WO2011135787A1 - Plated steel sheet for producing pipe having corrosion resistance against fuel vapor, and pipe and oil supply pipe using the plated steel sheet - Google Patents
Plated steel sheet for producing pipe having corrosion resistance against fuel vapor, and pipe and oil supply pipe using the plated steel sheet Download PDFInfo
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- WO2011135787A1 WO2011135787A1 PCT/JP2011/002160 JP2011002160W WO2011135787A1 WO 2011135787 A1 WO2011135787 A1 WO 2011135787A1 JP 2011002160 W JP2011002160 W JP 2011002160W WO 2011135787 A1 WO2011135787 A1 WO 2011135787A1
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- pipe
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- steel sheet
- corrosion resistance
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
- F02M37/0076—Details of the fuel feeding system related to the fuel tank
- F02M37/0082—Devices inside the fuel tank other than fuel pumps or filters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
- B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
- B60K15/03—Fuel tanks
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- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
Definitions
- the present invention relates to a surface-treated steel sheet and pipe having corrosion resistance against fuel vapor.
- Patent Document 1 discloses that the deposition amount is Cr on a Sn—Zn alloy plated surface having a plating deposition amount of 10 to 70 g / m 2 and Sn-1 to 50% Zn.
- a fuel container for automobiles having excellent corrosion resistance is described in which the flange portion of the vertical molded body is continuously seam welded.
- the material used for the automobile fuel container described in Patent Document 1 is a corrosion resistance of a portion such as a fuel tank that is immersed in an automobile fuel such as gasoline and directly contacts the automobile fuel, and is not corrosion resistant to steam.
- a pipe connected to a fuel tank, such as a fuel supply pipe is exposed to highly volatile automobile fuel vapor rather than being directly exposed to automobile fuel as an actual usage environment. Overwhelmingly many.
- the depletion of fossil fuels has become serious internationally, and the spread of bioethanol and biodiesel fuels has become widespread.
- gasoline which is a conventional automobile fuel
- a material having sufficient characteristics for both bioethanol and biodiesel fuel and its vapor has been demanded.
- an object of the present invention is to solve the above-described conventional problems, and fuel vapor having sufficient corrosion resistance against fuel vapor such as automobile fuel, particularly gasoline, light oil, bioethanol, or biodiesel fuel. It is providing the plated steel plate for pipe manufacture which has the corrosion resistance with respect to. Another object of the present invention is to provide a pipe and an oil supply pipe using the plated steel plate.
- the plated steel sheet for pipe production having corrosion resistance against the fuel vapor of the present invention is: It has a plating layer containing Zn, Co and Mo on the surface of the steel sheet, and the composition ratio of Co to Zn in the plating layer is 0.2 to 4.0 at% (atomic concentration)
- the steel sheet and the plating layer containing Zn, Co and Mo A plating layer containing Zn, Co, and Mo may be provided on the metal layer as a lower layer, and a metal layer may be provided on the plating layer containing Zn, Co, and Mo. You may provide as.
- the plated steel sheet for producing a pipe having corrosion resistance to the fuel vapor of the present invention is the above (1).
- the fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
- the pipe having corrosion resistance to the fuel vapor of the present invention is: It has a plating layer containing Zn, Co and Mo on the inner surface of a pipe made of a steel plate.
- the pipe having corrosion resistance to the fuel vapor of the present invention is the above (3).
- the fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
- a fuel supply pipe having corrosion resistance against the fuel vapor of the present invention is: A refueling pipe for refueling a fuel tank, A large-diameter pipe section through which fuel passes; It has a small diameter pipe part that ventilates the upper part and the lower part of the large diameter pipe part, At least on the inner surface of the large-diameter pipe part, It has corrosion resistance to fuel vapor, characterized by having a plating layer containing Zn, Co and Mo with a Co composition ratio of 0.2 to 4.0 at% (atomic concentration).
- the oil supply pipe having corrosion resistance to the fuel vapor of the present invention is the above (5).
- the fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
- the plated steel sheet for pipe production having corrosion resistance to the fuel vapor of the present invention, the pipe using the plated steel sheet, and the oil supply pipe may be exposed to fuel vapor such as gasoline, light oil, bioethanol, or biodiesel fuel as fuel. , Suppresses rusting and suppresses deterioration of the fuel itself.
- Step plate> A low-carbon aluminum killed hot-rolled coil is usually used as an original plate for a plated steel sheet for pipe production. Further, an ultra-low carbon steel having 0.003% by mass or less of carbon, or a coil manufactured from non-aging continuous cast steel by adding niobium or titanium to the steel is also used.
- ⁇ Plating pretreatment> As a pretreatment for plating containing Zn, Co, and Mo, a scale (oxide film) on the surface of the cold-rolled steel sheet is removed by performing degreasing by electrolysis or immersion in an alkaline solution usually containing caustic soda. After removal, the product is rolled to the product thickness in a cold rolling process.
- the rolling oil adhered by rolling is electrolytically cleaned and then annealed.
- the annealing may be either continuous annealing or box annealing and is not particularly particular. After annealing, the shape is corrected.
- a layer containing Zn, Co, and Mo is formed by plating.
- a layer containing Zn, Co, and Mo is formed by plating.
- the plating conditions in that case are as follows.
- Plating bath composition Zinc sulfate 180-280 g / L, Cobalt sulfate 0-100g / L, Ammonium molybdate 0.01-0.4 g / L, Ammonium sulfate 10-40 g / L, Sodium sulfate 20-50 g / L, pH: 2.7 to 3.7, Bath temperature: 30-50 ° C, Current density: 5 to 50 A / dm 2 , And
- the composition ratio of Co to Zn is 0.2 to 4.0 at% (atomic concentration, hereinafter “at%” means atomic concentration). It is preferable to be in the range.
- the thickness of the plating layer containing Zn, Co, and Mo is preferably 2.0 to 8.0 ⁇ m. Such adjustment of the plating thickness can be realized by adjusting the plating bath composition, pH, bath temperature, current density, and the like within a suitable range.
- a composition ratio of the plating layer containing Zn, Co, and Mo Co: 0.2 to 4.0 at%, Mo: 0.001 to 1 at%
- the balance is preferably Zn.
- composition ratio of Co in the plating layer containing Zn, Co, and Mo is less than 0.2 at%, sufficient corrosion resistance of the gas phase portion cannot be obtained.
- Co composition ratio of the plating containing Zn, Co, and Mo exceeds 4.0 at%, corrosion resistance is obtained with the plating layer on the flat plate, but the workability decreases due to the hardened film, and the pipe Cracking occurs during processing, and sufficient corrosion resistance of the gas phase portion cannot be obtained.
- Such adjustment of the composition ratio in the plating layer can be realized by adjusting the plating bath composition, pH, bath temperature, current density, and the like within a suitable range.
- Evaluation test pieces were prepared from steel sheets provided with plating layers containing Zn, Co, and Mo, having various Co composition ratios, and corrosion resistance was investigated by immersing them in bioethanol mixed gasoline. Corrosion resistance was confirmed by the presence or absence of rusting. A corrosive solution simulating bioethanol-mixed gasoline was used as a test. Formic acid and acetic acid were added to regular gasoline specified in JIS K2202, and 10% by mass of bioethanol specified in JASO M361 was added to purify the simulated deteriorated gasoline.
- corrosive water in which formic acid, acetic acid and chlorine were added to pure water was prepared, and 10% by mass was added to deteriorated gasoline to obtain a corrosive liquid.
- the corrosive liquid is in a state where the upper layer is divided into degraded gasoline and the lower layer is divided into two layers of corrosive water.
- the corrosive solution was placed in a sealed container so that an evaluation test piece provided with a plating layer containing Zn, Co, and Mo having the respective Co composition ratios was half-immersed, and was aged in a 45 ° C. constant temperature bath. Accordingly, as shown in FIG.
- the evaluation test pieces are, from the upper part, the gas phase portion 11 in contact with the fuel vapor (gas phase) of the deteriorated gasoline, the liquid phase portion 12 in contact with the deteriorated gasoline (liquid phase), and corrosion. It will be separated and evaluated in the water phase part 13 in contact with water (water phase). And the corrosion resistance with respect to the fuel vapor
- ⁇ Pipe processing> Using a plated steel sheet on which a plated layer containing Zn, Co, and Mo is formed, the shape is corrected by a leveler, slitted to a predetermined outer size with a slitter, and then formed into a pipe shape by a molding machine.
- Pipes are manufactured by seam welding end surfaces in the direction by high frequency induction welding.
- As the pipe there are an oil supply pipe for introducing fuel into the tank, a pipe for introducing fuel from the tank to the engine, and a pipe for venting.
