peak intensity I max can be used.
  • the ternary boride constituting the ternary boride phase is selected from Mo 2 FeB 2 , W 2 FeB 2 , Mo 2 NiB 2 , W 2 NiB 2 , Mo 2 CoB 2 , and W 2 CoB 2.
  • ternary borides When a plurality of ternary borides are contained (for example, when the ternary boride phase is composed of Mo 2 FeB 2 , Mo 2 NiB 2, W 2 FeB 2, etc.)
  • the sum of the peak intensities of the (211) plane derived from the ternary boride is used as the peak intensity I max .
  • the peak intensity used as it is, or may be the peak intensity I max.
  • the peak having the highest intensity among the peaks derived from the ternary boride phase is usually in WFeB.
  • the peak of the (112) plane is derived. Therefore, in this case, the peak intensity of (112) plane derived from WFeB is used as the peak intensity I max described above.
  • the peak intensity of (112) plane derived from WFeB is used as the peak intensity I max described above.
  • the peak intensity of (112) plane derived from WFeB is used as the peak intensity I max described above.
  • the ternary boride constituting the ternary boride phase mainly contains either MoCoB or WCoB
  • the peak having the highest intensity among the peaks derived from the ternary boride phase is Usually has a (112) plane peak derived from either MoCoB or WCoB.
  • the peak intensity of the (112) plane derived from either MoCoB or WCoB can be used, and this can be used as the peak intensity I max .
  • the ternary boride constituting the ternary boride phase includes a plurality of ternary borides selected from WFeB, MoCoB, and WCoB, the plurality of ternary borides are included.
  • the sum of the peak intensities of the (112) plane derived from can be used as the peak intensity I max .
  • the peak intensity may be used as it is to obtain the peak intensity I max .
  • the thermal spray coating 21 contains tungsten and a ternary boride, and an average value of the granule strength P (average of granule strength) is 10 MPa or more. It can be formed by flame spraying by flame spraying.
  • a ternary boride contained in the thermal spraying powder a ternary boride having a composition corresponding to the composition of the ternary boride phase contained in the sprayed coating 21 to be formed may be used.
  • the volume content of the ternary boride in the thermal spraying powder for forming the thermal spray coating 21 is preferably 1 to 30% by volume, more preferably 3 to 20% by volume.
  • the volume content of tungsten in the thermal spraying powder for forming the thermal spray coating 21 is preferably 70 to 99% by volume, more preferably 80 to 97% by volume.
  • the thermal spraying powder for forming the thermal spray coating 21 may also contain a binary boride in addition to tungsten and ternary boride, in order to form the thermal spray coating 21.
  • the volume content of the binary boride in the thermal spraying powder is preferably 0 to 20% by volume, more preferably 5 to 15% by volume.
  • the thermal spray coating 21 has higher hardness in normal temperature environment and high temperature environment without impairing corrosion resistance, and further improves wear resistance. be able to.
  • the binary boride to be contained in the thermal spraying powder one having a composition corresponding to the composition of the binary boride phase contained in the thermal spray coating 21 to be formed may be used.
  • the weight ratio of the ternary boride in the thermal spray coating 21 calculated from the thermal spraying powder composition and X-ray diffraction is preferably 0.5 to 16.0% by weight, more preferably 1.5 to 10.0% by weight. is there.
  • the thermal spray coating 21 can be further improved in corrosion resistance to the high temperature metal and to the atmosphere in the high temperature environment.
  • the weight ratio of tungsten in the thermal spray coating 21 calculated from the thermal spray powder composition and X-ray diffraction is preferably 84.0 to 99.5% by weight, more preferably 90.0 to 98.5% by weight.
  • the thermal spray coating 21 has a binary boron content from the viewpoint of further improving the hardness of the thermal spray coating 21 in a normal temperature environment and a high temperature environment. It is preferable that a binary boride phase composed of a fluoride is included.
