WO2024128115A1 - Manufacturing method for open rack vaporizer member and open rack vaporizer member - Google Patents

Manufacturing method for open rack vaporizer member and open rack vaporizer member Download PDF

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WO2024128115A1
WO2024128115A1 PCT/JP2023/043786 JP2023043786W WO2024128115A1 WO 2024128115 A1 WO2024128115 A1 WO 2024128115A1 JP 2023043786 W JP2023043786 W JP 2023043786W WO 2024128115 A1 WO2024128115 A1 WO 2024128115A1
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powder
thermal spray
spray coating
open rack
alloy
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PCT/JP2023/043786
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French (fr)
Japanese (ja)
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博紀 横田
隼也 上野
海人 高木
陽一郎 土生
将司 京
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トーカロ株式会社
関西電力株式会社
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Publication of WO2024128115A1 publication Critical patent/WO2024128115A1/en

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  • the present invention relates to a method for manufacturing an open rack type carburetor component, and to an open rack type carburetor component.
  • the present invention relates to a method for manufacturing an open rack type carburetor component that uses a refrigerant containing a corrosive component, such as seawater, and to an open rack type carburetor component.
  • An open rack type vaporizer is a device that vaporizes liquefied gas (e.g., LNG) that has been brought to a low-temperature liquid state by heat exchange with a refrigerant (e.g., seawater).
  • Figures 7 and 8 are partial schematic diagrams of an open rack type vaporizer with a portion enlarged, Figure 7 being a perspective view, and Figure 8 being a side view.
  • a lower header tube 102 and an upper header tube 104 are arranged at a distance in the vertical direction. LNG passes through a heat transfer tube 103 that connects the lower header tube 102 and the upper header tube 104.
  • the refrigerant that overflows from the refrigerant spray trough 106 flows along the outside of the heat transfer tube 103. Then, the LNG inside the heat transfer tube 103 and the refrigerant outside the heat transfer tube 103 exchange heat. As a result, the LNG is vaporized into gas.
  • Patent Document 1 describes a method in which an Al-2 mass% Zn alloy is flame-sprayed using a wire method to form a sacrificial anode layer on the outer surface of the Al alloy base material.
  • the manufacturing method of the open rack type carburetor member of the present invention is characterized in that a thermal spray coating is formed on the surface of a substrate made of Al or an Al alloy by feeding Al powder or Al alloy powder and Al 2 O 3 powder into a high-velocity flame.
  • a more preferred feature of the method for manufacturing an open rack type carburetor component of the present invention is that the volume ratio of the Al powder or Al alloy powder (A) to the Al 2 O 3 powder (B) is 0.1 ⁇ (B)/(A) ⁇ 3.5.
  • the open rack type carburetor component of the present invention comprises a substrate made of Al or an Al alloy and a thermal spray coating formed on the substrate surface, and the thermal spray coating includes a main phase made of Al or an Al alloy and Al 2 O 3 particles dispersed in the main phase.
  • the open rack type carburetor member of the present invention has the following three more preferable features.
  • the Al 2 O 3 content of the thermal spray coating is 10% or more and less than 30%.
  • the porosity of the thermal spray coating is less than 4%.
  • the adhesion strength of the thermal spray coating to the substrate is 25 MPa or more.
  • the present invention provides an open rack-type carburetor component equipped with a thermal spray coating that has excellent corrosion resistance and adhesion to the substrate.
  • FIG. 1 is a schematic perspective view showing an example of an open rack type vaporizer.
  • FIG. 2 is a schematic perspective view of an enlarged portion of the open rack vaporizer of FIG. 1.
  • 1 is a graph showing the relationship between the volume ratio (Al 2 O 3 /Al) of the material powder and the Al 2 O 3 content in the coating for the test pieces of Examples 1 to 7.
  • 1 is a graph showing the relationship between the volume ratio (Al 2 O 3 /Al) of the material powders and the porosity in the coating in the test pieces of Examples 1 to 7.
  • FIG. 4 is a partial cross-sectional view of a thermal spray coating formed by the method of Example 3.
  • FIG. 2 is a partial cross-sectional view of a thermal spray coating formed by the method of Comparative Example 1.
  • FIG. 2 is a schematic perspective view showing an enlarged portion of the open rack vaporizer.
  • FIG. 2 is a schematic side view of an open rack-type vaporizer with a portion enlarged.
  • FIG. 1 is a schematic perspective view showing an example of an open rack type vaporizer.
  • FIG. 2 is a schematic perspective view showing an enlarged portion of the open rack type vaporizer of FIG. 1.
  • the open rack type vaporizer 1 includes, for example, a lower header tube 2, a heat transfer tube 3, an upper header tube 4, a refrigerant supply member 5, a refrigerant spray trough 6, and a liquefied gas supply member 7.
  • Liquefied gas flows into the lower header tube 2. Gas obtained by vaporizing the liquefied gas flows out of the upper header tube 4.
  • the heat transfer tube 3 connects the lower header tube 2 and the upper header tube 4.
  • the liquefied gas that flows in from the lower header tube 2 is vaporized by heat from the external refrigerant as it flows upward.
  • the vaporized gas then flows from the heat transfer tube 3 into the upper header tube 4.
  • the refrigerant supply member 5 supplies a refrigerant to be heat exchanged with the liquefied gas to the outside of the heat transfer tube 3 in order to vaporize the liquefied gas.
  • the liquefied gas supply member 7 supplies the liquefied gas to be vaporized.
  • a plurality of lower header tubes 2 and upper header tubes 4 are installed and extend in a direction parallel to the surface on which the open rack type vaporizer 1 is installed.
  • the heat transfer tubes 3 extend in a direction perpendicular to the extension direction of the lower header tubes 2 and upper header tubes 4.
  • a plurality of heat transfer tubes 3 are gathered together to form a panel.
  • the refrigerant supply member 5 includes a portion that extends parallel to the upper header tube 4.
  • the refrigerant sprinkling trough 6 extends parallel to the upper header tube 4 and is bent to have an opening at the top.
  • the refrigerant sprinkling trough 6 is installed near the connection between the upper header tube 4 and the heat transfer tube 3.
  • the refrigerant supply member 5 and the refrigerant sprinkling trough 6 are connected.
  • LNG is used as the liquefied gas
  • seawater is used as the refrigerant.
  • the refrigerant is not limited to seawater, and may be fresh water, for example.
  • the lower header tube 2, the heat transfer tube 3, and the upper header tube 4 are made of Al or an Al alloy, which has high thermal conductivity.
  • an Al alloy refers to an alloy in which the proportion of Al is the highest among the elements constituting the alloy.
  • the Al content in the Al alloy is preferably 80 mass% or more, and more preferably 90 mass% or more.
  • Al alloy is not particularly limited, but examples that can be used include Al-Mn alloys, Al-Si alloys, Al-Mg alloys, Al-Cu alloys, Al-Zn alloys, Al-Mg-Si alloys, Al-Mg-Cu alloys, and Al-Zn-Mg alloys.
  • seawater is supplied to the carburetor components made of Al or Al alloy, such as the lower header tube 2, heat transfer tube 3, and upper header tube 4, so there is a concern that they may corrode. For this reason, a thermal spray coating with anti-corrosion properties is formed on the surface of the carburetor components.
  • the thermal spray coating in this embodiment is a thermal spray coating formed on the substrate surface of an open rack type vaporizer member mainly composed of Al or Al alloy by simultaneously feeding Al powder or Al alloy powder and Al 2 O 3 powder into a high-speed flame.
  • a film formation method is adopted in which Al powder or Al alloy powder and Al 2 O 3 powder are supplied into the same high-speed flame, whereby an Al film or Al alloy film is formed on the substrate surface, and unmelted Al 2 O 3 particles collide at high speed with the Al film or Al alloy film surface immediately after the film formation, so that pores formed during the film formation can be crushed.