- the fuel supply pipe 20 is attached to the fuel tank 23 as shown in FIG. 3A, and the fuel supply pipe 20 is attached to the fuel tank 23 from the upper part of the fuel tank 23 in an obliquely upward direction.
- a small-diameter pipe portion 22 that branches from the middle of the large-diameter pipe portion 21 through which the fuel passes and is connected to the upper and lower portions of the large-diameter pipe portion 21 is connected to the fuel supply pipe 20.
- the large diameter pipe part 21 is manufactured using the plated steel sheet of the present invention. In addition, you may manufacture the small diameter pipe part 22 using the plated steel plate of this invention.
- regulated by this invention is not restricted to a shape as shown to Fig.3 (a),
- Fig.3 (b) For example, as shown in FIG.3 (b), with the large diameter pipe part 21 through which fuel passes, Even if the small-diameter pipe portion 22 is attached to the fuel tank 23 in an independent shape, the corrosion resistance against the fuel vapor is still particularly required, and thus those of these forms are also included.
- Example 1 A cold-rolled and annealed low carbon aluminum killed steel plate having a thickness of 0.70 mm was used as the original plate.
- the components of the steel plate that is the plating original plate are as follows. C: 0.045 mass%, Mn: 0.23 mass%, Si: 0.02 mass%, P: 0.012 mass%, S: 0.009 mass%, Al: 0.063 mass%, N: 0.0036% by mass, balance: Fe and inevitable impurities.
- the steel sheet was subjected to alkaline electrolytic degreasing and pickling with sulfuric acid soaking, to obtain a plated steel sheet provided with a plating layer containing Zn, Co, and Mo having a thickness of 4.2 ⁇ m.
- the composition ratio of the formed plating layer containing Zn, Co, and Mo was 0.2 at% and the composition ratio of Mo was 0.01 at% with respect to Zn.
- the composition ratio in the plating layer was measured by EZ scan using a Rigaku fluorescent X-ray apparatus (ZSX 100e). The fluorescent X-ray apparatus was also used for measuring the plating thickness.
- Example 2 to 7 Comparative Examples 1 to 6> Examples 2 to 7 and Comparative Examples 1 to 6 were the same as Example 1 except that the composition ratio of Co in the plating layer containing Zn, Co, and Mo was changed to the values shown in Table 1. A plated steel sheet was obtained.
- the plated steel sheets provided with the plating layers containing Zn, Co, and Mo of Examples 1 to 7 of the present invention have no red rust, have a good plating appearance, and are suitable for pipe production. It was excellent as a plated steel sheet.
- the plated steel sheets of Comparative Examples 1 to 4 have red rust and are impractical as a plated steel sheet for pipe production that requires corrosion resistance.
- the plated steel sheet for manufacturing pipes of the present invention can suppress rust generation and exposure to fuel vapor such as gasoline, light oil, bioethanol, or biodiesel fuel, and can also suppress deterioration of the fuel itself. . Moreover, the pipe using the plated steel plate for pipe manufacture of this invention and an oil supply pipe are excellent in corrosion resistance with respect to fuel vapor
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Abstract
Provided are: a plated steel sheet for producing a pipe which has corrosion resistance against a fuel vapor such as vapor of gasoline, light oil, bioethanol, biodiesel fuel or the like; a pipe; and an oil supply pipe.
The plated steel sheet for producing a pipe, said pipe having corrosion resistance against a fuel vapor, is characterized by being provided with a plating layer containing Zn, Co and Mo on the surface of a steel sheet, wherein the composition ratio of Co, relative to Zn, in said plating layer is 0.2-4.0 at% (atomic percentage).
The pipe, which has corrosion resistance against a fuel vapor, is characterized by being provided with a plating layer, which contains Zn, Co and Mo, on the inner face of a pipe formed of a steel sheet.
The oil supply pipe (20), which is to be used for supplying a fuel oil to a fuel tank (23), comprises a large-diameter pipe section (21), through which the fuel passes, and a small-diameter pipe section (22) for aerating the upper part and lower part of the large-diameter pipe section, wherein a plating layer containing Zn, Co and Mo and having a composition ratio of Co, relative to Zn, of 0.2-4.0 at% is provided at least on the inner face of the large-diameter pipe section.
Description
本発明は、燃料蒸気に対して耐食性を有する表面処理鋼板、パイプに関する。
The present invention relates to a surface-treated steel sheet and pipe having corrosion resistance against fuel vapor.
近年、温室効果ガス削減のため、カーボンニュートラルとされるバイオエタノールをガソリンに混合したいわゆるバイオエタノール混合ガソリンを使用する動きが活発化している。しかしながら、ガソリンにエタノールを添加すると、ガソリンが吸湿しやすくなり、燃料タンク内に水が混入することが考えられる。
さらに、エタノール混合ガソリンを長期間放置したままであると、ガソリンが劣化しガソリン内に有機酸が形成される。
このように、吸湿状態とガソリンの劣化が発生した場合、エタノールは水とガソリンの両方に混合できるため、ガソリン内部に水と有機酸が含まれた状態になり、ガソリン表面から水と有機酸の混合物が気化することがある。
その場合には、通常は腐食性の殆ど無いガソリン蒸気にしか接触しないパイプの内面が、強い腐食環境下にさらされる。
よって、バイオエタノール混合ガソリンの雰囲気下に置かれるパイプにも、腐食環境を想定した耐食性が求められる。
これらの腐食環境に対応するものとして、例えば、特許文献１には、めっき付着量が１０～７０ｇ／ｍ２、Ｓｎ－１～５０％ＺｎであるＳｎ－Ｚｎ合金めっき面に、付着量がＣｒ換算で１００ｍｇ／ｍ２以下であるクロム酸、シリカ、無機リン酸や有機リン酸からなるクロメート被膜を処理、或いは更に有機樹脂を含有した樹脂クロメート被膜を処理した鋼板を用い、フランジを有する一対の椀型成型体のフランジ部を連続的にシーム溶接して一体とした耐食性に優れた自動車用燃料容器が記載されている。 In recent years, in order to reduce greenhouse gases, there has been an active movement to use so-called bioethanol-mixed gasoline in which bioethanol, which is carbon neutral, is mixed with gasoline. However, when ethanol is added to gasoline, it becomes easier for the gasoline to absorb moisture, and water may be mixed into the fuel tank.
Furthermore, if the ethanol mixed gasoline is left standing for a long time, the gasoline deteriorates and an organic acid is formed in the gasoline.
In this way, when moisture absorption and gasoline deterioration occur, ethanol can be mixed into both water and gasoline, so water and organic acids are contained inside the gasoline. The mixture may evaporate.
In that case, the inner surface of the pipe, which normally contacts only non-corrosive gasoline vapor, is exposed to a strong corrosive environment.
Therefore, pipes placed under an atmosphere of bioethanol mixed gasoline are also required to have corrosion resistance assuming a corrosive environment.
As a countermeasure to these corrosive environments, for example, Patent Document 1 discloses that the deposition amount is Cr on a Sn—Zn alloy plated surface having a plating deposition amount of 10 to 70 g / m 2 and Sn-1 to 50% Zn. A steel plate treated with a chromate film made of chromic acid, silica, inorganic phosphoric acid or organic phosphoric acid of 100 mg / m 2 or less in terms of conversion, or further treated with a resin chromate film containing an organic resin, and a pair of flanges A fuel container for automobiles having excellent corrosion resistance is described in which the flange portion of the vertical molded body is continuously seam welded.
さらに、エタノール混合ガソリンを長期間放置したままであると、ガソリンが劣化しガソリン内に有機酸が形成される。
このように、吸湿状態とガソリンの劣化が発生した場合、エタノールは水とガソリンの両方に混合できるため、ガソリン内部に水と有機酸が含まれた状態になり、ガソリン表面から水と有機酸の混合物が気化することがある。
その場合には、通常は腐食性の殆ど無いガソリン蒸気にしか接触しないパイプの内面が、強い腐食環境下にさらされる。
よって、バイオエタノール混合ガソリンの雰囲気下に置かれるパイプにも、腐食環境を想定した耐食性が求められる。
これらの腐食環境に対応するものとして、例えば、特許文献１には、めっき付着量が１０～７０ｇ／ｍ２、Ｓｎ－１～５０％ＺｎであるＳｎ－Ｚｎ合金めっき面に、付着量がＣｒ換算で１００ｍｇ／ｍ２以下であるクロム酸、シリカ、無機リン酸や有機リン酸からなるクロメート被膜を処理、或いは更に有機樹脂を含有した樹脂クロメート被膜を処理した鋼板を用い、フランジを有する一対の椀型成型体のフランジ部を連続的にシーム溶接して一体とした耐食性に優れた自動車用燃料容器が記載されている。 In recent years, in order to reduce greenhouse gases, there has been an active movement to use so-called bioethanol-mixed gasoline in which bioethanol, which is carbon neutral, is mixed with gasoline. However, when ethanol is added to gasoline, it becomes easier for the gasoline to absorb moisture, and water may be mixed into the fuel tank.
