JP6302696B2 - Magnesium alloy surface treatment method - Google Patents
Magnesium alloy surface treatment method Download PDFInfo
- Publication number
- JP6302696B2 JP6302696B2 JP2014025174A JP2014025174A JP6302696B2 JP 6302696 B2 JP6302696 B2 JP 6302696B2 JP 2014025174 A JP2014025174 A JP 2014025174A JP 2014025174 A JP2014025174 A JP 2014025174A JP 6302696 B2 JP6302696 B2 JP 6302696B2
- Authority
- JP
- Japan
- Prior art keywords
- magnesium alloy
- surface treatment
- treatment method
- magnesium
- steam heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910000861 Mg alloy Inorganic materials 0.000 title claims description 131
- 238000004381 surface treatment Methods 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 47
- 238000005260 corrosion Methods 0.000 claims description 61
- 230000007797 corrosion Effects 0.000 claims description 61
- 238000010438 heat treatment Methods 0.000 claims description 56
- 238000003754 machining Methods 0.000 claims description 43
- 238000012545 processing Methods 0.000 claims description 35
- 239000002335 surface treatment layer Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 96
- 239000000956 alloy Substances 0.000 description 25
- 239000012085 test solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000862 absorption spectrum Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000000873 masking effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Description
本発明は、マグネシウム合金の表面処理方法に関する。 The present invention relates to a surface treatment how a magnesium alloy.
マグネシウム合金は、軽量で強度が大きいため、軽量化が望まれる自動車や携帯電子機器などの材料として利用拡大が期待されている。しかしながら、マグネシウムは、卑金属であるため、マグネシウムを主成分とするマグネシウム合金は、空気中に放置すると酸化されやすく、その表面が腐食し易いことが知られている。 Magnesium alloys are lightweight and have high strength, and therefore are expected to expand their use as materials for automobiles and portable electronic devices that are desired to be lightweight. However, since magnesium is a base metal, it is known that a magnesium alloy containing magnesium as a main component is easily oxidized when left in the air and its surface is easily corroded.
そこで、マグネシウム合金を部材として用いる場合には、めっき、陽極酸化や塗装などの表面処理をマグネシウム合金に施すことが必要となる。例えば、下記特許文献１には、マグネシウム又はマグネシウム合金製品を、リン酸水素二アンモニウムを含む処理液により表面処理する表面処理方法が開示されている。 Therefore, when using a magnesium alloy as a member, it is necessary to subject the magnesium alloy to a surface treatment such as plating, anodizing, or painting. For example, Patent Document 1 below discloses a surface treatment method for treating a magnesium or magnesium alloy product with a treatment liquid containing diammonium hydrogen phosphate.
しかしながら、上掲した特許文献１に記載の表面処理方法では、種々の薬品や大がかりな設備が必要となり、コストや作業の上で負担が大きいという課題があった。 However, in the surface treatment method described in Patent Document 1 listed above, various chemicals and large-scale equipment are required, and there is a problem that the burden is high in terms of cost and work.
本発明は、上記の課題を鑑みて成されたものであり、その目的は、環境負荷が少なく、簡便かつ安価に、マグネシウム合金の耐食性の向上を実現することができる表面処理方法を見出すことにある。 The present invention has been made in view of the above-mentioned problems, and its object is to find a surface treatment method that can realize an improvement in corrosion resistance of a magnesium alloy in a simple and inexpensive manner with a low environmental load. is there.
本発明に係るマグネシウム合金の表面処理方法は、マグネシウム合金に機械加工処理を施す工程と、前記機械加工処理が施された前記マグネシウム合金を水蒸気の雰囲気中で加熱処理する水蒸気加熱処理を施す工程と、を含み、前記機械加工処理は、前記マグネシウム合金の表面に均一な加工ひずみを与え、前記水蒸気加熱処理は、温度が１４０℃以上１６０℃以下、相対湿度が７５％以上１００％以下、圧力が０．１２０８ＭＰａ以上０．４８８３ＭＰａ以下の水蒸気の雰囲気中で行われ、前記水蒸気加熱処理により前記マグネシウム合金に形成される表面処理層は、２．２μｍ以上１９μｍ以下の膜厚であり、さらに、前記表面処理層には、マグネシウムとアルミニウムの複合水酸化物が生成されないことを特徴とするものである。 The surface treatment method of a magnesium alloy according to the present invention includes the steps of subjecting a step of performing machining process in the magnesium alloy, the steam heating treatment for heating the said magnesium alloy machining process has been performed in an atmosphere of water vapor The mechanical processing treatment imparts uniform processing strain to the surface of the magnesium alloy, and the steam heating treatment has a temperature of 140 ° C. to 160 ° C. , a relative humidity of 75% to 100%, and a pressure of The surface treatment layer formed in the magnesium alloy by the steam heat treatment is performed in an atmosphere of water vapor of 0.1208 MPa or more and 0.4883 MPa or less , and has a film thickness of 2.2 μm or more and 19 μm or less. The treatment layer is characterized in that a composite hydroxide of magnesium and aluminum is not generated .
また、本発明に係るマグネシウム合金の表面処理方法において、前記水蒸気加熱処理は、１時間以上２時間以下の時間で行われることとすることができる。 Moreover, in the surface treatment method of a magnesium alloy according to the present invention, the steam heat treatment can be performed in a period of 1 hour or more and 2 hours or less.
さらに、本発明に係るマグネシウム合金の表面処理方法では、前記表面処理層によってマグネシウム合金の耐食性を高めることとすることができる。 Et al is, the surface treatment method of a magnesium alloy according to the present invention, it may be to improve the corrosion resistance of magnesium alloy by pre-Symbol table surface treated layer.
さらにまた、本発明に係るマグネシウム合金の表面処理方法では、前記表面処理層によって前記マグネシウム合金への塗装や着色を容易にすることができる。 Furthermore, in the surface treatment method of a magnesium alloy according to the present invention, the surface treatment layer can facilitate the coating and coloring of the magnesium alloy.
さらに、本発明に係るマグネシウム合金の表面処理方法において、前記表面処理層は、水酸化マグネシウム層を含むこととすることができる。 Furthermore, in the magnesium alloy surface treatment method according to the present invention, the surface treatment layer may include a magnesium hydroxide layer.
さらに、本発明に係るマグネシウム合金の表面処理方法において、前記機械加工処理は、前記マグネシウム合金の表面に付着するマグネシウム合金以外の物質を除去するものであることとすることができる。 Furthermore, in the surface treatment method of a magnesium alloy according to the present invention, the machining treatment may be to remove substances other than the magnesium alloy attached to the surface of the magnesium alloy.
さらにまた、本発明に係るマグネシウム合金の表面処理方法において、前記機械加工処理は、ヘアライン加工処理、鏡面加工処理、又はサンドブラスト加工処理であることとすることができる。 Furthermore, in the magnesium alloy surface treatment method according to the present invention, the machining process may be a hairline process, a mirror surface process, or a sandblast process.
また、本発明に係るマグネシウム合金の表面処理方法において、前記マグネシウム合金は、０質量％〜１５質量％のアルミニウムを含むこととすることができる。 In the magnesium alloy surface treatment method according to the present invention, the magnesium alloy may contain 0% by mass to 15% by mass of aluminum.
本発明によれば、環境負荷が少なく、簡便かつ安価にマグネシウム合金の耐食性の向上を実現することができるマグネシウム合金の表面処理方法を提供することができる。 According to the present invention, it is possible environmental load is small, to provide a surface treatment how a magnesium alloy which can be realized simply and inexpensively improve the corrosion resistance of magnesium alloy.