  • the thermal spray coating 21 can have higher hardness in a normal temperature environment and a high temperature environment, and the wear resistance can be further improved. From the viewpoint, W 2 B is preferable.
  • These binary borides can be used singly or as a mixture of two or more.
  • the weight ratio of the binary boride in the thermal spray coating 21 calculated from the powder composition for thermal spraying and X-ray diffraction is preferably 0 to 18.0% by weight, more preferably 5.0 to 14.0% by weight.
  • the total weight ratio of the ternary boride and the binary boride in the thermal spray coating 21 calculated from the thermal spray powder composition and X-ray diffraction is preferably 0.5 to 34.0% by weight, more preferably 6.5 to 24.0% by weight.
  • the thermal spray coating 21 can be used in a normal temperature environment and a high temperature environment without impairing the excellent corrosion resistance and toughness of tungsten. As the hardness increases, the wear resistance, adhesion resistance, thermal shock resistance and workability can be further improved.
  • the weight ratio of W in the thermal spray coating 21 calculated from the thermal spraying powder composition and X-ray diffraction is determined as the total weight ratio of components other than the ternary boride and the binary boride, and the ratio is preferably It is 66.0 to 99.5% by weight, more preferably 76.0 to 93.5% by weight.
  • the thermal spray coating 21 is further improved in corrosion resistance to high-temperature metals and to air in a high-temperature environment. Can do.
  • the thickness of the sprayed coating 21 is not particularly limited, but is preferably 0.1 to 2 mm, more preferably 0.3 to 1.5 mm.
  • the obtained laminated tube 2 can be made more excellent in corrosion resistance against molten metal, and further, the amount of expensive tungsten used is suppressed and required for thermal spraying of tungsten. From the viewpoint that the amount of energy used can be reduced, this is advantageous in terms of cost.
  • the sprayed coating 21 has a Vickers hardness (HV) measured in a range of 300 to 700 ° C. (that is, a Vickers hardness when measured at any temperature within a range of 300 to 700 ° C.).
  • HV Vickers hardness
  • it is 400 or more, More preferably, it is 450 or more, More preferably, it is 500 or more.
  • the second layer 22 can be formed by spraying a metal material such as a steel material on the sprayed coating 21.
  • the metal material composing the second layer 22 is not particularly limited, and examples thereof include ferritic steel materials such as SUS430 and SUS429, and martensitic steel materials such as SUS420 and SUS403.
  • ferritic steel materials such as SUS430 and SUS429
  • martensitic steel materials such as SUS420 and SUS403.
  • a ferritic steel material is preferable.
  • the thickness of the second layer 22 is not particularly limited, but is preferably 0.1 to 0.9 mm. By setting the thickness of the second layer 22 within the above range, it is possible to more effectively prevent cracks in the second layer 22 caused by cooling and shrinking after thermal spraying.
  • the third layer 23 can be formed by spraying a metal material such as a steel material on the second layer 22.
  • the metal material constituting the third layer 23 is not particularly limited, and examples thereof include ferritic steel materials such as SUS430 and SUS429, and martensitic steel materials such as SUS420 and SUS403.
  • ferritic steel materials such as SUS430 and SUS429
  • martensitic steel materials such as SUS420 and SUS403.
  • martensitic steel is preferable from the viewpoint that the generation of cracks in the third layer 23 can be more effectively prevented in the process in which the third layer 23 is cooled after spraying.
  • the thickness of the third layer 23 is not particularly limited, but is preferably 1.0 to 5.0 mm. By setting the thickness of the third layer 23 within the above range, the strength of the laminated tube 2 can be further increased.
  • the laminated tube 2 of the present embodiment is configured.
  • the laminated tube 2 of the present embodiment may further include a steel material layer formed by shrink fitting on the outer peripheral surface of the third layer 23.
  • the steel material layer that is shrink-fitted on the outer peripheral surface of the third layer 23 include a tubular member made of a chromium molybdenum steel material equivalent to SCM440 defined in Japanese Industrial Standard (JIS G 4053).