Furthermore, if the ethanol mixed gasoline is left standing for a long time, the gasoline deteriorates and an organic acid is formed in the gasoline.
In this way, when moisture absorption and gasoline deterioration occur, ethanol can be mixed into both water and gasoline, so water and organic acids are contained inside the gasoline. The mixture may evaporate.
In that case, the inner surface of the pipe, which normally contacts only non-corrosive gasoline vapor, is exposed to a strong corrosive environment.
Therefore, pipes placed under an atmosphere of bioethanol mixed gasoline are also required to have corrosion resistance assuming a corrosive environment.
As a countermeasure to these corrosive environments, for example, Patent Document 1 discloses that the deposition amount is Cr on a Sn—Zn alloy plated surface having a plating deposition amount of 10 to 70 g / m 2 and Sn-1 to 50% Zn. A steel plate treated with a chromate film made of chromic acid, silica, inorganic phosphoric acid or organic phosphoric acid of 100 mg / m 2 or less in terms of conversion, or further treated with a resin chromate film containing an organic resin, and a pair of flanges A fuel container for automobiles having excellent corrosion resistance is described in which the flange portion of the vertical molded body is continuously seam welded.
しかし、上記特許文献１記載の自動車用燃料容器に用いられる素材は、ガソリンなどの自動車用燃料に浸漬され、直接自動車燃料と接触する燃料タンクのような部分の耐食性であり、蒸気に対する耐食性ではない。
例えば、給油管のように燃料タンクに接続されるパイプは、実際の使用環境として、自動車用燃料に直接暴露されることよりも、揮発性の高い自動車燃料の蒸気に暴露されるケースの方が圧倒的に多い。
また、国際的に化石燃料の枯渇化が深刻化しており、バイオエタノールやバイオディーゼル燃料などの普及が広まっている。
このように、従来の自動車燃料であるガソリンに加え、バイオエタノールやバイオディーゼル燃料及びその蒸気の両方に対して十分な特性を有する素材が求められていた。
そこで、本発明の目的は、上記の従来の課題を解決することであり、自動車燃料、特にガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料などの燃料蒸気に対して十分な耐食性を有する、燃料蒸気に対する耐食性を有するパイプ製造用めっき鋼板を提供することである。
また、本発明の他の目的は、そのめっき鋼板を用いたパイプ及び給油パイプを提供することである。 However, the material used for the automobile fuel container described in Patent Document 1 is a corrosion resistance of a portion such as a fuel tank that is immersed in an automobile fuel such as gasoline and directly contacts the automobile fuel, and is not corrosion resistant to steam. .
For example, a pipe connected to a fuel tank, such as a fuel supply pipe, is exposed to highly volatile automobile fuel vapor rather than being directly exposed to automobile fuel as an actual usage environment. Overwhelmingly many.
In addition, the depletion of fossil fuels has become serious internationally, and the spread of bioethanol and biodiesel fuels has become widespread.
Thus, in addition to gasoline, which is a conventional automobile fuel, a material having sufficient characteristics for both bioethanol and biodiesel fuel and its vapor has been demanded.
Therefore, an object of the present invention is to solve the above-described conventional problems, and fuel vapor having sufficient corrosion resistance against fuel vapor such as automobile fuel, particularly gasoline, light oil, bioethanol, or biodiesel fuel. It is providing the plated steel plate for pipe manufacture which has the corrosion resistance with respect to.
Another object of the present invention is to provide a pipe and an oil supply pipe using the plated steel plate.
例えば、給油管のように燃料タンクに接続されるパイプは、実際の使用環境として、自動車用燃料に直接暴露されることよりも、揮発性の高い自動車燃料の蒸気に暴露されるケースの方が圧倒的に多い。
また、国際的に化石燃料の枯渇化が深刻化しており、バイオエタノールやバイオディーゼル燃料などの普及が広まっている。
このように、従来の自動車燃料であるガソリンに加え、バイオエタノールやバイオディーゼル燃料及びその蒸気の両方に対して十分な特性を有する素材が求められていた。
そこで、本発明の目的は、上記の従来の課題を解決することであり、自動車燃料、特にガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料などの燃料蒸気に対して十分な耐食性を有する、燃料蒸気に対する耐食性を有するパイプ製造用めっき鋼板を提供することである。
また、本発明の他の目的は、そのめっき鋼板を用いたパイプ及び給油パイプを提供することである。 However, the material used for the automobile fuel container described in Patent Document 1 is a corrosion resistance of a portion such as a fuel tank that is immersed in an automobile fuel such as gasoline and directly contacts the automobile fuel, and is not corrosion resistant to steam. .
For example, a pipe connected to a fuel tank, such as a fuel supply pipe, is exposed to highly volatile automobile fuel vapor rather than being directly exposed to automobile fuel as an actual usage environment. Overwhelmingly many.
In addition, the depletion of fossil fuels has become serious internationally, and the spread of bioethanol and biodiesel fuels has become widespread.
Thus, in addition to gasoline, which is a conventional automobile fuel, a material having sufficient characteristics for both bioethanol and biodiesel fuel and its vapor has been demanded.
Therefore, an object of the present invention is to solve the above-described conventional problems, and fuel vapor having sufficient corrosion resistance against fuel vapor such as automobile fuel, particularly gasoline, light oil, bioethanol, or biodiesel fuel. It is providing the plated steel plate for pipe manufacture which has the corrosion resistance with respect to.
Another object of the present invention is to provide a pipe and an oil supply pipe using the plated steel plate.
（１）本発明の燃料蒸気に対する耐食性を有するパイプ製造用めっき鋼板は、
鋼板の表面にＺｎ、Ｃｏ及びＭｏを含有するめっき層を有しており、前記めっき層中におけるＺｎに対するＣｏの組成割合が、０．２～４．０ａｔ％（原子濃度）とすることを特徴とする。なお、本発明においては表面処理鋼板が前記Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を有すれば本発明の耐食性の効果を得られるため、鋼板と前記Ｚｎ、Ｃｏ及びＭｏを含有するめっき層との間に金属層を下層として設けた上に前記Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を設けてもよく、また前記Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を設けた上に金属層を上層として設けてもよい。
（２）本発明の燃料蒸気に対する耐食性を有するパイプ製造用めっき鋼板は、前記（１）において、
前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする。
（３）本発明の燃料蒸気に対する耐食性を有するパイプは、
鋼板からなるパイプの内面に、Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を有していることを特徴とする。
（４）本発明の燃料蒸気に対する耐食性を有するパイプは、前記（３）において、
前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする。
（５）本発明の燃料蒸気に対する耐食性を有する給油パイプは、
燃料を燃料タンクに給油するための給油パイプであって、
燃料が通過する太径パイプ部と、
太径パイプ部の上部と下部とを通気する細径パイプ部とを有し、
少なくとも前記太径パイプ部の内面に、
Ｚｎに対するＣｏの組成割合が、０．２～４．０ａｔ％（原子濃度）であるＺｎ、Ｃｏ及びＭｏを含有するめっき層を有していることを特徴とする燃料蒸気に対する耐食性を有することを特徴とする。
（６）本発明の燃料蒸気に対する耐食性を有する給油パイプは、前記（５）において、
前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする。 (1) The plated steel sheet for pipe production having corrosion resistance against the fuel vapor of the present invention is:
It has a plating layer containing Zn, Co and Mo on the surface of the steel sheet, and the composition ratio of Co to Zn in the plating layer is 0.2 to 4.0 at% (atomic concentration) And In the present invention, if the surface-treated steel sheet has a plating layer containing Zn, Co and Mo, the corrosion resistance effect of the present invention can be obtained. Therefore, the steel sheet and the plating layer containing Zn, Co and Mo A plating layer containing Zn, Co, and Mo may be provided on the metal layer as a lower layer, and a metal layer may be provided on the plating layer containing Zn, Co, and Mo. You may provide as.
(2) The plated steel sheet for producing a pipe having corrosion resistance to the fuel vapor of the present invention is the above (1).
The fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
(3) The pipe having corrosion resistance to the fuel vapor of the present invention is:
It has a plating layer containing Zn, Co and Mo on the inner surface of a pipe made of a steel plate.