  • the entire area of the film becomes dense, and a thermal spray coating with excellent corrosion resistance without through pores is obtained.
  • the thermal spray coating formed in this embodiment is formed in a state that includes a main phase made of Al or an Al alloy and unmelted Al2O3 particles dispersed in the main phase.
  • the main phase refers to a phase in which the area ratio of the component in the thermal spray coating is 50% or more when the cross-section of the thermal spray coating is observed.
  • Al powder or Al alloy powder, and Al 2 O 3 powder are used as the material powder to be fed into the high-speed flame.
  • Al and Al alloys have high thermal conductivity and easily function as a sacrificial anticorrosion layer.
  • the types of Al alloy powders used include, for example, Al-Mn alloys, Al-Si alloys, Al-Mg alloys, Al-Cu alloys, Al-Zn alloys, Al-Mg-Si alloys, Al-Mg-Cu alloys, and Al-Zn-Mg alloys.
  • the average particle size of the Al powder or Al alloy powder is preferably 20 to 100 ⁇ m, and the average particle size of the Al 2 O 3 powder is preferably 8 to 450 ⁇ m.
  • the term "average particle size" is defined as the particle size (median diameter) at which the cumulative value is 50% when the particle size distribution is measured by the laser diffraction/scattering method (microtrack method).
  • the volume ratio of the Al powder or Al alloy powder (A) to the Al 2 O 3 powder (B) is preferably 0.1 ⁇ ((B)/(A)), and more preferably 1.0 ⁇ ((B)/(A)).
  • the volume ratio of the Al powder or Al alloy powder (A) to the Al 2 O 3 powder (B) is preferably ((B)/(A)) ⁇ 3.5.
  • the porosity in the thermal spray coating is preferably less than 4%, and more preferably 2.5% or less.
  • the content of particles in the Al or Al alloy coating is too large, the inherent properties of Al or Al alloy may be impaired, but if the content of Al 2 O 3 in the thermal spray coating is less than 30%, a sufficient anticorrosive effect can be obtained, and from the viewpoint of improving adhesion and reducing porosity, the content of Al 2 O 3 particles is preferably 10% or more.
  • the content of Al 2 O 3 in the thermal spray coating is preferably 10% or more, and preferably less than 30%.
  • the content of Al or Al alloy in the thermal spray coating is preferably 70% or more, and preferably less than 90%.
  • the porosity of the thermal spray coating and the content of the components constituting the thermal spray coating can be obtained by appropriately treating the cut surface of the coating cut out from the carburetor member with mirror polishing or the like and observing it with a microscope, and can be specified, for example, by performing image analysis on a photograph taken at 100 times magnification with a scanning electron microscope and calculating the area ratio of each part.
  • the thermal spray coating in this embodiment is formed by repeatedly colliding unmelted Al 2 O 3 particles at high speed against the surface of the Al coating (Al alloy coating) immediately after coating, so that the coating is dense throughout. In this way, the entire coating is dense, making it possible to form a coating that is less likely to have through-holes, and thus improving corrosion resistance.
  • the contact area between the substrate and the coating is increased near the substrate interface of the thermal spray coating, improving the anchor effect and making it possible to form a coating with high adhesion to the substrate.
  • the adhesion of the thermal spray coating to the substrate is preferably 25 MPa or more.
  • the open rack type vaporizer is a device that exchanges heat between a low-temperature liquefied gas located inside the vaporizer member and a refrigerant located outside the vaporizer member, so the temperature gradient between the inner and outer surfaces of the vaporizer member is very large. Therefore, due to the temperature difference between the substrate located on the inner surface of the vaporizer member and the thermal spray coating located on the outer surface of the vaporizer member, the thermal expansion difference between the substrate and the thermal spray coating becomes large, and as a result, there is a risk of the thermal spray coating peeling off.
  • the components to which the thermal spray coating in this embodiment is applied are not limited to heat transfer tubes, upper header tubes, and lower header tubes, but can also be applied to other components.
  • Example 1 A5052 alloy (Al-Mg alloy) with dimensions of 50 x 50 x 5 mmt was prepared as a substrate. Next, the substrate was roughened by blasting with WA (white alumina) F60 blasting material at a spray pressure of 0.3 MPa. Next, a film was formed on the roughened substrate in the following manner to form a test piece. Coating method: A powder mixture of materials 1 and 2 was added to the high-velocity flame generated by a high-velocity flame spraying device. Material 1: Al powder (average particle size: 38 ⁇ m) Material 2: Al2O3 powder (average particle size: 108 ⁇ m) Volume ratio ( Al2O3 powder /Al powder): 0.18
  • Example 2 A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 0.65.
  • Example 3 A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 1.05.
  • Example 4 A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 1.31.
  • Example 5 A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 1.98.
  • Example 6 A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 2.52.
  • Example 7 A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 3.31.
  • Example 8 A test piece was prepared in the same manner as in Example 1, except that A5083 (Al-Mg alloy) was used as the substrate, Al-3% Zn powder was used as material 1, and the volume ratio (Al 2 O 3 powder/Al powder) was 1.05.
  • Example 9 A test piece was prepared in the same manner as in Example 1, except that A5083 (Al-Mg alloy) was used as the substrate, Al-5% Mg powder was used as material 1, and the volume ratio (Al 2 O 3 powder/Al powder) was 1.05.
  • Test pieces were prepared in the same manner as in Example 1, except that A5083 (Al-Mg alloy) was used as the substrate and the film was formed as follows. Coating method: The following materials are added to the frame generated by the wire flame spraying device. Material: Al wire
  • Test pieces were prepared in the same manner as in Example 1, except that only Al powder was used as the material.
  • Adhesion test The adhesion test was carried out according to a method in accordance with JIS H 8402, and the adhesion between the substrate and the thermal spray coating was evaluated based on the fracture surface pressure (MPa).
  • Salt spray test The salt spray test was performed for 300 hours according to a method conforming to JIS Z2371:2015. After that, the cross section was observed to check for the presence or absence of corrosion products at the interface between the coating and the substrate, thereby evaluating the corrosion resistance.
  • the evaluation indexes for corrosion resistance have the following meanings: ⁇ : No corrosion products were observed after 300 hours. ⁇ : Corrosion products were observed after 300 hours.
  • Table 1 is a table summarizing the results of the above-mentioned measurements and tests performed on each test piece of Examples 1 to 9 and Comparative Examples 1 and 2.
  • Fig. 3 is a graph showing the relationship between the volume ratio (Al 2 O 3 powder/Al powder) and the Al 2 O 3 content in the coating for each test piece of Examples 1 to 7
  • Fig. 4 is a graph showing the relationship between the volume ratio (Al 2 O 3 powder/Al powder) and the porosity in the coating for each test piece of Examples 1 to 7.
  • test pieces of Examples 1 to 9 were found to have better results than Comparative Example 1 in terms of porosity, adhesion, and corrosion resistance.
  • Figure 5 shows a photograph of a partial cross section of the coating formed by the method of Example 3
  • Figure 6 shows a photograph of a partial cross section of the coating formed by the method of Comparative Example 1.
  • the thermal spray coating of Example 3 has a dense structure throughout the entire coating
  • the thermal spray coating of Comparative Example 1 has a structure with many pores.
  • the coatings of Examples 1 to 9 were all dense throughout the entire coating, as shown in Figure 5. From this, it is presumed that the reason why the test pieces of Examples 1 to 9 showed better results in terms of porosity, adhesion, and corrosion resistance than the test piece of Comparative Example 1 is because the coating structure was dense throughout.
  • the open rack type evaporator components of the present invention can be used, for example, as heat transfer tubes, upper header tubes, and lower header tubes.

