WO2019202720A1 - Buse pour pulvérisation à froid et dispositif de pulvérisation à froid - Google Patents

Buse pour pulvérisation à froid et dispositif de pulvérisation à froid Download PDF

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Publication number
WO2019202720A1
WO2019202720A1 PCT/JP2018/016234 JP2018016234W WO2019202720A1 WO 2019202720 A1 WO2019202720 A1 WO 2019202720A1 JP 2018016234 W JP2018016234 W JP 2018016234W WO 2019202720 A1 WO2019202720 A1 WO 2019202720A1
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WO
WIPO (PCT)
Prior art keywords
nozzle
powder material
cold spray
powder
cold
Prior art date
Application number
PCT/JP2018/016234
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English (en)
Japanese (ja)
Inventor
和真 高橋
佳弘 細谷
弘之 吉見
Original Assignee
株式会社特殊金属エクセル
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社特殊金属エクセル filed Critical 株式会社特殊金属エクセル
Priority to PCT/JP2018/016234 priority Critical patent/WO2019202720A1/fr
Priority to JP2018534880A priority patent/JP6404532B1/ja
Publication of WO2019202720A1 publication Critical patent/WO2019202720A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/14—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas designed for spraying particulate materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/16—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas incorporating means for heating or cooling the material to be sprayed
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles

Definitions

  • the present invention relates to a nozzle suitable for use in cold spray and a cold spray apparatus equipped with the nozzle.
  • the cold spray method is a technique in which a powder material (metal powder) is collided with a base material in a solid phase state below the melting temperature to form a film on the base material. This is essentially different from the thermal spraying method in which the material is melted and adhered to the substrate.
  • the cold spray method provides a dense film that does not oxidize in the atmosphere, has little thermal effect on the material particles, suppresses thermal alteration, has a high film formation rate, can be thickened, and has high adhesion efficiency Etc., and has excellent advantages that cannot be obtained by thermal spraying. For this reason, attention has been focused on effectively applying the metal material on which this film is formed to various structural materials.
  • the conventional cold spray method has a problem in that the powder material adheres to the inner wall portion of the nozzle due to the material of the nozzle and the powder material to be used.
  • the spraying temperature is higher than 500 ° C in order to increase the adhesion efficiency
  • the temperature of the inner wall of the nozzle rises, and the interatomic bonding between the powder material and the nozzle material easily proceeds to the nozzle.
  • the adhesion of becomes faster.
  • Fig. 3 (a) shows the internal state of the nozzle when stainless steel is used as the nozzle material and maraging steel is used as the powder material, and the nozzle is continuously operated for 120 minutes at a spraying pressure of 3.0 MPa and a spraying temperature of 800 ° C. Show.
  • FIG. 1 shows the internal state of the nozzle when stainless steel is used as the nozzle material and maraging steel is used as the powder material, and the nozzle is continuously operated for 120 minutes at a spraying pressure of 3.0 MPa and a spraying temperature of 800 ° C. Show. In FIG
  • the broken line portion indicates the location where the powder material is adhered, but it has been confirmed that 15% of the cross-sectional area is blocked.
  • the nozzle is blocked in a short time, and therefore, the nozzle needs to be frequently replaced. As a result, this has been an obstacle to the practical application of the continuous coating method that requires operation for 300 minutes or more.
  • known documents referring to the cold spray method and the thermal spraying method will be described.
  • Patent Document 1 describes that the portion of the nozzle inner wall surface on which particle adhesion is likely to occur can be effectively prevented by adhering the raw material powder by configuring it with either quartz glass or borosilicate glass.
  • Glass materials have a problem that wear progresses due to the spraying of high hardness powder material such as maraging steel.
  • Fig. 3 (b) shows a state in which maraging steel is used as a powder material, and a quartz glass tube having an outer diameter of ⁇ 8 and an inner diameter of ⁇ 6 is continuously operated for 15 minutes at a spraying pressure of 3.0 MPa and a spraying temperature of 800 ° C. It has been confirmed that as much as 40% of wear occurs per volume.
  • Patent Document 1 the entire divergent part is made of borosilicate glass, and using Inconel powder material, the operating gas temperature is 800 ° C, the powder supply rate is 200 g / min, and the chamber gas pressure is 3 MPa.
  • the evaluation relates to the observation of the turbulence of the jet flow of the powder material, the confirmation of the powder material adhesion on the inner wall of the nozzle and the film formation efficiency, and the degree of wear of the nozzle is not disclosed .
  • Patent Document 2 although it is a nozzle for a thermal spray gun, it is possible to control the plasma / arc adhesion region by the dynamic influence of heat by configuring the nozzle surface portion with any of tungsten, molybdenum, silver or iridium. It is disclosed. However, while the cold spray method causes the powder material to collide with the base material in the solid state below the melting temperature, the spraying method melts the material to be sprayed and attaches it to the base material. The occurrence of this proceeds by a completely different mechanism.
  • high-speed flame spraying and plasma spraying can be cited as spraying methods that operate in the supersonic region as in the cold spray method.
  • high-speed flame spraying the inner wall surface on the outlet side of the nozzle tends to be clogged, but the cause is that the powder material that has entered the high-speed frame is pulverized and refined, resulting in extremely poor fluidity.
  • measures such as lowering the combustion chamber pressure, increasing the particle size of the powder material, shortening the nozzle length, and lowering the supply amount of the powder material are effective.
  • Patent Document 3 discloses a method of preventing nozzle blockage by forming a part or all of a divergent portion, which is an enlarged portion of a nozzle, with a glass material.
  • the replacement work efficiency of the divergent portion is increased by using different materials such as metal and heat-resistant resin.
  • a combination of members having a difference in linear expansion coefficient may cause voids due to non-uniform thermal diffusion on the joint surface in addition to interface peeling due to thermal shock.
  • tungsten carbide is used for the linear convergence nozzle of the micro cold spray direct writing system.
  • Nozzle molding of tungsten carbide has a feature that the finished surface roughness is rough because a sintering method is common. Therefore, after sintering, it is necessary to smooth the inside of the nozzle by machining such as surface polishing.
  • tungsten carbide is a carbide, its workability is very poor, and it is difficult to satisfy the required dimensional accuracy within ⁇ 2.0 ⁇ m inside the sonic nozzle.