(4) The pipe having corrosion resistance to the fuel vapor of the present invention is the above (3).
The fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
(5) A fuel supply pipe having corrosion resistance against the fuel vapor of the present invention is:
A refueling pipe for refueling a fuel tank,
A large-diameter pipe section through which fuel passes;
It has a small diameter pipe part that ventilates the upper part and the lower part of the large diameter pipe part,
At least on the inner surface of the large-diameter pipe part,
It has corrosion resistance to fuel vapor, characterized by having a plating layer containing Zn, Co and Mo with a Co composition ratio of 0.2 to 4.0 at% (atomic concentration). Features.
(6) The oil supply pipe having corrosion resistance to the fuel vapor of the present invention is the above (5).
The fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
鋼板の表面にＺｎ、Ｃｏ及びＭｏを含有するめっき層を有しており、前記めっき層中におけるＺｎに対するＣｏの組成割合が、０．２～４．０ａｔ％（原子濃度）とすることを特徴とする。なお、本発明においては表面処理鋼板が前記Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を有すれば本発明の耐食性の効果を得られるため、鋼板と前記Ｚｎ、Ｃｏ及びＭｏを含有するめっき層との間に金属層を下層として設けた上に前記Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を設けてもよく、また前記Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を設けた上に金属層を上層として設けてもよい。
（２）本発明の燃料蒸気に対する耐食性を有するパイプ製造用めっき鋼板は、前記（１）において、
前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする。
（３）本発明の燃料蒸気に対する耐食性を有するパイプは、
鋼板からなるパイプの内面に、Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を有していることを特徴とする。
（４）本発明の燃料蒸気に対する耐食性を有するパイプは、前記（３）において、
前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする。
（５）本発明の燃料蒸気に対する耐食性を有する給油パイプは、
燃料を燃料タンクに給油するための給油パイプであって、
燃料が通過する太径パイプ部と、
太径パイプ部の上部と下部とを通気する細径パイプ部とを有し、
少なくとも前記太径パイプ部の内面に、
Ｚｎに対するＣｏの組成割合が、０．２～４．０ａｔ％（原子濃度）であるＺｎ、Ｃｏ及びＭｏを含有するめっき層を有していることを特徴とする燃料蒸気に対する耐食性を有することを特徴とする。
（６）本発明の燃料蒸気に対する耐食性を有する給油パイプは、前記（５）において、
前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする。 (1) The plated steel sheet for pipe production having corrosion resistance against the fuel vapor of the present invention is:
It has a plating layer containing Zn, Co and Mo on the surface of the steel sheet, and the composition ratio of Co to Zn in the plating layer is 0.2 to 4.0 at% (atomic concentration) And In the present invention, if the surface-treated steel sheet has a plating layer containing Zn, Co and Mo, the corrosion resistance effect of the present invention can be obtained. Therefore, the steel sheet and the plating layer containing Zn, Co and Mo A plating layer containing Zn, Co, and Mo may be provided on the metal layer as a lower layer, and a metal layer may be provided on the plating layer containing Zn, Co, and Mo. You may provide as.
(2) The plated steel sheet for producing a pipe having corrosion resistance to the fuel vapor of the present invention is the above (1).
The fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
(3) The pipe having corrosion resistance to the fuel vapor of the present invention is:
It has a plating layer containing Zn, Co and Mo on the inner surface of a pipe made of a steel plate.
(4) The pipe having corrosion resistance to the fuel vapor of the present invention is the above (3).
The fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
(5) A fuel supply pipe having corrosion resistance against the fuel vapor of the present invention is:
A refueling pipe for refueling a fuel tank,
A large-diameter pipe section through which fuel passes;
It has a small diameter pipe part that ventilates the upper part and the lower part of the large diameter pipe part,
At least on the inner surface of the large-diameter pipe part,
It has corrosion resistance to fuel vapor, characterized by having a plating layer containing Zn, Co and Mo with a Co composition ratio of 0.2 to 4.0 at% (atomic concentration). Features.
(6) The oil supply pipe having corrosion resistance to the fuel vapor of the present invention is the above (5).
The fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
本発明の燃料蒸気に対する耐食性を有するパイプ製造用めっき鋼板、そのめっき鋼板を用いたパイプ及び給油パイプは、燃料であるガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料などの燃料蒸気に暴露されても、発錆を抑え、燃料自体の劣化を抑制する。
The plated steel sheet for pipe production having corrosion resistance to the fuel vapor of the present invention, the pipe using the plated steel sheet, and the oil supply pipe may be exposed to fuel vapor such as gasoline, light oil, bioethanol, or biodiesel fuel as fuel. , Suppresses rusting and suppresses deterioration of the fuel itself.
以下、本発明の実施の形態を詳細に説明する。
＜鋼板＞
パイプ製造用めっき鋼板の原板としては、通常低炭素アルミキルド熱延コイルが用いられる。
また、炭素０．００３質量％以下の極低炭素鋼、または更にこれにニオブ、チタンを添加し非時効連続鋳造鋼から製造されたコイルも用いられる。 Hereinafter, embodiments of the present invention will be described in detail.
<Steel plate>
A low-carbon aluminum killed hot-rolled coil is usually used as an original plate for a plated steel sheet for pipe production.
Further, an ultra-low carbon steel having 0.003% by mass or less of carbon, or a coil manufactured from non-aging continuous cast steel by adding niobium or titanium to the steel is also used.
＜鋼板＞
パイプ製造用めっき鋼板の原板としては、通常低炭素アルミキルド熱延コイルが用いられる。
また、炭素０．００３質量％以下の極低炭素鋼、または更にこれにニオブ、チタンを添加し非時効連続鋳造鋼から製造されたコイルも用いられる。 Hereinafter, embodiments of the present invention will be described in detail.
<Steel plate>
A low-carbon aluminum killed hot-rolled coil is usually used as an original plate for a plated steel sheet for pipe production.
Further, an ultra-low carbon steel having 0.003% by mass or less of carbon, or a coil manufactured from non-aging continuous cast steel by adding niobium or titanium to the steel is also used.
＜めっき前処理＞
Ｚｎ、Ｃｏ、及びＭｏを含有するめっきの前処理としては、通常苛性ソーダを主剤としたアルカリ液に電解または浸漬による脱脂を行い、冷延鋼板表面のスケール（酸化膜）を除去する。除去後、冷間圧延工程にて製品厚みまで圧延する。 <Plating pretreatment>
As a pretreatment for plating containing Zn, Co, and Mo, a scale (oxide film) on the surface of the cold-rolled steel sheet is removed by performing degreasing by electrolysis or immersion in an alkaline solution usually containing caustic soda. After removal, the product is rolled to the product thickness in a cold rolling process.
Ｚｎ、Ｃｏ、及びＭｏを含有するめっきの前処理としては、通常苛性ソーダを主剤としたアルカリ液に電解または浸漬による脱脂を行い、冷延鋼板表面のスケール（酸化膜）を除去する。除去後、冷間圧延工程にて製品厚みまで圧延する。 <Plating pretreatment>
As a pretreatment for plating containing Zn, Co, and Mo, a scale (oxide film) on the surface of the cold-rolled steel sheet is removed by performing degreasing by electrolysis or immersion in an alkaline solution usually containing caustic soda. After removal, the product is rolled to the product thickness in a cold rolling process.
＜焼鈍＞
圧延で付着した圧延油を電解洗浄した後、焼鈍する。焼鈍は、連続焼鈍あるいは箱型焼鈍のどちらでもよく特にこだわらない。焼鈍した後、形状修正する。 <Annealing>
The rolling oil adhered by rolling is electrolytically cleaned and then annealed. The annealing may be either continuous annealing or box annealing and is not particularly particular. After annealing, the shape is corrected.
圧延で付着した圧延油を電解洗浄した後、焼鈍する。焼鈍は、連続焼鈍あるいは箱型焼鈍のどちらでもよく特にこだわらない。焼鈍した後、形状修正する。 <Annealing>
The rolling oil adhered by rolling is electrolytically cleaned and then annealed. The annealing may be either continuous annealing or box annealing and is not particularly particular. After annealing, the shape is corrected.
＜Ｚｎ、Ｃｏ、及びＭｏを含有するめっき＞
次に、Ｚｎ、Ｃｏ、及びＭｏを含有する層をめっきにより形成する。
本発明において、Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層を得るためには、Ｃｏ組成割合を制御することが重要である。その場合のめっき条件は以下のとおりである。
すなわち、
めっき浴組成：
硫酸亜鉛１８０～２８０ｇ／Ｌ、
硫酸コバルト０～１００ｇ／Ｌ、
モリブデン酸アンモニウム０．０１～０．４ｇ／Ｌ、
硫酸アンモニウム１０～４０ｇ／Ｌ、
硫酸ナトリウム２０～５０ｇ／Ｌ、
ｐＨ：２．７～３．７、
浴温：３０～５０℃、
電流密度：５～５０Ａ／ｄｍ２、
とする。 <Plating containing Zn, Co, and Mo>
Next, a layer containing Zn, Co, and Mo is formed by plating.