以下、本発明を実施するための好適な実施形態について、図面を用いて説明する。なお、以下の実施形態は、各請求項に係る発明を限定するものではなく、また、実施形態の中で説明されている特徴の組み合わせの全てが発明の解決手段に必須であるとは限らない。 DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments for carrying out the invention will be described with reference to the drawings. The following embodiments do not limit the invention according to each claim, and all combinations of features described in the embodiments are not necessarily essential to the solution means of the invention. .
発明者らは、上述した課題の解決のために鋭意研究を行った結果、環境負荷が少なく、簡便かつ安価にマグネシウム合金の耐食性の向上を実現することができる表面処理方法を見出すことに成功した。そこで、以下に記す実施形態では、発明者らが見出した製造方法および製造条件と、かかる製造方法および製造条件によって製造されたマグネシウム合金材の特徴を示す分析結果および試験結果について説明することとする。 As a result of diligent research to solve the above-mentioned problems, the inventors have succeeded in finding a surface treatment method that can reduce the environmental load, and can easily and inexpensively improve the corrosion resistance of the magnesium alloy. . Therefore, in the embodiment described below, the manufacturing method and manufacturing conditions found by the inventors, and the analysis results and test results indicating the characteristics of the magnesium alloy material manufactured by the manufacturing method and manufacturing conditions will be described. .
発明者らは、マグネシウム合金に対して、マグネシウム合金を一定の温度、湿度および圧力の水蒸気の雰囲気中で加熱処理する水蒸気加熱処理を施すことで、耐食性を向上させることを実験の目的とした。この実験において採用された実験試料は、マグネシウム合金（権田金属工業株式会社製、ＡＺ６１）である。 The inventors set the objective of the experiment to improve the corrosion resistance of the magnesium alloy by subjecting the magnesium alloy to heat treatment in a steam atmosphere having a constant temperature, humidity and pressure. The experimental sample employed in this experiment is a magnesium alloy (AZ61 manufactured by Gonda Metal Industry Co., Ltd.).
図１に示すように、実験試料に対して、機械加工処理を施すこととすることができる（ステップＳ１０）。実験試料に機械加工を施すことによって、実験試料の表面に加工ひずみを与えることができるようになる。また、実験試料に機械加工を施すことによって、当該実験試料の表面に付着する、例えば、スケールや油脂等のマグネシウム合金以外の物質を除去することができるようになる。機械加工としては、例えば、ヘアライン加工処理、鏡面加工処理、サンドブラスト加工処理などを採用することができる。ここで、ヘアライン加工とは、単一方向に髪の毛ほどの細かい傷をつける加工のことをいう。鏡面加工とは、鏡のように平坦に仕上げる加工のことをいう。サンドブラスト加工とは、砂または細かい鉄粉などを圧縮空気とともに材表面に吹き付ける加工のことをいう。実験試料に対して機械加工処理を施すことにより、実験試料としてのマグネシウム合金の表面に加工ひずみを与えることができる。また、実験試料に対して機械加工処理を施すことにより、実験試料の表面に付着するスケールや油脂などといったマグネシウム合金以外の物質を除去することができる。 As shown in FIG. 1, the experimental sample can be subjected to machining processing (step S10). By subjecting the experimental sample to machining, a processing strain can be applied to the surface of the experimental sample. Further, by performing machining on the experimental sample, it becomes possible to remove substances other than magnesium alloys such as scales and fats and oils attached to the surface of the experimental sample. As the machining, for example, hairline processing, mirror surface processing, sandblast processing, or the like can be employed. Here, the hairline process refers to a process of making fine scratches on the hair in a single direction. Mirror surface processing refers to processing that finishes flat like a mirror. Sand blasting refers to a process in which sand or fine iron powder is sprayed onto the material surface together with compressed air. By subjecting the experimental sample to machining, a processing strain can be applied to the surface of the magnesium alloy as the experimental sample. Further, by subjecting the experimental sample to a machining process, substances other than the magnesium alloy such as scales and fats and oils attached to the surface of the experimental sample can be removed.
そして、図１に示すように、機械加工処理が施された実験試料又は機械加工処理が施されていない実験試料に対して、温度が１０５℃以上１６０℃以下、相対湿度が７５％以上１００％以下、圧力が０．１２０８ＭＰａ以上０．４８８３ＭＰａ以下の水蒸気の雰囲気中で加熱処理する水蒸気加熱処理を施すことにより（ステップＳ２０）、マグネシウム合金材を得ることとした。 As shown in FIG. 1, the temperature is 105 ° C. or higher and 160 ° C. or lower and the relative humidity is 75% or higher and 100% relative to the experimental sample that has been subjected to the machining process or the experimental sample that has not been subjected to the machining process. Hereinafter, the magnesium alloy material was obtained by performing a steam heat treatment in which the heat treatment was performed in an atmosphere of steam having a pressure of 0.1208 MPa to 0.4883 MPa (Step S20).
［第一の実施形態］
第一の実施形態に係るマグネシウム合金の表面処理方法では、圧延によって製造された上記の実験試料に、機械加工としてのヘアライン加工を施した後、この実験試料を５０ｍｍ×３０ｍｍ×１ｍｍの寸法に切断し、アセトンで超音波洗浄を行い、試験片とした。
[First embodiment]
In the magnesium alloy surface treatment method according to the first embodiment, the experimental sample manufactured by rolling is subjected to hairline processing as machining, and then the experimental sample is cut into dimensions of 50 mm × 30 mm × 1 mm. Then, ultrasonic cleaning was performed with acetone to obtain a test piece.
上記の試験片に対して、高度加速寿命試験装置（エスペック株式会社製、ＨＡＳＴチャンバー）を使用し、温度が１０５℃〜１６０℃、相対湿度が７５％〜１００％、圧力が０．１２０８ＭＰａ〜０．４８８３ＭＰａの水蒸気の雰囲気中で、設定温度に達してからの保持時間が１〜２時間の時間で加熱処理を行い、試験片の酸化処理を行い、マグネシウム合金材としての試験片を得た。表１は、各実施例の任意の加熱処理条件を示した表である。そして、図２および図３は、第一の実施形態に係る表面処理を施したマグネシウム合金材の外観を示す写真図であり、特に、図２は、実施例１〜８に係る試験片の外観を示しており、図３は、実施例９〜１４に係る試験片の外観を示している。なお、図２および図３に示された図は、図面の見やすさのために二図に分けたものであり、第一の実施形態に係る表面処理を施したマグネシウム合金材の外観を示す一連の写真図である。 For the above test piece, an advanced accelerated life test apparatus (manufactured by ESPEC CORP., HAST chamber) is used, the temperature is 105 ° C. to 160 ° C., the relative humidity is 75% to 100%, and the pressure is 0.1208 MPa to 0. In a 4883 MPa water vapor atmosphere, heat treatment was performed for 1 to 2 hours after the set temperature was reached, and the test piece was oxidized to obtain a test piece as a magnesium alloy material. Table 1 is a table showing arbitrary heat treatment conditions of each example. 2 and 3 are photographic views showing the appearance of the magnesium alloy material subjected to the surface treatment according to the first embodiment. In particular, FIG. 2 shows the appearance of the test pieces according to Examples 1 to 8. FIG. 3 shows the appearance of the test pieces according to Examples 9-14. 2 and FIG. 3 are divided into two diagrams for easy viewing of the drawings, and a series showing the appearance of the magnesium alloy material subjected to the surface treatment according to the first embodiment. FIG.