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Abstract

The present invention is a manufacturing method for an open rack vaporizer member, said method involving forming a thermal spray coating on a surface of a substrate composed of Al or an Al alloy by feeding Al powder or an Al alloy powder and Al2O3 powder into a high-velocity flame.

Description

オープンラック式気化器部材の製造方法、及び、オープンラック式気化器部材Method for manufacturing open rack type vaporizer component, and open rack type vaporizer component
　本発明は、オープンラック式気化器部材の製造方法、及び、オープンラック式気化器部材に関する。特に、海水等、腐食成分を含むものを冷媒として使用するオープンラック式気化器部材の製造方法、及び、オープンラック式気化器部材に関する。 The present invention relates to a method for manufacturing an open rack type carburetor component, and to an open rack type carburetor component. In particular, the present invention relates to a method for manufacturing an open rack type carburetor component that uses a refrigerant containing a corrosive component, such as seawater, and to an open rack type carburetor component.
　オープンラック式気化器は、低温の液体状態にした液化ガス（例えばＬＮＧ）を冷媒（例えば海水）により熱交換し、液化ガスを気化させる装置である。図７及び図８はオープンラック式気化器の一部を拡大した部分概略図であり、図７は斜視図であり、図８は側面図である。図７、図８に示すように、オープンラック式気化器では、上下方向に距離を隔てて下部ヘッダ管１０２及び上部ヘッダ管１０４が配置される。下部ヘッダ管１０２と上部ヘッダ管１０４とを接続する伝熱管１０３をＬＮＧが通る。冷媒散水トラフ１０６から溢れる冷媒は伝熱管１０３の外部を沿うように流れる。そして、伝熱管１０３内部のＬＮＧと伝熱管１０３外部の冷媒が熱交換を行う。これにより、ＬＮＧがガスへと気化される。 　An open rack type vaporizer is a device that vaporizes liquefied gas (e.g., LNG) that has been brought to a low-temperature liquid state by heat exchange with a refrigerant (e.g., seawater). Figures 7 and 8 are partial schematic diagrams of an open rack type vaporizer with a portion enlarged, Figure 7 being a perspective view, and Figure 8 being a side view. As shown in Figures 7 and 8, in an open rack type vaporizer, a lower header tube 102 and an upper header tube 104 are arranged at a distance in the vertical direction. LNG passes through a heat transfer tube 103 that connects the lower header tube 102 and the upper header tube 104. The refrigerant that overflows from the refrigerant spray trough 106 flows along the outside of the heat transfer tube 103. Then, the LNG inside the heat transfer tube 103 and the refrigerant outside the heat transfer tube 103 exchange heat. As a result, the LNG is vaporized into gas.
　オープンラック式気化器の熱交換パネルに搭載される伝熱管１０３、ヘッダ管１０２、１０４等の気化器部材は、海水からの熱を吸収しやすくするために、熱伝導性の高いＡｌ合金（３０００系、５０００系、６０００系等）が用いられている。しかしながら、このような気化器部材は、上述のように、海水に晒されるような環境下において使用される場合、腐食の懸念がある。そのため、気化器部材には、防食処理が施されることが望ましい。 The carburetor components, such as the heat transfer tube 103 and header tubes 102 and 104 mounted on the heat exchange panel of the open rack type carburetor, are made of Al alloys (3000 series, 5000 series, 6000 series, etc.) with high thermal conductivity in order to facilitate the absorption of heat from seawater. However, as mentioned above, there is a concern that such carburetor components may corrode when used in an environment exposed to seawater. For this reason, it is desirable to subject the carburetor components to anti-corrosion treatment.
　従来、気化器部材への防食処理としては、例えば、特許文献１に、Ａｌ－２質量％Ｚｎ合金の溶線式フレーム溶射を行い、Ａｌ合金基材の外表面に犠牲陽極層を形成する方法が記載されている。 　Conventionally, as an anti-corrosion treatment for carburetor components, for example, Patent Document 1 describes a method in which an Al-2 mass% Zn alloy is flame-sprayed using a wire method to form a sacrificial anode layer on the outer surface of the Al alloy base material.
特開２０１１－１１２２９４号公報JP 2011-112294 A
　しかしながら、本発明者は、特許文献１に記載の溶射皮膜は、耐食性及びＡｌ合金基材に対する密着性が十分ではなく、改善の余地があることを見出した。 However, the inventors found that the thermal spray coating described in Patent Document 1 does not have sufficient corrosion resistance and adhesion to the Al alloy substrate, and there is room for improvement.
　本発明は、耐食性及び基材への密着性に優れた溶射皮膜を備えるオープンラック式気化器部材の製造方法、並びに、耐食性及び基材への密着性に優れた溶射皮膜を備えるオープンラック式気化器部材を提供することにある。 The present invention aims to provide a method for manufacturing an open rack-type carburetor component with a thermal spray coating that has excellent corrosion resistance and adhesion to the substrate, and an open rack-type carburetor component with a thermal spray coating that has excellent corrosion resistance and adhesion to the substrate.
　本発明のオープンラック式の気化器部材の製造方法は、Ａｌ又はＡｌ合金からなる基材の表面に対して、Ａｌ粉末又はＡｌ合金粉末と、Ａｌ２Ｏ３粉末と、を高速フレームに投入することにより溶射皮膜を形成することを特徴とする。 The manufacturing method of the open rack type carburetor member of the present invention is characterized in that a thermal spray coating is formed on the surface of a substrate made of Al or an Al alloy by feeding Al powder or Al alloy powder and Al 2 O 3 powder into a high-velocity flame.
　本発明のオープンラック式の気化器部材の製造方法のより好ましい特徴としては、Ａｌ粉末又はＡｌ合金粉末（Ａ）と、Ａｌ２Ｏ３粉末（Ｂ）との体積比が、０．１≦（Ｂ）／（Ａ）≦３．５であることが挙げられる。 A more preferred feature of the method for manufacturing an open rack type carburetor component of the present invention is that the volume ratio of the Al powder or Al alloy powder (A) to the Al 2 O 3 powder (B) is 0.1≦(B)/(A)≦3.5.
　また、本発明のオープンラック式の気化器部材は、Ａｌ又はＡｌ合金からなる基材と、前記基材表面に形成された溶射皮膜とを備え、前記溶射皮膜は、Ａｌ又はＡｌ合金からなる主相と、該主相中に分散したＡｌ２Ｏ３粒子と、を含むことを特徴とする。 In addition, the open rack type carburetor component of the present invention comprises a substrate made of Al or an Al alloy and a thermal spray coating formed on the substrate surface, and the thermal spray coating includes a main phase made of Al or an Al alloy and Al 2 O 3 particles dispersed in the main phase.
　本発明のオープンラック式の気化器部材のより好ましい特徴としては、以下の３つが挙げられる。
　（１）溶射皮膜のＡｌ２Ｏ３含有率は、１０％以上、３０％未満である。
　（２）溶射皮膜の気孔率が４％未満である。
　（３）溶射皮膜の基材との密着力が２５ＭＰａ以上である。 The open rack type carburetor member of the present invention has the following three more preferable features.
(1) The Al 2 O 3 content of the thermal spray coating is 10% or more and less than 30%.
(2) The porosity of the thermal spray coating is less than 4%.
(3) The adhesion strength of the thermal spray coating to the substrate is 25 MPa or more.
　本発明によれば、耐食性及び基材への密着性に優れた溶射皮膜を備えるオープンラック式気化器部材を提供することができる。 The present invention provides an open rack-type carburetor component equipped with a thermal spray coating that has excellent corrosion resistance and adhesion to the substrate.