In the present invention, in order to obtain a plating layer containing Zn, Co, and Mo, it is important to control the Co composition ratio. The plating conditions in that case are as follows.
That is,
Plating bath composition:
Zinc sulfate 180-280 g / L,
Cobalt sulfate 0-100g / L,
Ammonium molybdate 0.01-0.4 g / L,
Ammonium sulfate 10-40 g / L,
Sodium sulfate 20-50 g / L,
pH: 2.7 to 3.7,
Bath temperature: 30-50 ° C,
Current density: 5 to 50 A / dm 2 ,
And
次に、Ｚｎ、Ｃｏ、及びＭｏを含有する層をめっきにより形成する。
本発明において、Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層を得るためには、Ｃｏ組成割合を制御することが重要である。その場合のめっき条件は以下のとおりである。
すなわち、
めっき浴組成：
硫酸亜鉛１８０～２８０ｇ／Ｌ、
硫酸コバルト０～１００ｇ／Ｌ、
モリブデン酸アンモニウム０．０１～０．４ｇ／Ｌ、
硫酸アンモニウム１０～４０ｇ／Ｌ、
硫酸ナトリウム２０～５０ｇ／Ｌ、
ｐＨ：２．７～３．７、
浴温：３０～５０℃、
電流密度：５～５０Ａ／ｄｍ２、
とする。 <Plating containing Zn, Co, and Mo>
Next, a layer containing Zn, Co, and Mo is formed by plating.
In the present invention, in order to obtain a plating layer containing Zn, Co, and Mo, it is important to control the Co composition ratio. The plating conditions in that case are as follows.
That is,
Plating bath composition:
Zinc sulfate 180-280 g / L,
Cobalt sulfate 0-100g / L,
Ammonium molybdate 0.01-0.4 g / L,
Ammonium sulfate 10-40 g / L,
Sodium sulfate 20-50 g / L,
pH: 2.7 to 3.7,
Bath temperature: 30-50 ° C,
Current density: 5 to 50 A / dm 2 ,
And
上記めっき条件において形成されたＺｎ、Ｃｏ、及びＭｏを含有するめっき層中において、Ｚｎに対するＣｏの組成割合は、０．２～４．０ａｔ％（原子濃度、以下ａｔ％は原子濃度をいう）の範囲にすることが好ましい。
また、Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層の厚みは、２．０～８．０μｍとすることが好ましい。このようなめっき厚の調整は、前記めっき浴組成、ｐＨ、浴温、電流密度等を好適な範囲に調整することによって実現できる。
Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層の組成割合としては、
Ｃｏ：０．２～４．０ａｔ％、
Ｍｏ：０．００１～１ａｔ％、
残部Ｚｎとすることが好ましい。
Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層中のＣｏの組成割合が０．２ａｔ％未満の場合、気相部の十分な耐食性を得ることはできない。
また、Ｚｎ、Ｃｏ、及びＭｏを含有するめっきのＣｏの組成割合が４．０ａｔ％を超える場合、平板でのめっき層では耐食性は得られるが、皮膜の硬質化により、加工性が低下しパイプ加工時に割れが発生し、気相部の十分な耐食性を得ることはできない。
このようなめっき層中における組成割合の調整は、前記めっき浴組成、ｐＨ、浴温、電流密度等を好適な範囲に調整することによって実現できる。 In the plating layer containing Zn, Co, and Mo formed under the above plating conditions, the composition ratio of Co to Zn is 0.2 to 4.0 at% (atomic concentration, hereinafter “at%” means atomic concentration). It is preferable to be in the range.
In addition, the thickness of the plating layer containing Zn, Co, and Mo is preferably 2.0 to 8.0 μm. Such adjustment of the plating thickness can be realized by adjusting the plating bath composition, pH, bath temperature, current density, and the like within a suitable range.
As a composition ratio of the plating layer containing Zn, Co, and Mo,
Co: 0.2 to 4.0 at%,
Mo: 0.001 to 1 at%,
The balance is preferably Zn.
When the composition ratio of Co in the plating layer containing Zn, Co, and Mo is less than 0.2 at%, sufficient corrosion resistance of the gas phase portion cannot be obtained.
In addition, when the Co composition ratio of the plating containing Zn, Co, and Mo exceeds 4.0 at%, corrosion resistance is obtained with the plating layer on the flat plate, but the workability decreases due to the hardened film, and the pipe Cracking occurs during processing, and sufficient corrosion resistance of the gas phase portion cannot be obtained.
Such adjustment of the composition ratio in the plating layer can be realized by adjusting the plating bath composition, pH, bath temperature, current density, and the like within a suitable range.
また、Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層の厚みは、２．０～８．０μｍとすることが好ましい。このようなめっき厚の調整は、前記めっき浴組成、ｐＨ、浴温、電流密度等を好適な範囲に調整することによって実現できる。
Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層の組成割合としては、
Ｃｏ：０．２～４．０ａｔ％、
Ｍｏ：０．００１～１ａｔ％、
残部Ｚｎとすることが好ましい。
Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層中のＣｏの組成割合が０．２ａｔ％未満の場合、気相部の十分な耐食性を得ることはできない。
また、Ｚｎ、Ｃｏ、及びＭｏを含有するめっきのＣｏの組成割合が４．０ａｔ％を超える場合、平板でのめっき層では耐食性は得られるが、皮膜の硬質化により、加工性が低下しパイプ加工時に割れが発生し、気相部の十分な耐食性を得ることはできない。
このようなめっき層中における組成割合の調整は、前記めっき浴組成、ｐＨ、浴温、電流密度等を好適な範囲に調整することによって実現できる。 In the plating layer containing Zn, Co, and Mo formed under the above plating conditions, the composition ratio of Co to Zn is 0.2 to 4.0 at% (atomic concentration, hereinafter “at%” means atomic concentration). It is preferable to be in the range.
In addition, the thickness of the plating layer containing Zn, Co, and Mo is preferably 2.0 to 8.0 μm. Such adjustment of the plating thickness can be realized by adjusting the plating bath composition, pH, bath temperature, current density, and the like within a suitable range.
As a composition ratio of the plating layer containing Zn, Co, and Mo,
Co: 0.2 to 4.0 at%,
Mo: 0.001 to 1 at%,
The balance is preferably Zn.
When the composition ratio of Co in the plating layer containing Zn, Co, and Mo is less than 0.2 at%, sufficient corrosion resistance of the gas phase portion cannot be obtained.
In addition, when the Co composition ratio of the plating containing Zn, Co, and Mo exceeds 4.0 at%, corrosion resistance is obtained with the plating layer on the flat plate, but the workability decreases due to the hardened film, and the pipe Cracking occurs during processing, and sufficient corrosion resistance of the gas phase portion cannot be obtained.
Such adjustment of the composition ratio in the plating layer can be realized by adjusting the plating bath composition, pH, bath temperature, current density, and the like within a suitable range.
＜評価方法＞
種々のＣｏ組成割合にした、Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層を設けた鋼板から評価試験片を作製し、バイオエタノール混合ガソリンに浸漬させることにより耐食性を調査した。耐食性は発錆の有無で確認した。
バイオエタノール混合ガソリンを試験的に模した腐食液を使用した。
ＪＩＳ Ｋ２２０２に規定されているレギュラーガソリンに、ギ酸、酢酸を添加し、ＪＡＳＯ Ｍ３６１に規定されているバイオエタノールを１０質量％添加し、模擬的な劣化ガソリンを精製した。
更に腐食性を高めることを目的に、純水にギ酸、酢酸、塩素を添加した腐食水を作製し、劣化ガソリンに１０質量％添加して腐食液とした。
腐食液は、上層が劣化ガソリン、下層が腐食水の２層に分かれた状態となる。
この腐食液に各Ｃｏ組成割合のＺｎ、Ｃｏ、及びＭｏを含有するめっき層を設けた評価試験片が半分浸漬するように密閉容器中に配置し、４５℃の恒温槽にて経時した。
これにより、図２に示すように、評価試験片は、上部より、劣化ガソリンの燃料蒸気（気相）と接触した気相部１１、劣化ガソリン（液相）と接触した液相部１２，腐食水（水相）と接触した水相部１３に分離されて評価されることになる。
そして、評価試験片の気相部１１の腐食を調査することにより、評価試験片の燃料蒸気に対する耐食性を評価した。
多くの実験結果から、Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層のＣｏ組成割合を、０．２～４．０ａｔ％の範囲とした評価試験片の気相部での発錆が抑制されることが分かった。 <Evaluation method>
Evaluation test pieces were prepared from steel sheets provided with plating layers containing Zn, Co, and Mo, having various Co composition ratios, and corrosion resistance was investigated by immersing them in bioethanol mixed gasoline. Corrosion resistance was confirmed by the presence or absence of rusting.