表１に示した条件で水蒸気加熱処理を施した試験片および水蒸気加熱処理を行っていない比較例１に係る試験片に対して、耐食性試験を行った。 A corrosion resistance test was performed on the test piece subjected to the steam heat treatment under the conditions shown in Table 1 and the test piece according to Comparative Example 1 where the steam heat treatment was not performed.
耐食性試験は、それぞれの試験片を１０ｍｍ×３０ｍｍ×１ｍｍの寸法に切断し、当該試験片の切り口をマスキングテープで保護し、マスキングテープで保護された試験片を５％塩化ナトリウム水溶液１０ｍｌの試験溶液に浸漬し、所定時間経過後、浸漬された試験片を試験溶液から取り出し、目視で観察することにより評価を行った。その結果を、表２に示す。表２において、「○」は、耐食性試験の結果、耐食性を有し腐食がほとんど生じなかったことを示し、「×」は、耐食性試験の結果、耐食性を有さず腐食が生じたことを示している。 In the corrosion resistance test, each test piece is cut into a size of 10 mm × 30 mm × 1 mm, the cut end of the test piece is protected with a masking tape, and the test piece protected with the masking tape is a test solution of 10 ml of 5% sodium chloride aqueous solution. Evaluation was performed by taking out the immersed test piece from the test solution and observing it visually after a predetermined time. The results are shown in Table 2. In Table 2, “◯” indicates that the corrosion resistance test results in corrosion resistance and almost no corrosion occurred, and “×” indicates that the corrosion resistance test result indicates that corrosion occurred without corrosion resistance. ing.
水蒸気加熱処理を施していない比較例１に係る試験片は、試験溶液に浸漬後、すぐに腐食反応が見られた。一方。水蒸気加熱処理を施した実施例１〜１４の試験片は、試験溶液に浸漬後、すぐには腐食が生じなかったが、実施例１、２、および４に係る試験片は、試験溶液に浸漬後１時間で腐食が生じた。また、実施例３および６に係る試験片は、試験溶液に浸漬後１２０時間で腐食が生じた。そして、実施例６と同じ１３０℃の温度条件で、相対湿度を変化させて相対湿度１００％で水蒸気加熱処理を行った実施例７は、試験溶液に浸漬して１２０時間後にも腐食は生じなかった。また、１４０℃、１５０℃、および１６０℃の温度条件で水蒸気加熱処理が施された試験片については、相対湿度や水蒸気加熱処理の処理時間にかかわらず、試験溶液に浸漬して１２０時間後も腐食は生じなかった。これらの結果から、試験片に水蒸気加熱処理を施すことにより、試験片の耐食性が向上することが確認できた。 The test piece according to Comparative Example 1 that had not been subjected to the steam heat treatment showed a corrosion reaction immediately after being immersed in the test solution. on the other hand. The test pieces of Examples 1 to 14 subjected to the steam heat treatment did not corrode immediately after being immersed in the test solution, but the test pieces according to Examples 1, 2, and 4 were immersed in the test solution. Corrosion occurred 1 hour later. Further, the test pieces according to Examples 3 and 6 were corroded 120 hours after being immersed in the test solution. In Example 7, in which the relative humidity was changed and the water vapor heat treatment was performed at 100% relative humidity under the same temperature condition of 130 ° C. as in Example 6, no corrosion occurred even after 120 hours of immersion in the test solution. It was. Moreover, about the test piece by which water vapor | steam heat processing was performed on the temperature conditions of 140 degreeC, 150 degreeC, and 160 degreeC, irrespective of relative humidity and the processing time of water vapor | steam heat processing, 120 hours after immersed in a test solution. Corrosion did not occur. From these results, it was confirmed that the corrosion resistance of the test piece was improved by subjecting the test piece to steam heat treatment.
以上より、マグネシウム合金に水蒸気加熱処理を施すことによって、マグネシウム合金材の耐食性を向上させることができることが分かった。そして、水蒸気加熱処理の温度条件は、特に限定されないが、１０５℃〜１６０℃の範囲では、高温側である１４０℃〜１６０℃の方が、耐食性はより良好となることが示唆された。また、水蒸気加熱処理の温度条件が一定の場合には、相対湿度の高い方が、耐食性はより良好となることが示唆された。 From the above, it was found that the corrosion resistance of the magnesium alloy material can be improved by subjecting the magnesium alloy to steam heat treatment. And although the temperature conditions of water vapor | steam heat processing are not specifically limited, In the range of 105 to 160 degreeC, it was suggested that the direction of 140 to 160 degreeC which is a high temperature side becomes better in corrosion resistance. Moreover, it was suggested that when the temperature condition of the steam heat treatment is constant, the higher the relative humidity, the better the corrosion resistance.
また、表１における実施例１、３、５、８、１０、および１３に係る試験片について、Ｘ線回折装置（株式会社リガク製、ＵｌｔｉｍａＩＶ）を用いて、当該試験片の表面構造のＸ線回折の測定を行った。その結果を、図４に示す。ここで、図４は、第一の実施形態に係る表面処理を施したマグネシウム合金材のＸ線回折結果を示す図である。 Moreover, about the test piece which concerns on Example 1, 3, 5, 8, 10, and 13 in Table 1, X-ray of the surface structure of the said test piece is used using an X-ray-diffraction apparatus (Rigaku Corporation make, Ultimate IV). Diffraction measurements were taken. The result is shown in FIG. Here, FIG. 4 is a diagram showing an X-ray diffraction result of the magnesium alloy material subjected to the surface treatment according to the first embodiment.
１０５℃、１２０℃および１３０℃の温度条件で水蒸気加熱処理を行った実施例１、３、および５に係る試験片は、水蒸気加熱処理を行っていない未処理の比較例１に係る試験片に比べて、試験片の色合いの変化が観察されたものの、Ｘ線回折パターンに、明確な差異は見られなかった。一方、１４０℃、１５０℃および１６０℃の温度条件で水蒸気加熱処理を行った実施例８、１０、および１３に係る試験片は、水蒸気加熱処理を行っていない未処理の比較例１に係る試験片に比べて、試験片の色合いの変化とともに、図４において示すように、２θ＝３３．１°、３８．３°、５１．２°、５９．２°、６２．６°、および７２．７°の位置に回折ピークが観察された。そして、これらの回折パターンから、マグネシウムに加えて水酸化マグネシウムが同定された。これらの結果から、試験片に水蒸気加熱処理を施すことにより、試験片の表面に水酸化マグネシウムが生成されたことを確認できた。また、水蒸気加熱処理の処理温度が高くなるほど、水酸化マグネシウムのピークが顕著に現れた。したがって、第一の実施形態に係る表面処理方法によってマグネシウム合金に形成される表面処理層は、水酸化マグネシウム層を含むことが分かった。また、当該水酸化マグネシウムの生成膜厚は、第一の実施形態に係る水蒸気加熱処理の処理温度が高くなるほど、大きくなっていると考えられる。 The test pieces according to Examples 1, 3, and 5 that were subjected to the steam heat treatment under the temperature conditions of 105 ° C., 120 ° C., and 130 ° C. were the untreated test pieces according to Comparative Example 1 that were not subjected to the steam heat treatment. In comparison, although a change in the hue of the test piece was observed, no clear difference was observed in the X-ray diffraction pattern. On the other hand, the test pieces according to Examples 8, 10 and 13 which were subjected to the steam heat treatment under the temperature conditions of 140 ° C., 150 ° C. and 160 ° C. were the tests according to the untreated Comparative Example 1 where the steam heat treatment was not performed. As shown in FIG. 4, 2θ = 33.1 °, 38.3 °, 51.2 °, 59.2 °, 62.6 °, and 72. A diffraction peak was observed at a position of 7 °. And from these diffraction patterns, magnesium hydroxide was identified in addition to magnesium. From these results, it was confirmed that magnesium hydroxide was generated on the surface of the test piece by subjecting the test piece to steam heat treatment. Moreover, the peak of magnesium hydroxide appeared more prominently as the treatment temperature of the steam heat treatment was higher. Therefore, it was found that the surface treatment layer formed on the magnesium alloy by the surface treatment method according to the first embodiment includes a magnesium hydroxide layer. Moreover, it is thought that the production | generation film thickness of the said magnesium hydroxide is so large that the processing temperature of the water vapor | steam heat processing which concerns on 1st embodiment becomes high.