  • the steel material layer may be fixed to the outer peripheral surface of the third layer 23 by bolt fastening, pins, or the like. Since the laminated tube 2 has a steel material layer, the strength of the laminated tube 2 can be increased.
  • the laminated tube 2 of this embodiment showed the example provided with two layers of the 2nd layer 22 and the 3rd layer 23 in the outer surface side of the sprayed coating 21, the outer surface of the sprayed coating 21 was shown.
  • the layer formed on the side may be a single layer or three or more layers.
  • a core material 3 (see FIG. 4) and a thermal spraying powder for forming the thermal spray coating 21 are prepared.
  • the thermal spraying powder can be formed, for example, as follows. First, a tungsten powder for forming a tungsten phase is mixed with a powder of elements constituting these boride phases for forming a ternary boride phase or a binary boride phase, and a binder and After adding the organic solvent, the mixture is pulverized using a pulverizer such as a ball mill. Subsequently, the powder (primary particles of several ⁇ m) obtained by mixing and pulverizing is granulated with a spray dryer or the like to form secondary particles of several tens of ⁇ m.
  • a pulverizer such as a ball mill
  • the secondary particles are sintered by heat treatment, and classified as necessary to obtain thermal spraying powder having an average value of granule strength P (average of granule strength) of 10 MPa or more.
  • the granule strength P is determined by measuring the particle diameter ⁇ (unit: ⁇ m) of the particles constituting the thermal spraying powder and the load (destructive load N B (unit: (N)) at which the particles are broken. machine (manufactured by Shimadzu Corporation, MCT-510) was measured using a on the basis of the breaking load N B and the particle diameter ⁇ measured, can be determined by the following equation (1).
  • the average particle strength is The average value of the results obtained by measuring such a granule strength P a plurality of times, and preferably the average value obtained by measuring 5 times or more.
  • P (2.48 ⁇ N B ) / ( ⁇ ⁇ ⁇ 2 ) (1)
  • a thermal treatment in obtaining the thermal spraying powder for example, a thermal treatment in obtaining the thermal spraying powder.
  • the heat treatment temperature is preferably 1,100 to 1,500 ° C., more preferably 1,300 to 1,500 ° C., further preferably 1,300 to 1,400 ° C.
  • Particularly preferred is a method in which the temperature is 1,350 to 1,400 ° C. and the heat treatment time is preferably 60 to 120 minutes.
  • the bonding between the particles constituting the thermal spraying powder becomes weak, and the thermal spraying powder tends to collapse at the time of thermal spraying, and is not sufficiently accelerated in the thermal spraying frame, so that the adhesion efficiency may be reduced.
  • the heat treatment temperature is too high, the sintering proceeds and the bonding between the powders becomes too strong, and it becomes difficult to disintegrate the sintered body and it becomes difficult to take it out as a thermal spraying powder.
  • the average granule strength of the thermal spraying powder may be 10 MPa or more, but is preferably 50 MPa or more. However, since the bond between the powders tends to be too strong when greatly exceeding 400 MPa, and the adhesion efficiency is remarkably lowered due to being repelled from the base material at the time of thermal spraying, the upper limit of the average granular strength is preferably 400 MPa or less. . By setting the average granule strength of the thermal spraying powder within the above range, when spraying the thermal spraying powder, the adhesion efficiency of the thermal spraying powder to the metal base material is further improved, and the thermal spray coating to be formed Variations in thickness can be reduced.
  • the thermal spray coating 21 is formed by spraying the thermal spraying powder prepared as described above onto the core material 3 (see FIG. 4).
  • the gas used for thermal spraying is relatively low temperature (specifically, 3000 ° C. or lower), and ternary boron by thermal spraying is used. It is preferable to use a high-speed flame spraying method from the viewpoint that the change in the composition of the fluoride is suppressed and the thermal spray coating to be formed can contain a ternary boride.