A corrosive solution simulating bioethanol-mixed gasoline was used as a test.
Formic acid and acetic acid were added to regular gasoline specified in JIS K2202, and 10% by mass of bioethanol specified in JASO M361 was added to purify the simulated deteriorated gasoline.
Further, for the purpose of enhancing the corrosivity, corrosive water in which formic acid, acetic acid and chlorine were added to pure water was prepared, and 10% by mass was added to deteriorated gasoline to obtain a corrosive liquid.
The corrosive liquid is in a state where the upper layer is divided into degraded gasoline and the lower layer is divided into two layers of corrosive water.
The corrosive solution was placed in a sealed container so that an evaluation test piece provided with a plating layer containing Zn, Co, and Mo having the respective Co composition ratios was half-immersed, and was aged in a 45 ° C. constant temperature bath.
Accordingly, as shown in FIG. 2, the evaluation test pieces are, from the upper part, thegas phase portion 11 in contact with the fuel vapor (gas phase) of the deteriorated gasoline, the liquid phase portion 12 in contact with the deteriorated gasoline (liquid phase), and corrosion. It will be separated and evaluated in the water phase part 13 in contact with water (water phase).
And the corrosion resistance with respect to the fuel vapor | steam of an evaluation test piece was evaluated by investigating the corrosion of the gaseous-phase part 11 of an evaluation test piece.
From many experimental results, rusting at the gas phase part of the evaluation test piece in which the Co composition ratio of the plating layer containing Zn, Co, and Mo is in the range of 0.2 to 4.0 at% is suppressed. I understood that.
種々のＣｏ組成割合にした、Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層を設けた鋼板から評価試験片を作製し、バイオエタノール混合ガソリンに浸漬させることにより耐食性を調査した。耐食性は発錆の有無で確認した。
バイオエタノール混合ガソリンを試験的に模した腐食液を使用した。
ＪＩＳ Ｋ２２０２に規定されているレギュラーガソリンに、ギ酸、酢酸を添加し、ＪＡＳＯ Ｍ３６１に規定されているバイオエタノールを１０質量％添加し、模擬的な劣化ガソリンを精製した。
更に腐食性を高めることを目的に、純水にギ酸、酢酸、塩素を添加した腐食水を作製し、劣化ガソリンに１０質量％添加して腐食液とした。
腐食液は、上層が劣化ガソリン、下層が腐食水の２層に分かれた状態となる。
この腐食液に各Ｃｏ組成割合のＺｎ、Ｃｏ、及びＭｏを含有するめっき層を設けた評価試験片が半分浸漬するように密閉容器中に配置し、４５℃の恒温槽にて経時した。
これにより、図２に示すように、評価試験片は、上部より、劣化ガソリンの燃料蒸気（気相）と接触した気相部１１、劣化ガソリン（液相）と接触した液相部１２，腐食水（水相）と接触した水相部１３に分離されて評価されることになる。
そして、評価試験片の気相部１１の腐食を調査することにより、評価試験片の燃料蒸気に対する耐食性を評価した。
多くの実験結果から、Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層のＣｏ組成割合を、０．２～４．０ａｔ％の範囲とした評価試験片の気相部での発錆が抑制されることが分かった。 <Evaluation method>
Evaluation test pieces were prepared from steel sheets provided with plating layers containing Zn, Co, and Mo, having various Co composition ratios, and corrosion resistance was investigated by immersing them in bioethanol mixed gasoline. Corrosion resistance was confirmed by the presence or absence of rusting.
A corrosive solution simulating bioethanol-mixed gasoline was used as a test.
Formic acid and acetic acid were added to regular gasoline specified in JIS K2202, and 10% by mass of bioethanol specified in JASO M361 was added to purify the simulated deteriorated gasoline.
Further, for the purpose of enhancing the corrosivity, corrosive water in which formic acid, acetic acid and chlorine were added to pure water was prepared, and 10% by mass was added to deteriorated gasoline to obtain a corrosive liquid.
The corrosive liquid is in a state where the upper layer is divided into degraded gasoline and the lower layer is divided into two layers of corrosive water.
The corrosive solution was placed in a sealed container so that an evaluation test piece provided with a plating layer containing Zn, Co, and Mo having the respective Co composition ratios was half-immersed, and was aged in a 45 ° C. constant temperature bath.
Accordingly, as shown in FIG. 2, the evaluation test pieces are, from the upper part, the
And the corrosion resistance with respect to the fuel vapor | steam of an evaluation test piece was evaluated by investigating the corrosion of the gaseous-
From many experimental results, rusting at the gas phase part of the evaluation test piece in which the Co composition ratio of the plating layer containing Zn, Co, and Mo is in the range of 0.2 to 4.0 at% is suppressed. I understood that.
＜パイプ加工＞
上記Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層を形成しためっき鋼板を使用し、レベラーにより形状修正し、スリッターで所定の外寸径にスリットした後、成形機によりパイプ状に造管し、長手方向の端面同士を高周波誘導溶接によりシーム溶接することによりパイプを製造する。
パイプとしては、燃料をタンクに導入する給油パイプやタンクからエンジンに燃料を導入するパイプや、通気を行うパイプがある。
給油パイプ２０の燃料タンク２３への取り付けは、図３（ａ）に示すように、給油パイプ２０の燃料タンク２３への取り付けは、燃料タンク２３の上部から斜め上方向へ延出させた。
また、給油パイプ２０には、燃料が通過する太径パイプ部２１の途中から分岐をさせて、太径パイプ部２１の上部と下部とを通気する細径パイプ部２２を接続した。
太径パイプ部２１を本発明のめっき鋼板を用いて製造する。なお、細径パイプ部２２も本発明のめっき鋼板を用いて製造してもよい。
なお、本発明で規定する給油パイプ２０は、図３（ａ）に示すような形状に限らず、例えば、図３（ｂ）に示すように、燃料が通過する太径パイプ部２１とは、独立した形状で細径パイプ部２２が燃料タンク２３に取り付けられているものであっても、燃料蒸気に対する耐食性が特に要求されることに変わりはないので、これらの形態のものも含む。 <Pipe processing>
Using a plated steel sheet on which a plated layer containing Zn, Co, and Mo is formed, the shape is corrected by a leveler, slitted to a predetermined outer size with a slitter, and then formed into a pipe shape by a molding machine. Pipes are manufactured by seam welding end surfaces in the direction by high frequency induction welding.
As the pipe, there are an oil supply pipe for introducing fuel into the tank, a pipe for introducing fuel from the tank to the engine, and a pipe for venting.
Thefuel supply pipe 20 is attached to the fuel tank 23 as shown in FIG. 3A, and the fuel supply pipe 20 is attached to the fuel tank 23 from the upper part of the fuel tank 23 in an obliquely upward direction.
Further, a small-diameter pipe portion 22 that branches from the middle of the large-diameter pipe portion 21 through which the fuel passes and is connected to the upper and lower portions of the large-diameter pipe portion 21 is connected to the fuel supply pipe 20.
The largediameter pipe part 21 is manufactured using the plated steel sheet of the present invention. In addition, you may manufacture the small diameter pipe part 22 using the plated steel plate of this invention.
In addition, theoil supply pipe 20 prescribed | regulated by this invention is not restricted to a shape as shown to Fig.3 (a), For example, as shown in FIG.3 (b), with the large diameter pipe part 21 through which fuel passes, Even if the small-diameter pipe portion 22 is attached to the fuel tank 23 in an independent shape, the corrosion resistance against the fuel vapor is still particularly required, and thus those of these forms are also included.