オープンラック式気化器の一例を示す概略斜視図である。FIG. 1 is a schematic perspective view showing an example of an open rack type vaporizer. 図１のオープンラック式気化器の一部を拡大した概略斜視図である。FIG. 2 is a schematic perspective view of an enlarged portion of the open rack vaporizer of FIG. 1. 実施例１～７の試験片における、材料粉末の体積比（Ａｌ２Ｏ３／Ａｌ）と皮膜中のＡｌ２Ｏ３含有率との関係をグラフにしたものである。1 is a graph showing the relationship between the volume ratio (Al 2 O 3 /Al) of the material powder and the Al 2 O 3 content in the coating for the test pieces of Examples 1 to 7. 実施例１～７の試験片における、材料粉末の体積比（Ａｌ２Ｏ３／Ａｌ）と皮膜中の気孔率との関係をグラフにしたものである。1 is a graph showing the relationship between the volume ratio (Al 2 O 3 /Al) of the material powders and the porosity in the coating in the test pieces of Examples 1 to 7. 実施例３の方法により成膜した溶射皮膜の部分断面図である。FIG. 4 is a partial cross-sectional view of a thermal spray coating formed by the method of Example 3. 比較例１の方法により成膜した溶射皮膜の部分断面図である。FIG. 2 is a partial cross-sectional view of a thermal spray coating formed by the method of Comparative Example 1. オープンラック式気化器の一部を拡大した概略斜視図である。FIG. 2 is a schematic perspective view showing an enlarged portion of the open rack vaporizer. オープンラック式気化器の一部を拡大した概略側面図である。FIG. 2 is a schematic side view of an open rack-type vaporizer with a portion enlarged.
　以下に、本発明に係るオープンラック式気化器部材の一実施形態について、図を参照して説明する。 Below, one embodiment of an open rack-type vaporizer component according to the present invention will be described with reference to the drawings.
　図１は、オープンラック式気化器の一例を示す概略斜視図である。また、図２は、図１のオープンラック式気化器の一部を拡大した概略斜視図である。オープンラック式気化器１は、図１、図２に示すように、たとえば、下部ヘッダ管２と、伝熱管３と、上部ヘッダ管４と、冷媒供給部材５と、冷媒散水トラフ６と、液化ガス供給部材７と、を備える。下部ヘッダ管２には、液化ガスが流入する。上部ヘッダ管４からは、液化ガスが気化されたガスが流出する。伝熱管３は、下部ヘッダ管２と上部ヘッダ管４とを接続している。伝熱管３では、下部ヘッダ管２から流入した液化ガスが、上方に流れるにつれて外部の冷媒からの熱で気化する。そして、気化したガスは、伝熱管３から上部ヘッダ管４へと流入する。冷媒供給部材５は、液化ガスを気化させるため、伝熱管３の外部に液化ガスと熱交換させるための冷媒を供給する。液化ガス供給部材７は、気化させる液化ガスを供給する。 1 is a schematic perspective view showing an example of an open rack type vaporizer. FIG. 2 is a schematic perspective view showing an enlarged portion of the open rack type vaporizer of FIG. 1. As shown in FIGS. 1 and 2, the open rack type vaporizer 1 includes, for example, a lower header tube 2, a heat transfer tube 3, an upper header tube 4, a refrigerant supply member 5, a refrigerant spray trough 6, and a liquefied gas supply member 7. Liquefied gas flows into the lower header tube 2. Gas obtained by vaporizing the liquefied gas flows out of the upper header tube 4. The heat transfer tube 3 connects the lower header tube 2 and the upper header tube 4. In the heat transfer tube 3, the liquefied gas that flows in from the lower header tube 2 is vaporized by heat from the external refrigerant as it flows upward. The vaporized gas then flows from the heat transfer tube 3 into the upper header tube 4. The refrigerant supply member 5 supplies a refrigerant to be heat exchanged with the liquefied gas to the outside of the heat transfer tube 3 in order to vaporize the liquefied gas. The liquefied gas supply member 7 supplies the liquefied gas to be vaporized.
　オープンラック式気化器１では、下部ヘッダ管２及び上部ヘッダ管４がそれぞれ複数本設置され、オープンラック式気化器１が設置される面に対して平行な方向に延在されている。伝熱管３は、下部ヘッダ管２及び上部ヘッダ管４の延在方向に対して垂直な方向に延在されている。また、冷媒と液化ガスとが熱交換できる表面積を増やすために、伝熱管３を複数集めてパネルを構成している。冷媒供給部材５は、上部ヘッダ管４と平行に延びる部分を含む。冷媒散水トラフ６は上部ヘッダ管４と平行で、上方に開口部を有するように曲げられて延在される。冷媒散水トラフ６は、上部ヘッダ管４と伝熱管３との接続部分の近傍に設置される。冷媒供給部材５と冷媒散水トラフ６とは接続されている。 In the open rack type vaporizer 1, a plurality of lower header tubes 2 and upper header tubes 4 are installed and extend in a direction parallel to the surface on which the open rack type vaporizer 1 is installed. The heat transfer tubes 3 extend in a direction perpendicular to the extension direction of the lower header tubes 2 and upper header tubes 4. In addition, in order to increase the surface area for heat exchange between the refrigerant and the liquefied gas, a plurality of heat transfer tubes 3 are gathered together to form a panel. The refrigerant supply member 5 includes a portion that extends parallel to the upper header tube 4. The refrigerant sprinkling trough 6 extends parallel to the upper header tube 4 and is bent to have an opening at the top. The refrigerant sprinkling trough 6 is installed near the connection between the upper header tube 4 and the heat transfer tube 3. The refrigerant supply member 5 and the refrigerant sprinkling trough 6 are connected.
　本実施形態では、液化ガスとしてＬＮＧを、冷媒として海水を用いている。なお、冷媒は海水に限定されるものではなく、例えば、淡水であってもよい。下部ヘッダ管２、伝熱管３、及び、上部ヘッダ管４の基材材料は、熱伝導性の高いＡｌ又はＡｌ合金を用いている。ここで、Ａｌ合金とは、合金を構成する元素のうち、Ａｌの比率が最も高い合金のことを指す。このとき、Ａｌ合金におけるＡｌの含有率は、８０質量％以上が好ましく、９０質量％以上がより好ましい。Ａｌ合金の種類は特に限定されないが、例えば、Ａｌ－Ｍｎ系合金、Ａｌ－Ｓｉ系合金、Ａｌ－Ｍｇ系合金、Ａｌ－Ｃｕ系合金、Ａｌ－Ｚｎ系合金、Ａｌ－Ｍｇ－Ｓｉ系合金、Ａｌ－Ｍｇ－Ｃｕ系合金、Ａｌ－Ｚｎ－Ｍｇ系合金等が用いられる。 In this embodiment, LNG is used as the liquefied gas, and seawater is used as the refrigerant. The refrigerant is not limited to seawater, and may be fresh water, for example. The lower header tube 2, the heat transfer tube 3, and the upper header tube 4 are made of Al or an Al alloy, which has high thermal conductivity. Here, an Al alloy refers to an alloy in which the proportion of Al is the highest among the elements constituting the alloy. In this case, the Al content in the Al alloy is preferably 80 mass% or more, and more preferably 90 mass% or more. The type of Al alloy is not particularly limited, but examples that can be used include Al-Mn alloys, Al-Si alloys, Al-Mg alloys, Al-Cu alloys, Al-Zn alloys, Al-Mg-Si alloys, Al-Mg-Cu alloys, and Al-Zn-Mg alloys.
　次に、本発明に係るオープンラック式気化器部材の製造方法の一実施形態について説明する。 Next, we will explain one embodiment of a method for manufacturing an open rack-type vaporizer component according to the present invention.