なお、上記の試験片について、マグネシウムとアルミニウムの複合水酸化物の回折ピークである２θ＝１１．３°および２２．８°の位置には、回折ピークは観察されなかった。したがって、第一の実施形態に係る表面処理方法において、マグネシウム合金に形成される表面処理層には、マグネシウムとアルミニウムの複合水酸化物の生成は、確認されなかった。 In the above test piece, no diffraction peak was observed at the positions of 2θ = 11.3 ° and 22.8 °, which are diffraction peaks of the composite hydroxide of magnesium and aluminum. Therefore, in the surface treatment method according to the first embodiment, formation of a composite hydroxide of magnesium and aluminum was not confirmed in the surface treatment layer formed on the magnesium alloy.
表１における実施例１および実施例１３に係る試験片について、赤外分光光度計（日本分光株式会社製、ＦＴＩＲ６６０）を用いて、当該試験片の表面構造の赤外吸収スペクトルの測定を行った。その結果を、図５に示す。ここで、図５は、第一の実施形態に係る表面処理を施したマグネシウム合金材の赤外吸収スペクトルを示す図である。 About the test piece which concerns on Example 1 and Example 13 in Table 1, the infrared absorption spectrum of the surface structure of the said test piece was measured using the infrared spectrophotometer (The JASCO Corporation make, FTIR660). . The result is shown in FIG. Here, FIG. 5 is a diagram showing an infrared absorption spectrum of the magnesium alloy material subjected to the surface treatment according to the first embodiment.
赤外吸収スペクトルの測定の結果、実施例１および実施例１３の両方の赤外吸収スペクトルのパターンは、水酸化マグネシウムの赤外吸収スペクトルのパターンと一致しており、３７００ｃｍ−１付近に水酸基（−ＯＨ）の伸縮振動を示す赤外吸収スペクトルのピークが検出された。また、実施例３、５、８、および１０に係る試験片についても、同様に、赤外吸収スペクトルの測定を行ったところ、上記と同様の赤外吸収スペクトルの測定結果が得られた。これらの結果から、試験片に水蒸気加熱処理を施すことにより、試験片の表面に水酸化マグネシウムが生成されたことを確認できた。 Infrared absorption spectrum results of the measurement of the pattern of infrared absorption spectrum of both the Example 1 and Example 13, consistent with the pattern of infrared absorption spectrum of the magnesium hydroxide, hydroxyl groups at around 3700 cm -1 ( The peak of the infrared absorption spectrum showing the stretching vibration of -OH) was detected. In addition, the infrared absorption spectrum of the test pieces according to Examples 3, 5, 8, and 10 was measured in the same manner. As a result, the same measurement result of the infrared absorption spectrum as described above was obtained. From these results, it was confirmed that magnesium hydroxide was generated on the surface of the test piece by subjecting the test piece to steam heat treatment.
上述したように、１０５℃、１２０℃、および１３０℃の温度条件で水蒸気加熱処理を行った実施例１、３、および５に係る試験片について、Ｘ線回折の測定結果からは、水酸化マグネシウムの回折ピークを検出することができず、試験片の表面に水酸化マグネシウムの生成を確認することができなかった。一方、これらの試験片の赤外吸収スペクトルの測定結果から、上述したように、当該試験片の表面に水酸化マグネシウムが生成されたことを確認できた。 As described above, with respect to the test pieces according to Examples 1, 3, and 5 that were subjected to the steam heat treatment under the temperature conditions of 105 ° C., 120 ° C., and 130 ° C., from the measurement result of X-ray diffraction, magnesium hydroxide No diffraction peak could be detected, and formation of magnesium hydroxide could not be confirmed on the surface of the test piece. On the other hand, from the measurement result of the infrared absorption spectrum of these test pieces, it was confirmed that magnesium hydroxide was generated on the surface of the test piece as described above.
また、表１における実施例１、３、５、８、１０、および１３に係る試験片について、断面の組織構造の確認を行った。なお、この実験は、上記の試験片を樹脂に埋め込み、樹脂に埋め込まれた試験片を研磨によって鏡面仕上げすることで観察表面を形成し、その観察表面を顕微鏡でミクロ観察することで行われた。その結果を、図６に示す。ここで、図６は、第一の実施形態に係る表面処理を施したマグネシウム合金材のミクロ写真図である。 Moreover, about the test piece which concerns on Example 1, 3, 5, 8, 10, and 13 in Table 1, the structure structure of a cross section was confirmed. In addition, this experiment was performed by embedding the above-described test piece in a resin, forming an observation surface by polishing the test piece embedded in the resin by polishing, and micro-observing the observation surface with a microscope. . The result is shown in FIG. Here, FIG. 6 is a microphotograph of the magnesium alloy material subjected to the surface treatment according to the first embodiment.
１６０℃の温度条件で水蒸気加熱処理が行われた実施例１３に係る試験片では、１９μｍの表面処理層が確認され、１５０℃の温度条件で水蒸気加熱処理が行われた実施例１０に係る試験片では、８．３μｍの表面処理層が確認され、さらに、１４０℃の温度条件で水蒸気加熱処理が行われた実施例８の試験片では、２．２μｍの表面処理層が確認された。一方、１０５℃、１２０℃、および１３０℃の温度条件で水蒸気加熱処理が行われた実施例１、２、および５に係る試験片については、表面処理層が非常に薄く、測定をすることができなかった。これらの結果から、水蒸気加熱処理の温度条件の上昇に伴い、試験片の表面に生成される水酸化マグネシウムの表面処理層の増大が示唆され、上述したＸ線回折の測定結果とも対応していた。 In the test piece according to Example 13 in which the steam heat treatment was performed under a temperature condition of 160 ° C., a 19 μm surface treatment layer was confirmed, and the test according to Example 10 in which the steam heat treatment was performed under a temperature condition of 150 ° C. In the piece, a surface treatment layer of 8.3 μm was confirmed, and in the test piece of Example 8 in which the steam heat treatment was performed under the temperature condition of 140 ° C., a surface treatment layer of 2.2 μm was confirmed. On the other hand, for the test pieces according to Examples 1, 2, and 5 that were subjected to the steam heat treatment under the temperature conditions of 105 ° C., 120 ° C., and 130 ° C., the surface treatment layer was very thin, and measurement was possible. could not. From these results, it was suggested that the surface treatment layer of magnesium hydroxide generated on the surface of the test piece increased with an increase in the temperature condition of the steam heat treatment, which corresponded to the X-ray diffraction measurement results described above. .