上記Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層を形成しためっき鋼板を使用し、レベラーにより形状修正し、スリッターで所定の外寸径にスリットした後、成形機によりパイプ状に造管し、長手方向の端面同士を高周波誘導溶接によりシーム溶接することによりパイプを製造する。
パイプとしては、燃料をタンクに導入する給油パイプやタンクからエンジンに燃料を導入するパイプや、通気を行うパイプがある。
給油パイプ２０の燃料タンク２３への取り付けは、図３（ａ）に示すように、給油パイプ２０の燃料タンク２３への取り付けは、燃料タンク２３の上部から斜め上方向へ延出させた。
また、給油パイプ２０には、燃料が通過する太径パイプ部２１の途中から分岐をさせて、太径パイプ部２１の上部と下部とを通気する細径パイプ部２２を接続した。
太径パイプ部２１を本発明のめっき鋼板を用いて製造する。なお、細径パイプ部２２も本発明のめっき鋼板を用いて製造してもよい。
なお、本発明で規定する給油パイプ２０は、図３（ａ）に示すような形状に限らず、例えば、図３（ｂ）に示すように、燃料が通過する太径パイプ部２１とは、独立した形状で細径パイプ部２２が燃料タンク２３に取り付けられているものであっても、燃料蒸気に対する耐食性が特に要求されることに変わりはないので、これらの形態のものも含む。 <Pipe processing>
Using a plated steel sheet on which a plated layer containing Zn, Co, and Mo is formed, the shape is corrected by a leveler, slitted to a predetermined outer size with a slitter, and then formed into a pipe shape by a molding machine. Pipes are manufactured by seam welding end surfaces in the direction by high frequency induction welding.
As the pipe, there are an oil supply pipe for introducing fuel into the tank, a pipe for introducing fuel from the tank to the engine, and a pipe for venting.
The
Further, a small-
The large
In addition, the
以下に実施例を用いて、本発明を更に詳細に説明する。
＜実施例１＞
板厚０．７０ｍｍの、冷延、焼鈍済みの低炭素アルミキルド鋼板を原板とした。
めっき原板である鋼板の成分は以下のとおりである。
Ｃ：０．０４５質量％、Ｍｎ：０．２３質量％、Ｓｉ：０．０２質量％、Ｐ：０．０１２質量％、Ｓ：０．００９質量％、Ａｌ：０．０６３質量％、Ｎ：０．００３６質量％、残部：Ｆｅ及び不可避的不純物である。
この鋼板を、アルカリ電解脱脂、硫酸浸漬の酸洗を行った後、４．２μｍ厚のＺｎ、Ｃｏ、及びＭｏを含有するめっき層を設けためっき鋼板を得た。
形成されたＺｎ、Ｃｏ、及びＭｏを含有するめっき層の組成割合は、Ｚｎに対しＣｏの組成割合が０．２ａｔ％、Ｍｏの組成割合が０．０１ａｔ％であった。
なお、めっき層中の組成割合はリガク製蛍光X線装置（ＺＳＸ １００e）を使用し、ＥＺスキャンにより測定した。めっき厚の測定にも前記蛍光Ｘ線装置を用いた。 Hereinafter, the present invention will be described in more detail with reference to examples.
<Example 1>
A cold-rolled and annealed low carbon aluminum killed steel plate having a thickness of 0.70 mm was used as the original plate.
The components of the steel plate that is the plating original plate are as follows.
C: 0.045 mass%, Mn: 0.23 mass%, Si: 0.02 mass%, P: 0.012 mass%, S: 0.009 mass%, Al: 0.063 mass%, N: 0.0036% by mass, balance: Fe and inevitable impurities.
The steel sheet was subjected to alkaline electrolytic degreasing and pickling with sulfuric acid soaking, to obtain a plated steel sheet provided with a plating layer containing Zn, Co, and Mo having a thickness of 4.2 μm.
As for the composition ratio of the formed plating layer containing Zn, Co, and Mo, the composition ratio of Co was 0.2 at% and the composition ratio of Mo was 0.01 at% with respect to Zn.
The composition ratio in the plating layer was measured by EZ scan using a Rigaku fluorescent X-ray apparatus (ZSX 100e). The fluorescent X-ray apparatus was also used for measuring the plating thickness.
＜実施例１＞
板厚０．７０ｍｍの、冷延、焼鈍済みの低炭素アルミキルド鋼板を原板とした。
めっき原板である鋼板の成分は以下のとおりである。
Ｃ：０．０４５質量％、Ｍｎ：０．２３質量％、Ｓｉ：０．０２質量％、Ｐ：０．０１２質量％、Ｓ：０．００９質量％、Ａｌ：０．０６３質量％、Ｎ：０．００３６質量％、残部：Ｆｅ及び不可避的不純物である。
この鋼板を、アルカリ電解脱脂、硫酸浸漬の酸洗を行った後、４．２μｍ厚のＺｎ、Ｃｏ、及びＭｏを含有するめっき層を設けためっき鋼板を得た。
形成されたＺｎ、Ｃｏ、及びＭｏを含有するめっき層の組成割合は、Ｚｎに対しＣｏの組成割合が０．２ａｔ％、Ｍｏの組成割合が０．０１ａｔ％であった。
なお、めっき層中の組成割合はリガク製蛍光X線装置（ＺＳＸ １００e）を使用し、ＥＺスキャンにより測定した。めっき厚の測定にも前記蛍光Ｘ線装置を用いた。 Hereinafter, the present invention will be described in more detail with reference to examples.
<Example 1>
A cold-rolled and annealed low carbon aluminum killed steel plate having a thickness of 0.70 mm was used as the original plate.
The components of the steel plate that is the plating original plate are as follows.
C: 0.045 mass%, Mn: 0.23 mass%, Si: 0.02 mass%, P: 0.012 mass%, S: 0.009 mass%, Al: 0.063 mass%, N: 0.0036% by mass, balance: Fe and inevitable impurities.
The steel sheet was subjected to alkaline electrolytic degreasing and pickling with sulfuric acid soaking, to obtain a plated steel sheet provided with a plating layer containing Zn, Co, and Mo having a thickness of 4.2 μm.
As for the composition ratio of the formed plating layer containing Zn, Co, and Mo, the composition ratio of Co was 0.2 at% and the composition ratio of Mo was 0.01 at% with respect to Zn.
The composition ratio in the plating layer was measured by EZ scan using a Rigaku fluorescent X-ray apparatus (ZSX 100e). The fluorescent X-ray apparatus was also used for measuring the plating thickness.
＜実施例２～７、比較例１～６＞
Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層中のＣｏの組成割合を、表１に示す値に変更した以外は、実施例１と同様にして、実施例２～７、比較例１～６のめっき鋼板を得た。 <Examples 2 to 7, Comparative Examples 1 to 6>
Examples 2 to 7 and Comparative Examples 1 to 6 were the same as Example 1 except that the composition ratio of Co in the plating layer containing Zn, Co, and Mo was changed to the values shown in Table 1. A plated steel sheet was obtained.
Ｚｎ、Ｃｏ、及びＭｏを含有するめっき層中のＣｏの組成割合を、表１に示す値に変更した以外は、実施例１と同様にして、実施例２～７、比較例１～６のめっき鋼板を得た。 <Examples 2 to 7, Comparative Examples 1 to 6>
Examples 2 to 7 and Comparative Examples 1 to 6 were the same as Example 1 except that the composition ratio of Co in the plating layer containing Zn, Co, and Mo was changed to the values shown in Table 1. A plated steel sheet was obtained.
＜評価＞
実施例、比較例の各めっき鋼板から評価試験片を作製し、４５℃の恒温槽にて２０００時間経時させた後に、各Ｃｏ組成割合のＺｎ、Ｃｏ、及びＭｏを含有するめっき層を設けた評価試験片の外観を観察し、赤錆発生を調査した。
この結果を表１の「気相部の発錆発生結果」に示す。 <Evaluation>
An evaluation test piece was prepared from each plated steel sheet of Examples and Comparative Examples, and after aging for 2000 hours in a constant temperature bath at 45 ° C., a plating layer containing Zn, Co, and Mo of each Co composition ratio was provided. The appearance of the evaluation test piece was observed to investigate occurrence of red rust.
The results are shown in “Results of Rust Generation in Gas Phase” in Table 1.
実施例、比較例の各めっき鋼板から評価試験片を作製し、４５℃の恒温槽にて２０００時間経時させた後に、各Ｃｏ組成割合のＺｎ、Ｃｏ、及びＭｏを含有するめっき層を設けた評価試験片の外観を観察し、赤錆発生を調査した。
この結果を表１の「気相部の発錆発生結果」に示す。 <Evaluation>
An evaluation test piece was prepared from each plated steel sheet of Examples and Comparative Examples, and after aging for 2000 hours in a constant temperature bath at 45 ° C., a plating layer containing Zn, Co, and Mo of each Co composition ratio was provided. The appearance of the evaluation test piece was observed to investigate occurrence of red rust.
The results are shown in “Results of Rust Generation in Gas Phase” in Table 1.