　上述の通り、下部ヘッダ管２、伝熱管３、及び、上部ヘッダ管４等のＡｌ又はＡｌ合金からなる気化器部材には、海水が供給されるため、腐食の懸念がある。そのため、気化器部材の表面には、防食効果を備えた溶射皮膜を形成する。 As mentioned above, seawater is supplied to the carburetor components made of Al or Al alloy, such as the lower header tube 2, heat transfer tube 3, and upper header tube 4, so there is a concern that they may corrode. For this reason, a thermal spray coating with anti-corrosion properties is formed on the surface of the carburetor components.
　本実施形態における溶射皮膜は、Ａｌ粉末又はＡｌ合金粉末と、Ａｌ２Ｏ３粉末と、を同時に高速フレーム内に投入することにより、Ａｌ又はＡｌ合金を主成分とするオープンラック式気化器部材の基材表面に形成された溶射皮膜である。本実施形態では、Ａｌ粉末又はＡｌ合金粉末とＡｌ２Ｏ３粉末とを同一の高速フレーム内に供給する成膜方法を採用しており、それにより、基材表面に対してＡｌ皮膜又はＡｌ合金皮膜が成膜するとともに、成膜直後のＡｌ皮膜又はＡｌ合金皮膜表面に対して未溶融のＡｌ２Ｏ３粒子が高速で衝突し、成膜中に形成された気孔を潰すことができる。これが繰り返されることにより、皮膜の全域が緻密化し、貫通気孔のない耐食性に優れた溶射皮膜となる。特に、基材界面近傍の皮膜が基材面に押し込まれて塑性変形すると、基材と皮膜との接触面積が増える。その結果、アンカー効果が向上するため、従来の成膜方法に比べて、基材に対する密着性に優れた溶射皮膜を成膜することができる。高速フレームは、市販の高速フレーム溶射装置によって生成することができる。未溶融のＡｌ２Ｏ３粒子は、Ａｌ合金皮膜表面に対して衝突した際に、その一部がＡｌ合金皮膜に取り込まれる形で成膜される。例えば、図５の断面写真に示されるように、本実施形態において形成された溶射皮膜は、Ａｌ又はＡｌ合金からなる主相と、該主相中に分散した未溶融のＡｌ２Ｏ３粒子とを含んだ状態で成膜される。なお、本明細書においては、溶射皮膜を断面観察したときに、溶射皮膜に占める成分の面積率が５０％以上である相を主相という。 The thermal spray coating in this embodiment is a thermal spray coating formed on the substrate surface of an open rack type vaporizer member mainly composed of Al or Al alloy by simultaneously feeding Al powder or Al alloy powder and Al 2 O 3 powder into a high-speed flame. In this embodiment, a film formation method is adopted in which Al powder or Al alloy powder and Al 2 O 3 powder are supplied into the same high-speed flame, whereby an Al film or Al alloy film is formed on the substrate surface, and unmelted Al 2 O 3 particles collide at high speed with the Al film or Al alloy film surface immediately after the film formation, so that pores formed during the film formation can be crushed. By repeating this, the entire area of the film becomes dense, and a thermal spray coating with excellent corrosion resistance without through pores is obtained. In particular, when the film near the substrate interface is pressed into the substrate surface and plastically deformed, the contact area between the substrate and the film increases. As a result, the anchor effect is improved, and a thermal spray coating with excellent adhesion to the substrate can be formed compared to conventional film formation methods. The high-speed flame can be generated by a commercially available high-speed flame thermal spraying device. When unmelted Al2O3 particles collide with the surface of the Al alloy coating, a part of the particles is incorporated into the Al alloy coating to form a film. For example, as shown in the cross-sectional photograph of Fig. 5, the thermal spray coating formed in this embodiment is formed in a state that includes a main phase made of Al or an Al alloy and unmelted Al2O3 particles dispersed in the main phase. In this specification, the main phase refers to a phase in which the area ratio of the component in the thermal spray coating is 50% or more when the cross-section of the thermal spray coating is observed.
　本実施形態において、高速フレームに投入する材料粉末には、Ａｌ粉末又はＡｌ合金粉末、及びＡｌ２Ｏ３粉末が使用される。ＡｌやＡｌ合金は、熱伝導性が高く、かつ犠牲防食層として機能しやすい。Ａｌ合金粉末の種類は、例えば、Ａｌ－Ｍｎ系合金、Ａｌ－Ｓｉ系合金、Ａｌ－Ｍｇ系合金、Ａｌ－Ｃｕ系合金、Ａｌ－Ｚｎ系合金、Ａｌ－Ｍｇ－Ｓｉ系合金、Ａｌ－Ｍｇ－Ｃｕ系合金、Ａｌ－Ｚｎ－Ｍｇ系合金等が用いられる。また、Ａｌ粉末又はＡｌ合金粉末の平均粒径は２０～１００μｍであることが好ましく、Ａｌ２Ｏ３粉末の平均粒径は８～４５０μｍであることが好ましい。なお、本明細書において「平均粒径」とは、レーザ回析・散乱法（マイクロトラック法）によって粒度分布を測定したときに累積値が５０％となる粒径（メジアン径）と定義する。 In this embodiment, Al powder or Al alloy powder, and Al 2 O 3 powder are used as the material powder to be fed into the high-speed flame. Al and Al alloys have high thermal conductivity and easily function as a sacrificial anticorrosion layer. The types of Al alloy powders used include, for example, Al-Mn alloys, Al-Si alloys, Al-Mg alloys, Al-Cu alloys, Al-Zn alloys, Al-Mg-Si alloys, Al-Mg-Cu alloys, and Al-Zn-Mg alloys. The average particle size of the Al powder or Al alloy powder is preferably 20 to 100 μm, and the average particle size of the Al 2 O 3 powder is preferably 8 to 450 μm. In this specification, the term "average particle size" is defined as the particle size (median diameter) at which the cumulative value is 50% when the particle size distribution is measured by the laser diffraction/scattering method (microtrack method).