  • a metal material for forming the second layer 22 is prepared, and the second layer 22 is formed by spraying the prepared metal material on the sprayed coating 21 (see FIG. 4). Further, a metal material for forming the third layer 23 is prepared, and the prepared metal material is sprayed onto the second layer 22 to form the third layer 23 (see FIG. 4). As a result, as shown in FIG. 4, the thermal spray coating 21, the second layer 22, and the third layer 23 are formed in this order on the core material 3.
  • a thermal spraying method for forming the 2nd layer 22 and the 3rd layer 23 when using the steel material mentioned above as a metal material which comprises the 2nd layer 22 and the 3rd layer 23 Is preferably wire arc spraying.
  • a steel material layer may be formed by shrink fitting a tubular steel material on the outer peripheral surface of the third layer 23.
  • the core material 3 is cut using a drilling machine, a BTA (Boring and Trepanning Association) deep hole processing machine, or the like.
  • a BTA Biting and Trepanning Association
  • the core material 3 shown in FIG. 4 is removed, the laminated tube 2 as shown in FIG. 2, specifically, the inner surface becomes the thermal spray coating 21, and the second layer 22 and the third layer 23 on the thermal spray coating 21.
  • a laminated tube 2 is formed.
  • the laminated tube 2 of the present embodiment is manufactured as described above.
  • the ratio (L / D) of the length L of the laminated tube 2 to the inner diameter D of the thermal spray coating 21 is preferably 2 or more.
  • the inner diameter D of the thermal spray coating 21 is preferably 40 to 160 mm, more preferably 40 to 120 mm.
  • the ratio of the inner diameter D to the length L (L / D) is in the above range, and the laminated tube 2 is excellent even when the shape of the laminated tube 2 is relatively elongated. Can be manufactured.
  • a method of spraying a material containing tungsten on the inner surface of a tubular member prepared in advance can be considered.
  • the thermal spraying torch does not enter the inside of the member and thermal spraying cannot be performed.
  • a spraying distance of 100 to 150 mm is appropriate, and even when an inner diameter torch is used, spraying cannot be performed on an inner diameter of 100 mm or less.
  • the inner diameter is 100 mm or less, it must be sprayed at an angle from both ends of the laminated tube.
  • the coating properties are drastically reduced when the spray angle is smaller than 45 °, so that the inner surface of the tube is sprayed.
  • the L / D is 2 or more.
  • the laminated tube 2 of the present embodiment has the thermal spray coating 21 as an inner layer and the second layer 22 and the third layer 23 on the inner layer, and therefore has excellent corrosion resistance against molten metal.
  • This is advantageous in terms of cost. That is, if the entire laminated tube 2 is made of a material containing tungsten (such as a boride-based tungsten-based alloy), the corrosion resistance against the molten metal is improved, but the material containing tungsten is expensive, and the molding process is costly. There is a problem that it takes.
  • the laminated tube 2 of the present embodiment only the inner layer is constituted by a layer containing tungsten (thermal spray coating 21), and the exterior of the thermal spray coating 21 is the second layer 22 and the third layer made of steel or the like. 23, the corrosion resistance against molten metal can be improved, while it can be manufactured at a relatively low cost.
  • the total thickness of the laminated tube 2 of the present embodiment can be increased by the second layer 22 and the third layer 23, the strength of the laminated tube 2 can be improved.
  • by increasing the total thickness of the second layer 22 and the third layer 23 it becomes possible to form a steel material layer on the outer peripheral surface of the third layer 23 by shrink fitting as described above. The strength can be further improved.
  • the thermal spray coating 21 is the inner layer and two layers of the second layer 22 and the third layer 23 are formed thereon is shown.
  • the layer formed on the thermal spray coating 21 is a single layer. A layer may be sufficient and three or more layers may be sufficient.
  • the thermal spray coating of the present invention is applied to a sleeve (laminate tube) of a die casting apparatus, but the application of the thermal spray coating of the present invention is not limited to this.