したがって、機械加工処理としてのヘアライン加工を施されたマグネシウム合金に、水蒸気加熱処理を施すことにより、マグネシウム合金に表面処理層を形成することができ、このマグネシウム合金に形成された表面処理層によってマグネシウム合金の耐食性を向上させることができることが分かった。したがって、第一の実施形態に係る表面処理方法によれば、従来のように、リン酸水素二アンモニウムを含む処理液などの種々の薬品を用いる必要がないので環境負荷が少なく、マグネシウム合金を水蒸気の雰囲気中で加熱処理することにより表面処理が施されたマグネシウム合金材を得るので、簡便かつ安価にマグネシウム合金材の耐食性を向上させることができるようになる。なお、このマグネシウム合金に形成された表面処理層によって、マグネシウム合金への塗装や着色を容易にすることができるようになる。 Therefore, a surface treatment layer can be formed on the magnesium alloy by subjecting the magnesium alloy that has been subjected to hairline processing as a machining treatment to steam heating treatment, and the surface treatment layer formed on the magnesium alloy can form magnesium. It has been found that the corrosion resistance of the alloy can be improved. Therefore, according to the surface treatment method according to the first embodiment, it is not necessary to use various chemicals such as a treatment liquid containing diammonium hydrogen phosphate as in the prior art. Since the magnesium alloy material subjected to the surface treatment is obtained by performing the heat treatment in this atmosphere, the corrosion resistance of the magnesium alloy material can be improved easily and inexpensively. In addition, the surface treatment layer formed on the magnesium alloy can facilitate the coating and coloring of the magnesium alloy.
［第二の実施形態］
次に、圧延によって製造された以下の表３に示す３種のマグネシウム合金（権田金属工業株式会社製、ＡＺ６１）を実験試料として用いて、耐食性試験を行った。
[Second Embodiment]
Next, a corrosion resistance test was performed using three kinds of magnesium alloys (AZ61 manufactured by Gonda Metal Industry Co., Ltd.) manufactured by rolling as shown in Table 3 below as experimental samples.
表３における実験試料を５０ｍｍ×１０ｍｍ×１ｍｍの寸法に切断し、アセトンで超音波洗浄を行い、試験片とした。実施例１５〜１７に係る試験片に対して、オートクレーブ（日東高圧株式会社製）を用いて、温度が１４０℃、相対湿度が１００％、圧力が０．３６１４ＭＰａの水蒸気の雰囲気中で、設定温度に達してからの保持時間が１時間の時間で加熱処理をする水蒸気加熱処理を行った。そして、水蒸気加熱処理が施された実施例１５〜１７に係る試験片、および水蒸気加熱処理が施されていない比較例２〜４に係る試験片について、耐食性試験を行った。耐食性試験は、上述した場合と同様に、各試験片の切り口をマスキングテープで保護し、マスキングテープで保護された各試験片の約半分を５％塩化ナトリウム水溶液１０ｍｌの試験溶液に浸漬し、２４時間経過後、浸漬された試験片を試験溶液から取り出して、目視で観察を行った。図７は、第二の実施形態の比較例における耐食性試験後のマグネシウム合金の外観を示す写真図であり、水蒸気加熱処理を施していない比較例２〜４の耐食性試験後の外観を示す写真図である。図８は、第二の実施形態に係る表面処理を施したマグネシウム合金材の耐食性試験前後の外観を示す写真図であり、水蒸気加熱処理を施した実施例１５〜１７に係る試験片の耐食性試験前後の外観を示す写真図である。 The experimental sample in Table 3 was cut into a size of 50 mm × 10 mm × 1 mm and subjected to ultrasonic cleaning with acetone to obtain a test piece. For the test pieces according to Examples 15 to 17, using an autoclave (manufactured by Nitto High Pressure Co., Ltd.), in a steam atmosphere having a temperature of 140 ° C., a relative humidity of 100%, and a pressure of 0.3614 MPa, a set temperature. A steam heat treatment was performed in which the heat treatment was carried out for a time of 1 hour after reaching this value. And the corrosion resistance test was done about the test piece which concerns on Examples 15-17 in which the steam heat processing was performed, and the test piece which concerns on the comparative examples 2-4 in which the steam heat processing was not performed. In the corrosion resistance test, as in the case described above, the cut end of each test piece was protected with masking tape, and about half of each test piece protected with the masking tape was immersed in a test solution of 10 ml of 5% sodium chloride solution. After a lapse of time, the immersed test piece was taken out from the test solution and visually observed. FIG. 7 is a photographic diagram showing the appearance of the magnesium alloy after the corrosion resistance test in the comparative example of the second embodiment, and a photographic diagram showing the appearance after the corrosion resistance test of Comparative Examples 2 to 4 not subjected to the steam heat treatment. It is. FIG. 8 is a photographic view showing the appearance before and after the corrosion resistance test of the magnesium alloy material subjected to the surface treatment according to the second embodiment, and the corrosion resistance test of the test pieces according to Examples 15 to 17 subjected to the steam heat treatment. It is a photograph figure which shows the external appearance before and behind.
図７に示すように、機械加工処理および水蒸気加熱処理が施されていない比較例２および比較例３に係る試験片は、試験溶液に浸漬後、すぐに腐食反応が見られ、その後も継続的に腐食が進行した。機械加工処理が施され水蒸気加熱処理が施されていない比較例４に係る試験片は、試験溶液に浸漬したとき、腐食反応は極わずかで、試験溶液に浸漬して２４時間経過後の観察において、図７に示すような腐食が確認された。これらの結果から、マグネシウム合金に水蒸気加熱処理が施されない場合、機械加工処理が施されていないマグネシウム合金よりも機械加工処理が施されたマグネシウム合金の方が、耐食性が向上することが分かった。 As shown in FIG. 7, the test pieces according to Comparative Example 2 and Comparative Example 3 that were not subjected to the machining process and the steam heating process exhibited a corrosion reaction immediately after being immersed in the test solution, and continued thereafter. Corrosion progressed. When the test piece according to Comparative Example 4 which has been subjected to the machining process and not subjected to the steam heat treatment has a very slight corrosion reaction when immersed in the test solution, the specimen is immersed in the test solution and observed after 24 hours. Corrosion as shown in FIG. 7 was confirmed. From these results, it was found that when the magnesium alloy was not subjected to the steam heat treatment, the corrosion resistance of the magnesium alloy subjected to the machining treatment was improved compared to the magnesium alloy not subjected to the machining treatment.
一方、図８に示すように、水蒸気加熱処理が施された実施例１５〜１７に係る試験片は、機械加工処理の有無にかかわらず、試験溶液に浸漬して数時間後には腐食反応は見られなかった。そして、実施例１５〜１７に係る試験片は、試験溶液に浸漬して２４時間経過後に、図８に示すような点状の腐食が確認された。図８からわかるように、腐食の程度は、実施例１５と実施例１６とが同程度で、実施例１７は、２、３点の点状の腐食はあるものの最も耐食性が良好だった。これらの結果から、マグネシウム合金に水蒸気加熱処理が施される場合、機械加工処理が施されていないマグネシウム合金よりも機械加工処理が施されたマグネシウム合金の方が、耐食性が向上することが分かった。 On the other hand, as shown in FIG. 8, the test pieces according to Examples 15 to 17 subjected to the steam heat treatment were immersed in the test solution regardless of the presence or absence of the machining treatment, and no corrosion reaction was observed after several hours. I couldn't. And after the test piece which concerns on Examples 15-17 immersed in a test solution and 24 hours passed, the dotted | punctate corrosion as shown in FIG. 8 was confirmed. As can be seen from FIG. 8, the degree of corrosion was the same in Example 15 and Example 16, and Example 17 had the best corrosion resistance although there were a few point-like corrosions. From these results, it was found that when magnesium alloy was subjected to steam heat treatment, the corrosion resistance of the magnesium alloy that was subjected to the machining treatment was improved compared to the magnesium alloy that was not subjected to the machining treatment. .