本発明の実施例１～７のＺｎ、Ｃｏ、及びＭｏを含有するめっき層を設けためっき鋼板は、表１から明らかなように、赤錆の発生が無く、めっき外観も良好でありパイプ製造用めっき鋼板として優れていた。
一方、比較例１～４のめっき鋼板は、赤錆が発生し、耐食性が要求されるパイプ製造用めっき鋼板として実用性に乏しい。 As is apparent from Table 1, the plated steel sheets provided with the plating layers containing Zn, Co, and Mo of Examples 1 to 7 of the present invention have no red rust, have a good plating appearance, and are suitable for pipe production. It was excellent as a plated steel sheet.
On the other hand, the plated steel sheets of Comparative Examples 1 to 4 have red rust and are impractical as a plated steel sheet for pipe production that requires corrosion resistance.
一方、比較例１～４のめっき鋼板は、赤錆が発生し、耐食性が要求されるパイプ製造用めっき鋼板として実用性に乏しい。 As is apparent from Table 1, the plated steel sheets provided with the plating layers containing Zn, Co, and Mo of Examples 1 to 7 of the present invention have no red rust, have a good plating appearance, and are suitable for pipe production. It was excellent as a plated steel sheet.
On the other hand, the plated steel sheets of Comparative Examples 1 to 4 have red rust and are impractical as a plated steel sheet for pipe production that requires corrosion resistance.
本発明のパイプ製造用めっき鋼板は、燃料であるガソリン、軽油、バイオエタノール、又は、バイオディーゼル燃料などの燃料蒸気への暴露において発錆発生を抑え、燃料自体の劣化も抑えることが可能である。
また、本発明のパイプ製造用めっき鋼板を用いたパイプ及び給油パイプは、燃料蒸気に対する耐食性が優れており、産業上の利用可能性が極めて高い。 The plated steel sheet for manufacturing pipes of the present invention can suppress rust generation and exposure to fuel vapor such as gasoline, light oil, bioethanol, or biodiesel fuel, and can also suppress deterioration of the fuel itself. .
Moreover, the pipe using the plated steel plate for pipe manufacture of this invention and an oil supply pipe are excellent in corrosion resistance with respect to fuel vapor | steam, and its industrial applicability is very high.
また、本発明のパイプ製造用めっき鋼板を用いたパイプ及び給油パイプは、燃料蒸気に対する耐食性が優れており、産業上の利用可能性が極めて高い。 The plated steel sheet for manufacturing pipes of the present invention can suppress rust generation and exposure to fuel vapor such as gasoline, light oil, bioethanol, or biodiesel fuel, and can also suppress deterioration of the fuel itself. .
Moreover, the pipe using the plated steel plate for pipe manufacture of this invention and an oil supply pipe are excellent in corrosion resistance with respect to fuel vapor | steam, and its industrial applicability is very high.
１１：気相部
１２：液相部
１３：水相部
２０：給油パイプ
２１：太径パイプ部
２２：細径パイプ部
２３：燃料タンク 11: Gas phase part 12: Liquid phase part 13: Water phase part 20: Oil supply pipe 21: Large diameter pipe part 22: Small diameter pipe part 23: Fuel tank
１２：液相部
１３：水相部
２０：給油パイプ
２１：太径パイプ部
２２：細径パイプ部
２３：燃料タンク 11: Gas phase part 12: Liquid phase part 13: Water phase part 20: Oil supply pipe 21: Large diameter pipe part 22: Small diameter pipe part 23: Fuel tank
Claims (6)
- 鋼板の表面にＺｎ、Ｃｏ及びＭｏを含有するめっき層を有しており、前記めっき層中におけるＺｎに対するＣｏの組成割合が、０．２～４．０ａｔ％（原子濃度）とすることを特徴とする、燃料蒸気に対する耐食性を有するパイプ製造用めっき鋼板。 It has a plating layer containing Zn, Co and Mo on the surface of the steel sheet, and the composition ratio of Co to Zn in the plating layer is 0.2 to 4.0 at% (atomic concentration) A plated steel sheet for pipe production having corrosion resistance against fuel vapor.
- 前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする請求項１に記載の燃料蒸気に対する耐食性を有するパイプ製造用めっき鋼板。 The plated steel sheet for pipe production having corrosion resistance against fuel vapor according to claim 1, wherein the fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
- 鋼板からなるパイプの内面に、Ｚｎ、Ｃｏ及びＭｏを含有するめっき層を有していることを特徴とする、燃料蒸気に対する耐食性を有するパイプ。 A pipe having corrosion resistance against fuel vapor, characterized by having a plating layer containing Zn, Co and Mo on the inner surface of a pipe made of a steel plate.
- 前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする請求項３に記載の燃料蒸気に対する耐食性を有するパイプ。 The pipe having corrosion resistance against fuel vapor according to claim 3, wherein the fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
- 燃料を燃料タンクに給油するための給油パイプであって、
燃料が通過する太径パイプ部と、
太径パイプ部の上部と下部とを通気する細径パイプ部とを有し、
少なくとも前記太径パイプ部の内面に、
Ｚｎに対するＣｏの組成割合が、０．２～４．０ａｔ％（原子濃度）であるＺｎ、Ｃｏ及びＭｏを含有するめっき層を有していることを特徴とする燃料蒸気に対する耐食性を有する給油パイプ。 A refueling pipe for refueling a fuel tank,
A large-diameter pipe section through which fuel passes;
It has a small diameter pipe part that ventilates the upper part and the lower part of the large diameter pipe part,
At least on the inner surface of the large-diameter pipe part,
An oil supply pipe having corrosion resistance to fuel vapor, characterized by having a plating layer containing Zn, Co and Mo having a composition ratio of Co to Zn of 0.2 to 4.0 at% (atomic concentration) . - 前記燃料が、ガソリン、軽油、バイオエタノール、又はバイオディーゼル燃料を含むことを特徴とする請求項５に記載の燃料蒸気に対する耐食性を有する給油パイプ。 The fuel pipe according to claim 5, wherein the fuel includes gasoline, light oil, bioethanol, or biodiesel fuel.
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| JP2010-101116 | 2010-04-26 | ||
| JP2010101116A JP2011231358A (en) | 2010-04-26 | 2010-04-26 | Plated steel sheet for manufacturing pipe having corrosion resistance against fuel vapor, and pipe and oil supply pipe using the plated steel sheet |
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| US20180142335A1 (en) | 2015-06-22 | 2018-05-24 | Jfe Steel Corporation | Steel for storage equipment and transportation equipment for ethanol (as amended) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3791801A (en) * | 1971-07-23 | 1974-02-12 | Toyo Kohan Co Ltd | Electroplated steel sheet |
| JPS4919979B1 (en) * | 1970-12-15 | 1974-05-21 | ||
| JPS56174324U (en) * | 1980-05-27 | 1981-12-23 | ||
| JP2000313969A (en) * | 1999-04-27 | 2000-11-14 | Sumitomo Metal Ind Ltd | Steel sheet for fuel tank excellent in corrosion resistance and adhesion for finish coat of outer face |
| JP2006291279A (en) * | 2005-04-11 | 2006-10-26 | Toyo Kohan Co Ltd | Electrically conductive black plated steel sheet |
| JP2006291280A (en) * | 2005-04-11 | 2006-10-26 | Toyo Kohan Co Ltd | Heat radiating black steel sheet |
| JP2006336089A (en) * | 2005-06-03 | 2006-12-14 | Nippon Steel Corp | Highly corrosion resistant surface-treated steel, and coated steel |
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| JP2009298347A (en) * | 2008-06-16 | 2009-12-24 | Fts:Kk | Fuel vapor recovering device of fuel injection port |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4919979B1 (en) * | 1970-12-15 | 1974-05-21 | ||
| US3791801A (en) * | 1971-07-23 | 1974-02-12 | Toyo Kohan Co Ltd | Electroplated steel sheet |
| JPS56174324U (en) * | 1980-05-27 | 1981-12-23 | ||
| JP2000313969A (en) * | 1999-04-27 | 2000-11-14 | Sumitomo Metal Ind Ltd | Steel sheet for fuel tank excellent in corrosion resistance and adhesion for finish coat of outer face |
| JP2006291279A (en) * | 2005-04-11 | 2006-10-26 | Toyo Kohan Co Ltd | Electrically conductive black plated steel sheet |
| JP2006291280A (en) * | 2005-04-11 | 2006-10-26 | Toyo Kohan Co Ltd | Heat radiating black steel sheet |
| JP2006336089A (en) * | 2005-06-03 | 2006-12-14 | Nippon Steel Corp | Highly corrosion resistant surface-treated steel, and coated steel |
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