　本実施形態において、Ａｌ粉末又はＡｌ合金粉末（Ａ）とＡｌ２Ｏ３粉末（Ｂ）との体積比は、０．１≦（（Ｂ）／（Ａ））であることが好ましく、１．０≦（（Ｂ）／（Ａ））であることがより好ましい。また、Ａｌ粉末又はＡｌ合金粉末（Ａ）とＡｌ２Ｏ３粉末（Ｂ）との体積比は、（（Ｂ）／（Ａ））≦３．５であることが好ましい。体積比がこのような関係であると、溶射皮膜の基材に対する密着力がより向上するとともに、気孔率をより低下させることができる。溶射皮膜中の気孔率が高いと、溶射皮膜中に貫通気孔が生じる可能性が高くなる。貫通気孔が存在すると、溶射皮膜の表面から海水が侵入し、基材との界面まで到達する虞がある。海水が溶射皮膜と基材との界面まで侵入すると、腐食が進行する。したがって、腐食の進行を抑制するために、溶射皮膜中の気孔率は、４％未満とすることが好ましく、２．５％以下とすることがより好ましい。また、Ａｌ又はＡｌ合金皮膜中の粒子の含有率が大きすぎると、Ａｌ又はＡｌ合金の本来の特性が損なわれる可能性があるが、溶射皮膜中のＡｌ２Ｏ３含有率が３０％未満であれば、十分な防食効果が得られ、むしろ密着力向上や気孔率低減の観点からは、Ａｌ２Ｏ３粒子の含有率が１０％以上であることが好ましい。したがって、溶射皮膜中のＡｌ２Ｏ３含有率は、１０％以上であることが好ましく、３０％未満であることが好ましい。また、溶射皮膜においてＡｌ又はＡｌ合金を主相とする観点から、溶射皮膜中のＡｌ又はＡｌ合金の含有率は７０％以上であることが好ましく、９０％未満であることが好ましい。溶射皮膜の気孔率や溶射皮膜を構成する成分の含有率は、気化器部材を切り出した皮膜切断面を、鏡面研磨等、適宜処理して顕微鏡にて観察して求めればよく、例えば走査型電子顕微鏡にて１００倍で撮影した写真を画像解析し、各部位の面積率を算定することで、特定することができる。 In this embodiment, the volume ratio of the Al powder or Al alloy powder (A) to the Al 2 O 3 powder (B) is preferably 0.1≦((B)/(A)), and more preferably 1.0≦((B)/(A)). The volume ratio of the Al powder or Al alloy powder (A) to the Al 2 O 3 powder (B) is preferably ((B)/(A))≦3.5. When the volume ratio has such a relationship, the adhesion of the thermal spray coating to the substrate is further improved and the porosity can be further reduced. If the porosity in the thermal spray coating is high, there is a high possibility that through-holes will be generated in the thermal spray coating. If through-holes are present, there is a risk that seawater will penetrate from the surface of the thermal spray coating and reach the interface with the substrate. If seawater penetrates to the interface between the thermal spray coating and the substrate, corrosion will progress. Therefore, in order to suppress the progress of corrosion, the porosity in the thermal spray coating is preferably less than 4%, and more preferably 2.5% or less. In addition, if the content of particles in the Al or Al alloy coating is too large, the inherent properties of Al or Al alloy may be impaired, but if the content of Al 2 O 3 in the thermal spray coating is less than 30%, a sufficient anticorrosive effect can be obtained, and from the viewpoint of improving adhesion and reducing porosity, the content of Al 2 O 3 particles is preferably 10% or more. Therefore, the content of Al 2 O 3 in the thermal spray coating is preferably 10% or more, and preferably less than 30%. In addition, from the viewpoint of making Al or Al alloy the main phase in the thermal spray coating, the content of Al or Al alloy in the thermal spray coating is preferably 70% or more, and preferably less than 90%. The porosity of the thermal spray coating and the content of the components constituting the thermal spray coating can be obtained by appropriately treating the cut surface of the coating cut out from the carburetor member with mirror polishing or the like and observing it with a microscope, and can be specified, for example, by performing image analysis on a photograph taken at 100 times magnification with a scanning electron microscope and calculating the area ratio of each part.
　本実施形態における溶射皮膜は、上述の通り、成膜直後のＡｌ皮膜（Ａｌ合金皮膜）表面に対して未溶融のＡｌ２Ｏ３粒子が高速で衝突し、それが繰り返し行われることで成膜されるため、皮膜全域において緻密となる。このように、皮膜全域が緻密となることにより、貫通気孔の生じにくい皮膜を形成することが可能となるため、耐食性がより向上する。また、溶射皮膜の基材界面近傍において、基材と皮膜との接触面積が大きくなることによりアンカー効果が向上し、基材に対する密着力の高い皮膜を形成することが可能となる。 As described above, the thermal spray coating in this embodiment is formed by repeatedly colliding unmelted Al 2 O 3 particles at high speed against the surface of the Al coating (Al alloy coating) immediately after coating, so that the coating is dense throughout. In this way, the entire coating is dense, making it possible to form a coating that is less likely to have through-holes, and thus improving corrosion resistance. In addition, the contact area between the substrate and the coating is increased near the substrate interface of the thermal spray coating, improving the anchor effect and making it possible to form a coating with high adhesion to the substrate.
　本実施形態において、溶射皮膜の基材との密着力は２５ＭＰａ以上であることが好ましい。上述の通り、オープンラック式気化器は、気化器部材内部に位置する低温の液化ガスと、気化器部材外部に位置する冷媒とを熱交換する装置であるため、気化器部材の内面と外面との間の温度勾配は非常に大きくなる。そのため、気化器部材の内面に位置する基材と気化器部材の外面に位置する溶射皮膜との間の温度差により、基材と溶射皮膜との熱膨張差が大きくなる結果、溶射皮膜が剥離する虞がある。また、オープンラック式気化器が運転稼働と運転停止を繰り返すことにより、気化器部材が熱サイクルに晒され、溶射皮膜が剥離する虞がある。これに対し、溶射皮膜の基材との密着力を２５ＭＰａ以上とすることにより、溶射皮膜の剥離を抑制することが可能となる。 In this embodiment, the adhesion of the thermal spray coating to the substrate is preferably 25 MPa or more. As described above, the open rack type vaporizer is a device that exchanges heat between a low-temperature liquefied gas located inside the vaporizer member and a refrigerant located outside the vaporizer member, so the temperature gradient between the inner and outer surfaces of the vaporizer member is very large. Therefore, due to the temperature difference between the substrate located on the inner surface of the vaporizer member and the thermal spray coating located on the outer surface of the vaporizer member, the thermal expansion difference between the substrate and the thermal spray coating becomes large, and as a result, there is a risk of the thermal spray coating peeling off. In addition, when the open rack type vaporizer is repeatedly operated and stopped, the vaporizer member is exposed to a thermal cycle, and there is a risk of the thermal spray coating peeling off. In response to this, by setting the adhesion of the thermal spray coating to the substrate to 25 MPa or more, it is possible to suppress the peeling off of the thermal spray coating.
　なお、本実施形態における溶射皮膜が適用される部材は、伝熱管、上部ヘッダ管、下部ヘッダ管に限定されるものではなく、他の部材にも適用することができる。 In addition, the components to which the thermal spray coating in this embodiment is applied are not limited to heat transfer tubes, upper header tubes, and lower header tubes, but can also be applied to other components.
　以下に、本発明を適用した実施例について説明する。本実施例は、本発明について例示するものであり、発明の範囲を限定するものではない。 Below, we will explain an embodiment in which the present invention is applied. This embodiment is intended to illustrate the present invention and does not limit the scope of the invention.
　［実施例１］
　基材として、寸法が５０×５０×５ｍｍｔのＡ５０５２合金（Ａｌ－Ｍｇ系合金）を用意した。次に、基材に対して、ＷＡ（ホワイトアルミナ）Ｆ６０のブラスト材を噴射圧０．３ＭＰａでブラストし、粗面化処理を行った。次に、粗面化された基材に対して、下記の要領で成膜することにより、試験片を形成した。
　　成膜方法：高速フレーム溶射装置によって生成した高速フレームに材料１及び材料２を混合した材料粉末を投入
　　材料１：Ａｌ粉末（平均粒径：３８μｍ）
　　材料２：Ａｌ２Ｏ３粉末（平均粒径：１０８μｍ）
　　体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）：０．１８ [Example 1]
A5052 alloy (Al-Mg alloy) with dimensions of 50 x 50 x 5 mmt was prepared as a substrate. Next, the substrate was roughened by blasting with WA (white alumina) F60 blasting material at a spray pressure of 0.3 MPa. Next, a film was formed on the roughened substrate in the following manner to form a test piece.
Coating method: A powder mixture of materials 1 and 2 was added to the high-velocity flame generated by a high-velocity flame spraying device. Material 1: Al powder (average particle size: 38 μm)
Material 2: Al2O3 powder (average particle size: 108 μm)
Volume ratio ( Al2O3 powder /Al powder): 0.18
　［実施例２］
　材料粉末の体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）が０．６５であること以外、実施例１と同様の方法により、試験片を作製した。 [Example 2]
A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 0.65.
　［実施例３］
　材料粉末の体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）が１．０５であること以外、実施例１と同様の方法により、試験片を作製した。 [Example 3]
A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 1.05.
　［実施例４］
　材料粉末の体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）が１．３１であること以外、実施例１と同様の方法により、試験片を作製した。 [Example 4]
A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 1.31.
　［実施例５］
　材料粉末の体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）が１．９８であること以外、実施例１と同様の方法により、試験片を作製した。 [Example 5]
A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 1.98.