比較例２〜４および実施例１５〜１７の耐食性試験の結果から、マグネシウム合金に水蒸気加熱処理を施すことにより、マグネシウム合金材の耐食性を向上させることができることが分かった。また、機械加工処理が施されていないマグネシウム合金よりも機械加工処理が施されたマグネシウム合金の方が、耐食性が向上することが分かった。さらに、マグネシウム合金に機械加工処理が施されるとともに水蒸気加熱処理が施されたマグネシウム合金材が最も耐食性が良好であることが分かった。 From the results of the corrosion resistance tests of Comparative Examples 2 to 4 and Examples 15 to 17, it was found that the corrosion resistance of the magnesium alloy material can be improved by subjecting the magnesium alloy to steam heating treatment. Moreover, it turned out that the corrosion resistance of the magnesium alloy by which the machining process was performed improves rather than the magnesium alloy by which the machining process was not performed. Furthermore, it has been found that a magnesium alloy material that has been subjected to a machining process and a steam heating process has the best corrosion resistance.
また、水蒸気加熱処理が施された実施例１５〜１７に係る試験片について、断面の組織構造の確認を行った。なお、この実験は、上述した場合と同様に、試験片を樹脂に埋め込み、樹脂に埋め込まれた試験片を研磨によって鏡面仕上げすることで観察表面を形成し、その観察表面を顕微鏡を用いてミクロ観察することで行われた。 Moreover, about the test piece which concerns on Examples 15-17 in which the steam heat processing was performed, the structure structure of a cross section was confirmed. In this experiment, as in the case described above, a test piece is embedded in a resin, and the test surface embedded in the resin is mirror-finished by polishing to form an observation surface. It was done by observing.
実施例１５および実施例１６に係る試験片は５μｍ程度、実施例１７に係る試験片は２μｍ程度の表面処理層が確認された。しかしながら、実施例１５および実施例１６に係る試験片に形成された表面処理層は、膜厚が不均一である様子が見られた。また、ヘアライン加工処理の有無以外の条件が同じである実施例１６および実施例１７のミクロ観察の結果から、試験片に機械加工処理を施すことにより、水蒸気加熱処理を施すことによって試験片に形成される表面処理層がより均一となることが分かった。なお、実施例１５および実施例１６のミクロ観察の結果から、焼鈍の有無により試験片に形成される表面処理層の変化はあまり見られないことが分かった。したがって、本発明に係る表面処理方法において、機械加工処理としてのヘアライン加工が施されたマグネシウム合金の方が、機械加工処理を施されていないマグネシウム合金よりも、マグネシウム合金に形成される表面処理層が均一となることが分かった。なお、マグネシウム合金に対して機械加工処理を施すことにより、マグネシウム合金の表面に均一な加工ひずみを与えることができるため、機械加工処理が施されたマグネシウム合金に水蒸気加熱処理を施すと、マグネシウム合金に形成される表面処理層が均一になると考えられる。 A surface treatment layer of about 5 μm was confirmed for the test pieces according to Example 15 and Example 16, and about 2 μm was confirmed for the test piece according to Example 17. However, the surface treatment layer formed on the test pieces according to Example 15 and Example 16 was found to have a non-uniform film thickness. In addition, from the results of micro observation of Example 16 and Example 17 where the conditions other than the presence or absence of hairline processing are the same, the test piece is formed by subjecting it to a steaming heat treatment by subjecting it to a machining process. It has been found that the surface treatment layer is more uniform. From the results of micro observations of Example 15 and Example 16, it was found that the change in the surface treatment layer formed on the test piece was hardly observed depending on the presence or absence of annealing. Therefore, in the surface treatment method according to the present invention, the magnesium alloy that has been subjected to hairline machining as a machining process is formed on the magnesium alloy rather than the magnesium alloy that has not been machined. Was found to be uniform. In addition, since it is possible to give a uniform processing strain to the surface of the magnesium alloy by performing a machining process on the magnesium alloy, when the magnesium alloy subjected to the machining process is subjected to a steam heat treatment, the magnesium alloy It is considered that the surface treatment layer formed on the surface becomes uniform.
耐食性試験およびミクロ試験の結果より、マグネシウム合金に形成される表面処理層が均一である方が、マグネシウム合金材の耐食性が向上することが分かった。そして、マグネシウム合金に形成される表面処理層を均一にするためには、マグネシウム合金に機械加工処理を施すことが有意であることが分かった。 From the results of the corrosion resistance test and the micro test, it was found that the uniformity of the surface treatment layer formed on the magnesium alloy improves the corrosion resistance of the magnesium alloy material. And in order to make the surface treatment layer formed in a magnesium alloy uniform, it turned out that it is significant to perform a machining process to a magnesium alloy.
［第三の実施形態］
次に、圧延によって製造されたマグネシウム合金（権田金属工業株式会社製、ＡＺ６１）を実験試料として用いて、上述した場合と同様に、それぞれの実験試料を５０ｍｍ×１０ｍｍ×１ｍｍの寸法に切断し、アセトンで超音波洗浄を行い、試験片とした。実施例１８〜２０に係る試験片に対して表４に示す機械加工処理を施した後、オートクレーブ（日東高圧株式会社製）を用いて、温度が１４０℃、相対湿度が１００％、圧力が０．３６１４ＭＰａの水蒸気の雰囲気中で、設定温度に達してからの保持時間が１時間の時間で加熱処理する水蒸気加熱処理を施した。そして、当該試験片について、機械加工処理および水蒸気加熱処理を施していない比較例５とともに、耐食性試験を行った。
[Third embodiment]
Next, using the magnesium alloy produced by rolling (manufactured by Gonda Metal Industry Co., Ltd., AZ61) as an experimental sample, each experimental sample was cut into dimensions of 50 mm × 10 mm × 1 mm, as described above, Ultrasonic cleaning was performed with acetone to obtain a test piece. After subjecting the test pieces according to Examples 18 to 20 to the machining process shown in Table 4, using an autoclave (manufactured by Nitto High Pressure Co., Ltd.), the temperature was 140 ° C., the relative humidity was 100%, and the pressure was 0. In an atmosphere of steam of 3614 MPa, steam heat treatment was performed in which heat treatment was performed for 1 hour after the set temperature was reached. And about the said test piece, the corrosion resistance test was done with the comparative example 5 which has not performed the machining process and the steam heat processing.