  • the thermal spray coating of the present invention is in direct contact with a high-temperature metal such as a molten metal, such as a low-pressure casting method, a gravity mold casting method, or a device part used for hot stamping, in addition to a die-casting device part. It can be suitably used as a component used as a part.
  • Example 1 First, B: 0.8% by weight, Mo: 3.5% by weight, Ni: 1.1% by weight, Ti: 0.9% by weight, W: 100 parts by weight of the raw material mixed at the ratio of the balance Then, 5 parts by weight of paraffin was added, and this was wet pulverized in acetone with a vibration ball mill for 25 hours to prepare a pulverized powder. Next, primary particles were obtained by drying the prepared pulverized powder at 150 ° C. for 18 hours in a nitrogen atmosphere. And after mixing the obtained primary particle with acetone in the weight ratio of 1: 1, the secondary particle was obtained by granulating with a spray dryer. Next, the obtained secondary particles were sintered by holding them at 1,350 ° C. for 1 hour in a vacuum for heat treatment, and classifying them to prepare thermal spraying powders.
  • the photograph obtained by observing a cross section with SEM about the produced test piece is shown in FIG. From the result of FIG. 7, the cross section of the test piece shows W 2 constituting the tungsten phase, Mo 2 FeB 2 , Mo 2 NiB 2 and W 2 FeB 2 constituting the ternary boride phase, and the binary boride phase. W 2 B constituting each was observed.
  • the X-ray-diffraction measurement was performed by the X-ray-diffraction method using the X-ray-diffraction apparatus (Rigaku company make, model number: RINT-2500).
  • a graph obtained by X-ray diffraction measurement is shown in FIG.
  • the results are shown in Table 1.
  • the Vickers hardness (HV) of the prepared test piece was measured at a load of 200 g using a Vickers hardness meter (manufactured by Akashi Seisakusho, product number: MVK-G2) in an environment of 20 ° C. did.
  • a Vickers hardness meter manufactured by Akashi Seisakusho, product number: MVK-G2
  • the Vickers hardness (HV) of the test piece is measured with a high-temperature hardness meter (manufactured by Nikon Corporation, model number). : QM-2). The results are shown in FIG.
  • Example 2 Except that the spraying distance was changed from 250 mm to 300 mm when performing high-speed flame spraying, a sprayed coating was formed on the substrate in the same manner as in Example 1, and a test piece having a block shape of 10 mm ⁇ 10 mm ⁇ 5 mm was formed. Obtained. In addition, when the cross section of the prepared test piece was observed by SEM in the same manner as in Example 1, the cross section of the test piece showed W constituting the tungsten phase and Mo 2 FeB constituting the ternary boride phase. 2 , Mo 2 NiB 2 and W 2 FeB 2 , and W 2 B constituting the binary boride phase were observed, respectively.
  • Example 2 In the same manner as in Example 1, for to prepare a test piece was subjected to X-ray diffraction measurement, in Example 2, to the peak intensity I w of from tungsten phase (110) plane, ternary the boron The ratio (I max / I w ) of peak intensity I max (peak intensity of (211) plane derived from Mo 2 NiB 2 ) of the peak having the highest intensity among the peaks derived from the chemical phase is 1/9. It was 5. Further, the obtained test piece was evaluated for corrosion resistance in a high-temperature atmosphere in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 When producing the thermal spraying powder, the composition was as follows: B: 0.4% by weight, Mo: 3.2% by weight, Ni: 1.0% by weight, W: balance (Ti is substantially 0).
  • the powder for thermal spraying was prepared in the same manner as in Example 1 except that the heat treatment temperature of the secondary particles was changed from 1,350 ° C. to 1,150 ° C. And except having used the obtained thermal spraying powder, it carried out similarly to Example 1, and formed the thermal spray coating on the base material, and obtained the test piece of the block shape of 10 mm x 10 mm x 5 mm.
  • Example 3 to the peak intensity I w of from tungsten phase (110) plane, ternary the boron The ratio (I max / I w ) of peak intensity I max (peak intensity of (211) plane derived from Mo 2 NiB 2 ) of the peak having the highest intensity among the peaks derived from the chemical phase is 1/16. It was 9. Further, the obtained test piece was evaluated for corrosion resistance in a high-temperature atmosphere in the same manner as in Example 1. The results are shown in Table 1.
  • a thermal spraying powder was produced in the same manner as in Example 1.
  • 55 ⁇ 60 ⁇ 13 mm SKD61 steel was prepared as a base material for thermal spraying.
  • a thermal spray coating is formed on the base material by spraying the thermal spraying powder from a distance of 250 mm on the base material with a plasma spraying machine (product number: EUTRONIC PLASMA SYSTEM 5000, manufactured by Nihon Utec Co., Ltd.). did.
  • the test piece was produced by processing this into the shape of 55x12x13 mm.
  • the photograph obtained by observing with an optical microscope (100 times magnification) is shown in FIG.
  • FIG. 12 (A) the photograph obtained by observing with a scanning electron microscope (SEM) is shown in FIG. 12 (B). Respectively. From the results of FIGS. 12A and 12B, it was confirmed that a sprayed coating was formed on the surface of the test piece.
  • Example 1 the surface of the prepared test piece was subjected to X-ray diffraction measurement in the same manner as in Example 1.
  • the results are shown in FIG. From the results of FIG. 6, in Comparative Example 1, no peak derived from the ternary boride phase could be observed. Therefore, the peak intensity ratio I max / I w of Comparative Example 1 was 1/247.
  • the results are shown in Table 1.
  • the peak derived from the binary boride in Comparative Example 1 was confirmed partially, to the peak intensity I w of from tungsten phase (110) plane, a peak derived from binary borides Among them, the peak intensity I max-2 ratio (I max-2 / I w ) of the peak having the highest intensity was 1 / 29.7.
  • Example 1 the corrosion resistance (part 1) in high-temperature air was evaluated and the Vickers hardness was measured.
  • Table 1 the corrosion resistance (part 1) in high-temperature air was evaluated and the Vickers hardness was measured.
  • FIG. 9 (B) the results are shown in Table 1, FIG. 9 (B) and FIG.
  • Comparative Example 1 the measurement of Vickers hardness is performed only in an environment of 100 ° C., 200 ° C., 300 ° C., 400 ° C., 500 ° C., 600 ° C., 700 ° C., and 800 ° C. as shown in FIG. It was.
  • ⁇ Comparative example 2> Except for changing the spraying distance from 250 mm to 300 mm when performing plasma spraying, a sprayed coating is formed on the substrate in the same manner as in Comparative Example 1 to obtain a 10 mm ⁇ 10 mm ⁇ 5 mm block-shaped test piece. It was. Incidentally, in the same manner as in Example 1, was subjected to X-ray diffraction measurement, in Comparative Example 2, to the peak intensity I w of from tungsten phase (110) plane, a peak derived from the ternary boride The ratio (I max / I w ) of the peak intensity I max (peak intensity of the (211) plane derived from Mo 2 NiB 2 ) of the peak with the highest intensity was 1/148. Further, the obtained test piece was evaluated for corrosion resistance in a high-temperature atmosphere in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 First, primary particles were produced in the same manner as in Example 1. Next, the produced primary particles are subjected to pressure sintering with an SPS (discharge plasma sintering apparatus) and sintered at a temperature of 1300 to 1500 ° C. for 10 minutes to obtain a sintered body made of a hard sintered alloy. It was. The heating rate during sintering was 100 ° C./min. Subsequently, the obtained sintered body was processed into a block shape of 15 mm ⁇ 15 mm ⁇ 5 mm to prepare a test piece. And using the produced test piece, it carried out similarly to Example 1, and evaluated corrosion resistance (the 2) in high temperature air
  • Example 2 A test piece was prepared by processing SKD61 steel (SKD61 nitride material) having a nitrided layer formed on the surface thereof into a 10 mm ⁇ 5 mm ⁇ 5 mm block shape. And the Vickers hardness was measured like Example 1 using the produced test piece. The results are shown in FIG.
  • the thermal spray coating having a peak intensity ratio I max / I w of 1/100 or more when the surface is measured by the X-ray diffraction method is Similar to Reference Example 1 (sintered specimen), it was excellent in corrosion resistance in high-temperature air (Examples 1 to 3).
  • a ternary boride phase is present in the thermal spray coating as shown in FIG. 7, and this ternary boride phase serves as a binding phase to bond the tungsten phases together.
  • the sprayed coating becomes dense, and gas permeation can be suppressed. Therefore, it is considered that the corrosion resistance in high-temperature air is excellent.
  • Example 1 the hardness is higher than that of Comparative Example 1 (sprayed coating formed by plasma spraying method), and the environment is higher than that of Reference Example 2 (SKD61 nitride material).
  • the lowering of the hardness is suppressed, so that even when in direct contact with a high-temperature metal such as molten metal (particularly in direct contact with molten aluminum at about 600 to 700 ° C.), it is resistant to wear. It was confirmed that it was excellent in property.
  • the hardness is higher than that in Comparative Example 1, and further, the decrease in hardness under a high temperature environment is suppressed as compared with Reference Example 2. there were.
  • the thermal spray coating in which the peak intensity ratio I max / I w is less than 1/100 when the surface is measured by the X-ray diffraction method is The corrosion resistance was inferior (Comparative Examples 1 and 2).
  • Comparative Examples 1 and 2 as shown in FIG. 5, there is no ternary boride phase acting as a binder phase in the thermal spray coating, and as a result, the thermal spray coating is sparse as shown in FIG. Thus, it is considered that the gas easily permeates, and the corrosion resistance in the high-temperature atmosphere is inferior.
  • Example 3 A thermal spraying powder was prepared in the same manner as in Example 1 except that the heat treatment conditions for the secondary particles were changed to a condition of holding at 1,100 ° C. for 1 hour in a vacuum.
  • the particle diameter ⁇ (unit: ⁇ m) of the particles constituting the thermal spraying powder at normal temperature (20 ° C.) and the load (destructive load N (unit: (N)) was measured using a micro compression tester (manufactured by Shimadzu Corporation, product number: MCT-510), and based on the measured particle diameter ⁇ and breaking load N, The granule strength P of the thermal spraying powder was obtained, and the granule strength P of the thermal spraying powder was obtained 5 times in this way, and the average value of the obtained 5 granule strengths P was obtained as the average of the granule strength.
  • the results are shown in Table 2.
  • P (2.48 ⁇ N) / ( ⁇ ⁇ ⁇ 2 ) (1)

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  • Mechanical Engineering (AREA)
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Abstract

L'invention concerne un revêtement par pulvérisation contenant une phase tungstène et une phase borure tri-élémentaire. Lorsqu'elle est soumise à un essai de diffraction des rayons X, la surface du revêtement par pulvérisation présente un rapport (Imax/Iw), qui représente l'intensité de crête Imax pour le pic ayant la plus grande intensité parmi des pics provenant de la phase borure tri-élémentaire rapportée à l'intensité de pic Iw sur la surface (110) provenant de la phase tungstène, de 1/100 ou plus.
PCT/JP2018/015514 2017-04-21 2018-04-13 Revêtement par pulvérisation, tuyau stratifié et procédé de fabrication d'un revêtement par pulvérisation WO2018193982A1 (fr)

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JP2017066465A (ja) * 2015-09-29 2017-04-06 株式会社フジミインコーポレーテッド 溶射用粉末及び溶射皮膜の形成方法

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