  • the present invention has been made in view of the above circumstances, and as a nozzle material, a cold spray that prevents clogging due to adhesion of the powder material to the inner wall of the nozzle and prevents the nozzle from being worn even when a high-hardness powder material is used.
  • An object is to provide a nozzle and a cold spray device.
  • the present inventors have conducted intensive research, and the powder material does not adhere to the inner wall of the nozzle even when a long-time cold spray is performed.
  • the design of the material and shape of the nozzle is particularly important as will be described later.
  • the present inventors use a metal having a cohesive energy of 170 kcal / g-atom or more and an alloy thereof as the nozzle material, so that the powder material can be applied to the nozzle inner wall even when cold spray is performed for a long time. It has been found that the nozzle does not wear even when a high hardness powder material is not used. In other words, the reason why the powder material does not adhere to the nozzle is that the metal with higher cohesive energy, which is the force for separating the constituent atoms of the solid, is more stable as a solid, and the interatomic bond between the powder material and the nozzle material is less likely to occur. Can be mentioned.
  • FIG. 4 is a graph showing the relationship between each period and the cohesive energy in the periodic table. Further, the cause of the nozzle not being worn is that the nozzle material has characteristics of a high melting point and a high hardness.
  • the spraying temperature is higher than 500 ° C. in order to increase the adhesion efficiency
  • the temperature of the inner wall surface of the nozzle rises, and the higher the temperature, the more brittle the nozzle material becomes and the more easily it is worn.
  • Metals with high cohesive energy are characterized by having a high melting point of 1900 ° C. or higher and are not easily embrittled at high temperatures.
  • a material of HV150 or higher for the nozzle it is possible to further prevent nozzle wear.
  • tantalum has a hardness of HV220
  • tungsten has a hardness of HV350
  • osmium has a high hardness of HV410 and is hard to wear.
  • vanadium of HV120 and the like is easily worn.
  • tungsten is disclosed in the nozzle for a thermal spray gun in Patent Document 2, the purpose of this document is to use a high melting point material that can withstand direct contact with a plasma arc.
  • the cold spray method is not limited to this, and molybdenum and iridium, which are high melting point materials disclosed in Patent Document 2, cannot be used because the cohesive energy is less than 170 kcal / mol.
  • molybdenum is 155 kcal / mol and iridium is 165 kcal / mol.
  • FIG. 3 (c) shows the internal state of the nozzle when operated continuously for 120 minutes at a spraying pressure of 3.0 MPa and a spraying temperature of 800 ° C. using molybdenum as the nozzle material and maraging steel as the powder material.
  • a blockage of 5% occurs in the cross-sectional area.
  • the cohesive energy is less than 170 kcal / mol, it can be said that an interatomic bond between the powder material and the nozzle material occurs and is likely to adhere.
  • the present invention has been made by integrating the above findings and has the following configuration.
  • Nozzle inlet portion to which gas for accelerating powder material and heating powder material is supplied a nozzle reduction portion following this nozzle inlet portion, a divergent nozzle enlargement portion following this nozzle reduction portion, and this nozzle
  • a powder material inlet provided in the enlarged portion, and a powder material charged from the powder material inlet and heated below the melting point of the powder material by the gas is conveyed to the gas, and the substrate is supersonic.
  • a nozzle for cold spray formed with a nozzle outlet part sprayed on The nozzle is made of a metal or an alloy having a cohesive energy of 170 kcal / g-atom or more, and a nozzle for cold spraying.
  • a cold spray device comprising means for supplying the powder material into the nozzle from the inlet.
  • the present invention by using a metal or alloy having a cohesive energy of 170 kcal / g-atom or more as a material for a nozzle, it is possible to prevent the powder material from adhering to the inner wall of the nozzle and to have a high hardness. Can be used to produce a cold spray coating without wear on the nozzle. As a result, it is possible to produce a continuous coating that requires 300 minutes or more of operation for all powder materials regardless of hardness. The film position accuracy can be obtained. Moreover, since the material of the nozzle is not tungsten carbide but a metal or an alloy as in the invention of Patent Document 4, the moldability is good and the inside of the nozzle can be made smooth.
  • FIG. 1 is a schematic sectional view showing an example of a main body portion of a cold spray nozzle according to the present invention.
  • FIG. 2 is an explanatory diagram showing an overall outline of the cold spray apparatus.
  • FIG. 3 is a photograph showing the internal state of the nozzle when continuously operated using a nozzle made of a material that does not fall within the scope of the present invention.
  • FIG. 3A shows the internal state of the nozzle when continuously operating for 120 minutes at a spraying pressure of 3.0 MPa and a spraying temperature of 800 ° C. using stainless steel as the nozzle material and maraging steel as the powder material.
  • FIG. 3 (b) shows the state when maraging steel is used as the powder material and the quartz glass tube with an outer diameter of ⁇ 8 and an inner diameter of ⁇ 6 is continuously operated for 15 minutes at a spraying pressure of 3.0 MPa and a spraying temperature of 800 ° C.
  • Fig. 3 (c) shows the inside of the nozzle when operated continuously for 120 minutes at a spraying pressure of 3.0 MPa and a spraying temperature of 800 ° C, using molybdenum as the nozzle material and maraging steel as the powder material. It is a photograph showing the state.