耐食性試験は、それぞれの試験片を１８ｍｍ×１０ｍｍ×１ｍｍの寸法に切断し、当該試験片の切り口をマスキングテープで保護し、マスキングテープで保護された試験片を５％塩化ナトリウム水溶液１０ｍｌの試験溶液に浸漬し、４８時間経過後、浸漬された試験片を試験溶液から取り出して、目視で観察を行った。その結果を、図９に示す。ここで、図９は、第三の実施形態に係る表面処理を施したマグネシウム合金の耐食性試験前後の外観を示す写真図である。 In the corrosion resistance test, each test piece is cut into a size of 18 mm × 10 mm × 1 mm, the cut end of the test piece is protected with a masking tape, and the test piece protected with the masking tape is a test solution of 10 ml of 5% sodium chloride aqueous solution. After 48 hours, the immersed test piece was taken out of the test solution and visually observed. The result is shown in FIG. Here, FIG. 9 is a photograph showing external appearances of the magnesium alloy subjected to the surface treatment according to the third embodiment before and after the corrosion resistance test.
耐食性試験の結果、図９からわかるように、機械加工処理および水蒸気加熱処理を施していない比較例５よりも、機械加工処理および水蒸気加熱処理を施した実施例１８〜２０の方が、耐食性が良好になることが確認できた。上述したように、マグネシウム合金に対して機械加工処理を施すことにより、マグネシウム合金の表面に均一な加工ひずみを与えることができるため、機械加工処理が施されたマグネシウム合金に水蒸気加熱処理を施すと、マグネシウム合金に形成される表面処理層は均一となると考えられる。そして、マグネシウム合金に形成される表面処理層が均一であるため、機械加工処理が施された後に水蒸気加熱処理が施されたマグネシウム合金は、耐食性が向上すると考えられる。 As a result of the corrosion resistance test, as can be seen from FIG. 9, Examples 18 to 20 subjected to the machining treatment and the steam heating treatment are more resistant to corrosion than Comparative Example 5 where the machining treatment and the steam heating treatment are not performed. It was confirmed that the condition was improved. As described above, by applying a machining process to the magnesium alloy, it is possible to give a uniform processing strain to the surface of the magnesium alloy. The surface treatment layer formed on the magnesium alloy is considered to be uniform. And since the surface treatment layer formed in a magnesium alloy is uniform, it is thought that the corrosion resistance improves the magnesium alloy by which the water vapor | steam heat processing was performed after performing a machining process.
以上、本発明の好適な実施形態について説明したが、本発明の技術的範囲は上記各実施形態に記載の範囲には限定されない。 As mentioned above, although preferred embodiment of this invention was described, the technical scope of this invention is not limited to the range as described in said each embodiment.
例えば、上記の各実施形態に係る表面処理方法では、マグネシウム合金として板状のマグネシウム合金を用いたが、これに限定されることはなく、種々の形状を有するマグネシウム合金に対して本発明に係る表面処理方法を用いることができる。 For example, in the surface treatment method according to each of the above embodiments, a plate-like magnesium alloy is used as the magnesium alloy, but the present invention is not limited to this, and the present invention is applied to magnesium alloys having various shapes. A surface treatment method can be used.
また例えば、上記の各実施形態に係る表面処理方法では、機械加工処理として、ヘアライン加工、鏡面加工、およびサンドブラスト加工を用いたが、これらに限定されず、マグネシウム合金の表面に均一な加工ひずみを与えることができるものであれば良く、また、特に限定されないが、マグネシウム合金の表面に付着するマグネシウム合金以外の物質を除去するものであることが好ましい。 Further, for example, in the surface treatment method according to each of the above embodiments, hairline processing, mirror surface processing, and sandblasting processing are used as the machining processing, but the present invention is not limited thereto, and uniform processing strain is applied to the surface of the magnesium alloy. Any material can be used as long as it can be applied, and although not particularly limited, it is preferable to remove substances other than the magnesium alloy that adhere to the surface of the magnesium alloy.
さらに、本発明に係る表面処理方法における水蒸気を構成する水は、特に限定されず、純水、イオン交換水、蒸留水などの不純物の少ない水の他に、水道水、工業用水などの水も用いることができる。 Furthermore, the water constituting the water vapor in the surface treatment method according to the present invention is not particularly limited, and water such as tap water and industrial water is also available in addition to water with few impurities such as pure water, ion exchange water, and distilled water. Can be used.
また、本発明に係る表面処理方法に含まれる水蒸気加熱処理の処理時間は、特に限定されるものではなく、所望のマグネシウム合金材の耐食性等に応じて、適宜選択することができる。 Moreover, the treatment time of the steam heat treatment included in the surface treatment method according to the present invention is not particularly limited, and can be appropriately selected according to the corrosion resistance of the desired magnesium alloy material.
さらに、本発明に係る表面処理方法で形成されるマグネシウム合金の表面処理層の膜厚は、２．２μｍ以上１９μｍ以下に限定されず、所望の耐食性を有するマグネシウム合金材が得られれば良く、例えば、１μｍ以上３０μｍ以下であっても良い。 Furthermore, the film thickness of the surface treatment layer of the magnesium alloy formed by the surface treatment method according to the present invention is not limited to 2.2 μm or more and 19 μm or less, as long as a magnesium alloy material having desired corrosion resistance is obtained. It may be 1 μm or more and 30 μm or less.
また、本発明に係る表面処理方法に用いられるマグネシウム合金は、０質量％〜１５質量％のアルミニウムを含有することが好ましいが、これに限定されることはなく、所望のマグネシウム合金材の耐食性等に応じて、適宜変更することができる。アルミニウムを過剰添加したマグネシウム合金よりも、上記の範囲でアルミニウムを含有するマグネシウム合金の方が、耐食性が良いためである。 Further, the magnesium alloy used in the surface treatment method according to the present invention preferably contains 0% by mass to 15% by mass of aluminum, but is not limited thereto, and the corrosion resistance of a desired magnesium alloy material, etc. Depending on the situation, it can be changed appropriately. This is because the magnesium alloy containing aluminum in the above range has better corrosion resistance than the magnesium alloy with excessive addition of aluminum.
なお、上記各実施形態には、多様な変更又は改良を加えることが可能である。その様な変更又は改良を加えた形態も本発明の技術的範囲に含まれ得ることが、特許請求の範囲の記載から明らかである。 Various modifications or improvements can be added to the above embodiments. It is apparent from the description of the scope of claims that embodiments with such changes or improvements can be included in the technical scope of the present invention.
Ｓ１０ 機械加工処理、Ｓ２０ 水蒸気加熱処理。 S10 machining process, S20 steam heating process.
Claims (8)
前記機械加工処理が施された前記マグネシウム合金を水蒸気の雰囲気中で加熱処理する水蒸気加熱処理を施す工程と、
を含み、
前記機械加工処理は、
前記マグネシウム合金の表面に均一な加工ひずみを与え、
前記水蒸気加熱処理は、
温度が１４０℃以上１６０℃以下、相対湿度が７５％以上１００％以下、圧力が０．１２０８ＭＰａ以上０．４８８３ＭＰａ以下の水蒸気の雰囲気中で行われ、
前記水蒸気加熱処理により前記マグネシウム合金に形成される表面処理層は、２．２μｍ以上１９μｍ以下の膜厚であり、さらに、
前記表面処理層には、マグネシウムとアルミニウムの複合水酸化物が生成されないことを特徴とするマグネシウム合金の表面処理方法。 A process of machining the magnesium alloy ;
A step of performing a steam heat treatment for heat-treating the magnesium alloy that has undergone the machining treatment in an atmosphere of steam ;
Including
The machining process is
Giving uniform processing strain to the surface of the magnesium alloy,
The steam heat treatment is
The temperature is 140 ° C. or more and 160 ° C. or less , the relative humidity is 75% or more and 100% or less, and the pressure is 0.1208 MPa or more and 0.4883 MPa or less in an atmosphere of water vapor ,
The surface treatment layer formed on the magnesium alloy by the steam heat treatment has a film thickness of 2.2 μm or more and 19 μm or less,
A magnesium alloy surface treatment method characterized in that a composite hydroxide of magnesium and aluminum is not produced in the surface treatment layer .