　［実施例６］
　材料粉末の体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）が２．５２であること以外、実施例１と同様の方法により、試験片を作製した。 [Example 6]
A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 2.52.
　［実施例７］
　材料粉末の体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）が３．３１であること以外、実施例１と同様の方法により、試験片を作製した。 [Example 7]
A test piece was prepared in the same manner as in Example 1, except that the volume ratio of the material powders (Al 2 O 3 powder/Al powder) was 3.31.
　［実施例８］
　基材にＡ５０８３（Ａｌ－Ｍｇ系合金）を使用し、材料１にＡｌ－３％Ｚｎ粉末を使用し、かつ、体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）が１．０５であること以外、実施例１と同様の方法により、試験片を作製した。 [Example 8]
A test piece was prepared in the same manner as in Example 1, except that A5083 (Al-Mg alloy) was used as the substrate, Al-3% Zn powder was used as material 1, and the volume ratio (Al 2 O 3 powder/Al powder) was 1.05.
　［実施例９］
　基材にＡ５０８３（Ａｌ－Ｍｇ系合金）を使用し、材料１にＡｌ－５％Ｍｇ粉末を使用し、かつ、体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）が１．０５であること以外、実施例１と同様の方法により、試験片を作製した。 [Example 9]
A test piece was prepared in the same manner as in Example 1, except that A5083 (Al-Mg alloy) was used as the substrate, Al-5% Mg powder was used as material 1, and the volume ratio (Al 2 O 3 powder/Al powder) was 1.05.
　［比較例１］
　基材にＡ５０８３（Ａｌ－Ｍｇ系合金）を使用し、かつ、下記の要領で成膜したこと以外は、実施例１と同様の方法で試験片を作製した。
　　成膜方法：溶線式フレーム溶射装置によって生成したフレームに以下の材料を投入
　　材料：Ａｌワイヤー [Comparative Example 1]
Test pieces were prepared in the same manner as in Example 1, except that A5083 (Al-Mg alloy) was used as the substrate and the film was formed as follows.
Coating method: The following materials are added to the frame generated by the wire flame spraying device. Material: Al wire
　［比較例２］
　材料にＡｌ粉末のみを使用したこと以外、実施例１と同様の方法により、試験片を作製した。 [Comparative Example 2]
Test pieces were prepared in the same manner as in Example 1, except that only Al powder was used as the material.
　実施例１～９に係る方法、及び、比較例１、２に係る方法により、試験片を作製した後、各試験片に対して、以下の測定を行った。 After preparing test specimens using the methods of Examples 1 to 9 and Comparative Examples 1 and 2, the following measurements were performed on each test specimen.
　[Ａｌ２Ｏ３含有率]
　各試験片を皮膜が形成されている面に対して垂直に切断し、この切断物を樹脂に埋めて切断で生じた断面を研磨した後、この皮膜断面の画像を走査型電子顕微鏡（日本電子社製、ＪＳＭ－ＩＴ３００ＬＡ）により撮影した。次に、この断面画像を画像解析ソフト（三谷商事社製、ＷｉｎＲＯＯＦ２０１８）で二値化処理してＡｌ２Ｏ３粒子を特定し、Ａｌ２Ｏ３粒子の面積が溶射皮膜断面に占める割合を算出した。 [ Al2O3 content ]
Each test piece was cut perpendicular to the surface on which the coating was formed, the cut pieces were embedded in resin, and the cross section resulting from the cutting was polished, after which an image of the cross section of the coating was taken with a scanning electron microscope (JSM-IT300LA, manufactured by JEOL Ltd.). Next, the cross-sectional image was binarized with image analysis software (WinROOF2018, manufactured by Mitani Shoji Co., Ltd.) to identify the Al2O3 particles, and the proportion of the area of the Al2O3 particles in the cross section of the thermal spray coating was calculated.
　[気孔率]
　各試験片を皮膜が形成されている面に対して垂直に切断し、この切断物を樹脂に埋めて切断で生じた断面を研磨した後、この皮膜断面の画像を走査型電子顕微鏡（日本電子社製、ＪＳＭ－ＩＴ３００ＬＡ）により撮影した。次に、この断面画像を画像解析ソフト（三谷商事社製、ＷｉｎＲＯＯＦ２０１８）で二値化処理して気孔を特定し、気孔部分の面積が溶射皮膜断面に占める割合を算出した。 [Porosity]
Each test piece was cut perpendicularly to the surface on which the coating was formed, the cut pieces were embedded in resin, and the cross section resulting from the cutting was polished, after which an image of the cross section of the coating was taken with a scanning electron microscope (JSM-IT300LA, manufactured by JEOL Ltd.). Next, the cross-sectional image was binarized using image analysis software (WinROOF2018, manufactured by Mitani Shoji Co., Ltd.) to identify the pores, and the proportion of the area of the pores to the cross section of the thermal spray coating was calculated.
　実施例１～９に係る方法、及び、比較例１、２に係る方法により、試験片を作製した後、各試験片に対して、以下の試験を行った。 After preparing test specimens using the methods of Examples 1 to 9 and Comparative Examples 1 and 2, the following tests were performed on each test specimen.
　[密着力試験]
　密着力試験は、ＪＩＳ  Ｈ  ８４０２に準拠した方法で行い、破断面圧（ＭＰａ）を基準に基材と溶射皮膜との密着力を評価した。 [Adhesion test]
The adhesion test was carried out according to a method in accordance with JIS H 8402, and the adhesion between the substrate and the thermal spray coating was evaluated based on the fracture surface pressure (MPa).
　[塩水噴霧試験]
　塩水噴霧試験は、ＪＩＳ　Ｚ２３７１：２０１５に準拠した方法で３００時間行った。その後、断面観察を行い、皮膜と基材との界面の腐食生成物の有無を確認することにより、耐食性を評価した。耐食性の評価指標の意味は以下のとおりである。
　〇：３００時間経過後において腐食生成物は見られなかった。
　×：３００時間経過後において腐食生成物が見られた。 [Salt spray test]
The salt spray test was performed for 300 hours according to a method conforming to JIS Z2371:2015. After that, the cross section was observed to check for the presence or absence of corrosion products at the interface between the coating and the substrate, thereby evaluating the corrosion resistance. The evaluation indexes for corrosion resistance have the following meanings:
◯: No corrosion products were observed after 300 hours.
×: Corrosion products were observed after 300 hours.
　表１は、実施例１～９、比較例１、２の各試験片に対して、上述の測定・試験を行った結果をまとめた表である。また、図３は、実施例１～７の各試験片における、体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）と皮膜中のＡｌ２Ｏ３含有率との関係をグラフにしたものであり、図４は、実施例１～７の各試験片における、体積比（Ａｌ２Ｏ３粉末／Ａｌ粉末）と皮膜中の気孔率との関係をグラフにしたものである。 Table 1 is a table summarizing the results of the above-mentioned measurements and tests performed on each test piece of Examples 1 to 9 and Comparative Examples 1 and 2. In addition, Fig. 3 is a graph showing the relationship between the volume ratio (Al 2 O 3 powder/Al powder) and the Al 2 O 3 content in the coating for each test piece of Examples 1 to 7, and Fig. 4 is a graph showing the relationship between the volume ratio (Al 2 O 3 powder/Al powder) and the porosity in the coating for each test piece of Examples 1 to 7.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１中の密着力の項目において、いずれの試験片も、基材と溶射皮膜との間では破断せず、２５ＭＰａ未満の応力で溶射皮膜と接着剤層との間で破断が生じたため、表中には、少なくとも確認された最小の大きさの密着力を記載している。実施例１～９の溶射皮膜は、いずれも２５ＭＰａ以上の密着力を有することが分かった。このことから、密着力においては、従来の溶線式フレーム溶射で成膜した溶射皮膜に比べて、少なくとも３倍以上の向上効果を確認することができた。 In the adhesion section of Table 1, none of the test pieces broke between the substrate and the sprayed coating, but broke between the sprayed coating and the adhesive layer at a stress of less than 25 MPa, so the table lists at least the minimum adhesion strength that was confirmed. It was found that all of the sprayed coatings of Examples 1 to 9 had an adhesion strength of 25 MPa or more. This confirmed that the adhesion strength was at least three times better than that of sprayed coatings formed by conventional wire-type flame spraying.
　表１に示す通り、実施例１～９の試験片は、気孔率、密着力、耐食性のいずれにおいても比較例１と比べて良好な結果となることが分かった。 As shown in Table 1, the test pieces of Examples 1 to 9 were found to have better results than Comparative Example 1 in terms of porosity, adhesion, and corrosion resistance.
　実施例３の方法により成膜した皮膜の部分断面図の写真を図５に示し、比較例１の方法により成膜した皮膜の部分断面図の写真を図６に示す。実施例３の溶射皮膜は皮膜全域において緻密な組織となっているが、比較例１の溶射皮膜は、気孔が多い組織となっている事が分かる。なお、図示していないが、実施例１～９の皮膜は、いずれも図５のように皮膜全域が緻密な皮膜となっていた。このことから、実施例１～９の試験片が、比較例１の試験片に比べて気孔率、密着力、耐食性のいずれにおいても良好な結果となったのは、全域が緻密な皮膜組織であることによるものと推察される。 Figure 5 shows a photograph of a partial cross section of the coating formed by the method of Example 3, and Figure 6 shows a photograph of a partial cross section of the coating formed by the method of Comparative Example 1. It can be seen that the thermal spray coating of Example 3 has a dense structure throughout the entire coating, while the thermal spray coating of Comparative Example 1 has a structure with many pores. Although not shown, the coatings of Examples 1 to 9 were all dense throughout the entire coating, as shown in Figure 5. From this, it is presumed that the reason why the test pieces of Examples 1 to 9 showed better results in terms of porosity, adhesion, and corrosion resistance than the test piece of Comparative Example 1 is because the coating structure was dense throughout.
　また、図３及び図４に示す通り、実施例３～７の試験片のＡｌ２Ｏ３含有率は、実施例１，２のＡｌ２Ｏ３含有率に比べて大きく、実施例３～７の試験片の気孔率は、実施例１，２の気孔率に比べて小さいことが分かる。すなわち、材料粉末ないし皮膜中のＡｌ２Ｏ３含有率が一定以上大きいと、気孔率が大幅に低下することが分かる。 3 and 4, it is understood that the Al 2 O 3 contents of the test pieces of Examples 3 to 7 are larger than those of Examples 1 and 2, and the porosity of the test pieces of Examples 3 to 7 is smaller than those of Examples 1 and 2. In other words, it is understood that when the Al 2 O 3 content in the material powder or coating is larger than a certain level, the porosity is significantly reduced.
　本発明に係るオープンラック式気化器部材は、例えば、伝熱管、上部ヘッダ管、下部ヘッダ管として使用できる。 The open rack type evaporator components of the present invention can be used, for example, as heat transfer tubes, upper header tubes, and lower header tubes.
１　　オープンラック式気化器
２　　下部ヘッダ管
３　　伝熱管
４　　上部ヘッダ管
５　　冷媒供給部材
６　　冷媒散水トラフ
７　　液化ガス供給部材
１０２　　下部ヘッダ管
１０３　　伝熱管
１０４　　上部ヘッダ管
１０６　　冷媒散水トラフ Reference Signs List 1 Open rack type vaporizer 2 Lower header tube 3 Heat transfer tube 4 Upper header tube 5 Refrigerant supply member 6 Refrigerant water sprinkling trough 7 Liquefied gas supply member 102 Lower header tube 103 Heat transfer tube 104 Upper header tube 106 Refrigerant water sprinkling trough

Claims (6)

  1. 　オープンラック式の気化器部材の製造方法であって、
    　Ａｌ又はＡｌ合金からなる基材の表面に対して、Ａｌ粉末又はＡｌ合金粉末と、Ａｌ２Ｏ３粉末と、を高速フレームに投入することにより溶射皮膜を形成することを特徴とするオープンラック式の気化器部材の製造方法。     1. A method for manufacturing an open rack type carburetor component, comprising the steps of:
    A manufacturing method for an open rack type carburetor member , characterized in that a thermal spray coating is formed on the surface of a substrate made of Al or an Al alloy by feeding Al powder or Al alloy powder and Al2O3 powder into a high-velocity flame.
  2. 　前記Ａｌ粉末又はＡｌ合金粉末（Ａ）と、前記Ａｌ２Ｏ３粉末（Ｂ）との体積比は、０．１≦（Ｂ）／（Ａ）≦３．５である請求項１に記載の気化器部材の製造方法。 2. The method for manufacturing a carburetor member according to claim 1, wherein a volume ratio of the Al powder or Al alloy powder (A) to the Al 2 O 3 powder (B) satisfies 0.1≦(B)/(A)≦3.5.
  3. 　Ａｌ又はＡｌ合金からなる基材と、前記基材表面に形成された溶射皮膜とを備え、
    　前記溶射皮膜は、Ａｌ又はＡｌ合金からなる主相と、該主相中に分散したＡｌ２Ｏ３粒子と、を含むことを特徴とするオープンラック式の気化器部材。     A substrate made of Al or an Al alloy and a thermal spray coating formed on a surface of the substrate,
    The open rack type carburetor member, wherein the thermal spray coating includes a main phase made of Al or an Al alloy, and Al 2 O 3 particles dispersed in the main phase.
  4. 　前記溶射皮膜のＡｌ２Ｏ３含有率は、１０％以上、３０％未満である請求項３に記載のオープンラック式の気化器部材。 The open rack type carburetor component according to claim 3, wherein the Al2O3 content of the thermal spray coating is 10% or more and less than 30%.
  5. 　前記溶射皮膜の気孔率が４％未満である請求項３に記載のオープンラック式の気化器部材。 The open rack type carburetor component according to claim 3, wherein the porosity of the thermal spray coating is less than 4%.
  6. 　前記溶射皮膜の前記基材との密着力が２５ＭＰａ以上である請求項３に記載のオープンラック式の気化器部材。 The open rack type carburetor component according to claim 3, wherein the adhesion strength of the thermal spray coating to the substrate is 25 MPa or more.
PCT/JP2023/043786 2022-12-13 2023-12-07 Manufacturing method for open rack vaporizer member and open rack vaporizer member WO2024128115A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0364444A (en) * 1989-08-01 1991-03-19 Kobe Steel Ltd Wire for forming surface film
JP2000064021A (en) * 1998-06-12 2000-02-29 Osaka Gas Co Ltd Thermally sprayed coating, evaporator, heat exchanger, fluid heater and fluid cooler
JP2003286559A (en) * 2002-03-28 2003-10-10 Kurimoto Ltd Corrosion prevention coating on ferrous substrate and corrosion prevention method
JP2011112294A (en) * 2009-11-27 2011-06-09 Kobe Steel Ltd Heat transfer tube and header pipe for open rack type vaporizer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0364444A (en) * 1989-08-01 1991-03-19 Kobe Steel Ltd Wire for forming surface film
JP2000064021A (en) * 1998-06-12 2000-02-29 Osaka Gas Co Ltd Thermally sprayed coating, evaporator, heat exchanger, fluid heater and fluid cooler
JP2003286559A (en) * 2002-03-28 2003-10-10 Kurimoto Ltd Corrosion prevention coating on ferrous substrate and corrosion prevention method
JP2011112294A (en) * 2009-11-27 2011-06-09 Kobe Steel Ltd Heat transfer tube and header pipe for open rack type vaporizer

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