  • FIG. 4 is a graph showing the relationship between each period in the periodic table and the cohesive energy, and the solid line with the highest peak indicates the sixth period in the periodic table. This table is quoted from 2006/10 literature, the origin of manufacturing – the world of science vol30 “Iron in metal”.
  • FIG. 5 shows a rewinding device that sprays a powder material onto the center of the width of the base material while winding the base material.
  • the form of the nozzle according to the present invention will be described based on the sectional view of the nozzle body shown in FIG.
  • the nozzle body continues through a reduction part 1 following a nozzle inlet part 11 a to which acceleration gas (flow direction is indicated by an arrow) is supplied, and a throat part 2 (minimum reduction part) to the reduction part 1. It is comprised from the elongate wide end expansion part 3 and the nozzle exit part 11b.
  • the nozzle according to the present invention only needs to include the reduced portion 1, the throat portion 2, and the enlarged portion 3 between the nozzle inlet portion 11a and the nozzle outlet portion 11b, and other shapes are arbitrary.
  • the enlarged portion 3 may be a quadrangular pyramid divergent shape, and a parallel portion may be provided on the nozzle outlet side from the enlarged portion 3.
  • the enlarged portion 3 is provided with a powder inlet 4 into which a powder material is charged.
  • the powder inlet 4 is preferably located close to the throat portion 2 in the enlarged portion 3.
  • the cold spray nozzle (nozzle body) shown in FIG. 1 is an example in which one powder inlet 4 is provided, but a plurality of nozzles may be provided as necessary.
  • the powder materials may be supplied from a plurality of powder inlets 4 using a required number of powder supply devices.
  • all of the reduced portion 1, the throat portion 2 and the enlarged portion 3 are formed of a metal or alloy having a cohesive energy of 170 kcal / g-atom or more, and as a result, adhesion and wear of the nozzle inner wall portion are prevented. be able to.
  • the nozzle body may be configured by combining a plurality of metals or alloys. Therefore, it is preferable to limit the dimensional accuracy to any one of them.
  • the method for producing the nozzle is not particularly limited, but machining by a machine tool such as machining, machining by a press, or the like is common.
  • the nozzle body may be manufactured by combining a plurality of members, but it is preferable that the entire nozzle is an integral type because there is a possibility that a gap is generated due to non-uniform thermal diffusion of the joint surface.
  • the material of the nozzle (nozzle body) is selected from tungsten, tantalum, rhenium, hafnium, niobium and alloys thereof having a cohesive energy of 170 kcal / g-atom or more. Niobium is preferred.
  • As the alloy an alloy such as tungsten-niobium, tantalum-tungsten, or tantalum-niobium is preferable because it is easily dissolved.
  • the accelerating gas examples include air, nitrogen, helium, argon, or a mixture thereof. Copper and other materials that easily oxidize powder can improve the adhesion efficiency by using helium as an acceleration gas, so an appropriate acceleration gas can be selected depending on the powder material and the material of the substrate to be laminated. preferable.
  • FIG. 2 is an overall schematic diagram of the cold spray apparatus according to the present invention.
  • the accelerating gas is supplied in the order of the compression cylinder 5 and the transport pipe 6, and is heated by a heater 7 provided in the transport pipe as necessary. Since the heating temperature increases the adhesion efficiency as the temperature increases, the lower limit is preferably 100 ° C. or higher and the upper limit is preferably within the range of the melting point of the material powder used.
  • the powder material is supplied in the order of the powder supply device 8 and the transport pipe 9, but when mixing a plurality of powder materials, it is necessary to prepare the necessary number of powder supply devices.
  • the powder material supplied from the powder inlet 4 is ejected from the nozzle outlet 11 in a state where the acceleration gas transported into the chamber 10 passes through the nozzle throat 2 and is accelerated at supersonic speed.
  • the “supersonic speed” is a speed higher than the sound speed of 1225 km / h, and the upper limit of operation in the present invention is 3960 km / h.
  • reference numeral 12 denotes a nozzle body
  • 13 denotes a rewinding device.
  • Table 3 shows the evaluation results of nozzle clogging, adhesion efficiency, and location accuracy with respect to the stacking conditions.
  • Evaluation of nozzle clogging is when the inner wall of the nozzle is observed after 300 minutes of operation, and the case where adhesion of the material powder is not confirmed is set to “Yes”, and the powder material does not come out due to clogging during 300 minutes of operation. Was rejected as “x”.
  • the film position accuracy was evaluated by measuring the stacking position and stacking width of the central part of the pure nickel base material at the time when the length of 1 meter elapsed after the start of spraying and when the length of 1 meter after the end of spraying was measured. A case where the difference in the stacking position or stacking width was 0.5 mm or less was evaluated as “good”, and a case where it exceeded 0.5 mm was determined as “failed”.
  • the metal or alloy having a cohesive energy of 170 kcal / g-atom or more is used as the material of the nozzle body, so that the powder material adheres to the inner wall of the nozzle.
  • the nozzle is not worn even when a powder material with high hardness is used, and continuous coating production requiring operation for 300 minutes or more can be performed and high film position accuracy can be obtained.

Abstract

Le problème décrit par la présente invention est de fournir une buse pour pulvérisation à froid et un dispositif de pulvérisation à froid qui empêchent le colmatage dû à l'adhérence de matériaux en poudre sur une partie de paroi interne de la buse pour pulvérisation à froid et qui a une buse qui n'est pas abrasée même lors de l'utilisation de matériaux en poudre à dureté élevée. La solution selon l'invention porte sur une buse pour pulvérisation à froid destinée à pulvériser des matériaux en poudre comprenant une partie réduite (1), une partie gorge (2), une partie élargie (3) s'élargissant vers une extrémité, et un corps de buse (12) dans lequel est ménagé un orifice de chargement de matériau en poudre (4). Le corps de buse (12) est constitué d'un matériau en métal ou en alliage ayant une énergie de cohésion d'au moins 170 kcal/g-atome. Le dispositif de pulvérisation à froid est un dispositif destiné à effectuer une pulvérisation à froid à l'aide de la buse pour pulvérisation à froid dont la constitution est décrite ci-dessus.
PCT/JP2018/016234 2018-04-20 2018-04-20 Buse pour pulvérisation à froid et dispositif de pulvérisation à froid WO2019202720A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2018/016234 WO2019202720A1 (fr) 2018-04-20 2018-04-20 Buse pour pulvérisation à froid et dispositif de pulvérisation à froid
JP2018534880A JP6404532B1 (ja) 2018-04-20 2018-04-20 コールドスプレー用ノズル及びコールドスプレー装置

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PCT/JP2018/016234 WO2019202720A1 (fr) 2018-04-20 2018-04-20 Buse pour pulvérisation à froid et dispositif de pulvérisation à froid

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005095886A (ja) * 2003-09-02 2005-04-14 Nippon Steel Corp コールドスプレー用ノズル並びにコールドスプレー被膜及び製造方法
JP2008093635A (ja) * 2006-10-16 2008-04-24 Plasma Giken Kogyo Kk コールドスプレー用ノズル及びコールドスプレー装置
JP2009179831A (ja) * 2008-01-29 2009-08-13 Plasma Giken Kogyo Kk コールドスプレー用ノズル及びコールドスプレー装置
JP2011000584A (ja) * 2009-06-18 2011-01-06 Honda Motor Co Ltd コールドスプレー用ノズル
JP2012025983A (ja) * 2010-07-20 2012-02-09 Startack Kk 被膜形成方法及びその方法により形成される複合材
JP2015218353A (ja) * 2014-05-16 2015-12-07 株式会社日立製作所 ノズル及びアタッチメント

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005095886A (ja) * 2003-09-02 2005-04-14 Nippon Steel Corp コールドスプレー用ノズル並びにコールドスプレー被膜及び製造方法
JP2008093635A (ja) * 2006-10-16 2008-04-24 Plasma Giken Kogyo Kk コールドスプレー用ノズル及びコールドスプレー装置
JP2009179831A (ja) * 2008-01-29 2009-08-13 Plasma Giken Kogyo Kk コールドスプレー用ノズル及びコールドスプレー装置
JP2011000584A (ja) * 2009-06-18 2011-01-06 Honda Motor Co Ltd コールドスプレー用ノズル
JP2012025983A (ja) * 2010-07-20 2012-02-09 Startack Kk 被膜形成方法及びその方法により形成される複合材
JP2015218353A (ja) * 2014-05-16 2015-12-07 株式会社日立製作所 ノズル及びアタッチメント

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