前記水蒸気加熱処理は、
設定温度に達してからの保持時間が、１時間以上２時間以下の時間で行われることを特徴とするマグネシウム合金の表面処理方法。 In the magnesium alloy surface treatment method according to claim 1 ,
The steam heat treatment is
A magnesium alloy surface treatment method, wherein the holding time after reaching the set temperature is 1 hour to 2 hours.
前記表面処理層によってマグネシウム合金の耐食性を高めることを特徴とするマグネシウム合金の表面処理方法。 In the surface treatment method of the magnesium alloy according to claim 1 or 2 ,
The surface treatment method of a magnesium alloy, characterized in that to increase the corrosion resistance of magnesium alloy by pre-Symbol table surface treated layer.
前記表面処理層によって前記マグネシウム合金への塗装や着色を容易にすることができることを特徴とするマグネシウム合金の表面処理方法。 In the surface treatment method of the magnesium alloy of any one of Claims 1-3 ,
A magnesium alloy surface treatment method characterized in that the surface treatment layer can facilitate coating and coloring of the magnesium alloy.
前記表面処理層は、水酸化マグネシウム層を含むことを特徴とするマグネシウム合金の表面処理方法。 In the surface treatment method of the magnesium alloy according to any one of claims 1 to 4 ,
The magnesium alloy surface treatment method, wherein the surface treatment layer includes a magnesium hydroxide layer.
前記機械加工処理は、前記マグネシウム合金の表面に付着するマグネシウム合金以外の物質を除去するものであることを特徴とするマグネシウム合金の表面処理方法。 In the surface treatment method of the magnesium alloy according to any one of claims 1 to 5 ,
The surface treatment method for a magnesium alloy, wherein the machining treatment is to remove substances other than the magnesium alloy adhering to the surface of the magnesium alloy.
前記機械加工処理は、
ヘアライン加工処理、鏡面加工処理、又はサンドブラスト加工処理であることを特徴とするマグネシウム合金の表面処理方法。 In the surface treatment method of the magnesium alloy according to any one of claims 1 to 6 ,
The machining process is
A surface treatment method for a magnesium alloy, characterized by being hairline processing, mirror surface processing, or sandblast processing.
前記マグネシウム合金は、０質量％〜１５質量％のアルミニウムを含むことを特徴とするマグネシウム合金の表面処理方法。 In the surface treatment method of the magnesium alloy according to any one of claims 1 to 7 ,
The magnesium alloy contains 0% by mass to 15% by mass of aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014025174A JP6302696B2 (en) | 2014-02-13 | 2014-02-13 | Magnesium alloy surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014025174A JP6302696B2 (en) | 2014-02-13 | 2014-02-13 | Magnesium alloy surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015151565A JP2015151565A (en) | 2015-08-24 |
| JP6302696B2 true JP6302696B2 (en) | 2018-03-28 |
Family
ID=53894164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014025174A Active JP6302696B2 (en) | 2014-02-13 | 2014-02-13 | Magnesium alloy surface treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6302696B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6407453B2 (en) * | 2015-12-25 | 2018-10-17 | 日本パーカライジング株式会社 | Surface modifier, coated magnesium material or magnesium alloy material, and method for producing the same |
| JP6872987B2 (en) * | 2017-06-22 | 2021-05-19 | 日本パーカライジング株式会社 | Magnesium-containing metal material with film |
| JP7148992B2 (en) * | 2017-10-02 | 2022-10-06 | 学校法人 芝浦工業大学 | Highly corrosion-resistant magnesium alloy material and its manufacturing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005054238A (en) * | 2003-08-05 | 2005-03-03 | Araco Corp | Method for surface treatment of magnesium material or magnesium alloy material |
| JP5056267B2 (en) * | 2007-08-24 | 2012-10-24 | 日立金属株式会社 | Rare earth permanent magnet having Al coating containing Mg on its surface and method for producing the same |
| JP5142275B2 (en) * | 2008-06-27 | 2013-02-13 | 独立行政法人産業技術総合研究所 | Magnesium alloy material and surface treatment method of magnesium alloy |
| JP5602573B2 (en) * | 2010-10-07 | 2014-10-08 | 独立行政法人産業技術総合研究所 | Magnesium alloy surface treatment method |
-
2014
- 2014-02-13 JP JP2014025174A patent/JP6302696B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015151565A (en) | 2015-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Amanov et al. | Fretting wear and friction reduction of CP titanium and Ti–6Al–4V alloy by ultrasonic nanocrystalline surface modification | |
| JP6302696B2 (en) | Magnesium alloy surface treatment method | |
| JP5602573B2 (en) | Magnesium alloy surface treatment method | |
| Khedir et al. | Robust superamphiphobic nanoscale copper sheet surfaces produced by a simple and environmentally friendly technique | |
| Sharma et al. | Influence of γ-alumina coating on surface properties of direct metal laser sintered 316L stainless steel | |
| WO2015082993A1 (en) | Method of producing hot-stamped article | |
| Forooshani et al. | Superhydrophobic copper surfaces by shot peening and chemical treatment | |
| Mohammed et al. | Reduction the corrosion rate of 304 stainless steel using pulsed laser shock penning method | |
| Jeong et al. | Identification of the intermetallic compound layer formed at the interface of roll-bonded aluminum-clad steel by thermal annealing | |
| RU2621088C1 (en) | Method for producing coating on steel plate | |
| Ruktuev et al. | Structure and corrosion resistance of Ti-Ta-Nb coatings obtained by electron beam cladding in the air-atmosphere | |
| CN111471954A (en) | In-situ synthesis coherent Ti on surfaces of pure titanium and titanium alloy2N film method | |
| Qi et al. | Evolution of the mechanical and tribological properties of DLC thin films doped with low-concentration hafnium on 316L steel | |
| Fedirko et al. | Increasing the serviceability of products from single-phase titanium alloys by thermochemical treatment | |
| Hammood et al. | Corrosion behavior evaluation in simulated body fluid of a modified Ti–6Al–4V alloy by DC glow plasma nitriding | |
| Stamenković et al. | The influence of the ageing temperature on different properties of the EN AW-7075 aluminium alloy | |
| Arkhipov et al. | Gas-dynamic coatings | |
| Cirstea et al. | Phase relation in the NiTiCu shape memory materials used in medicine applications | |
| Darsono et al. | The effect of case hardening treatment on aluminum 7075 toward its hardness and tensile strength | |
| Takeda et al. | Enhancement of bending fatigue life in TiNi shape-memory alloy tape by nitrogen ion implantation | |
| Patel et al. | An investigation of diverse surface finishes on fatigue properties of superelastic Nitinol wire | |
| Gul et al. | The effect of low temperature plasma nitriding on wear resistance of Ti6Al4V Alloy | |
| RU2635989C2 (en) | Method for producing titanium alloy blank for gas turbine engine parts | |
| Volkova et al. | The Structure and Main Characteristics of Diamond-Bearing Ni–P Coatings | |
| Bobzin et al. | Development and qualification of a MSIP PVD iridium coating for precision glass moulding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161102 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170814 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170822 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171016 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180227 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180305 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6302696 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |