JP3217768B2 - Aluminum alloy material for zinc phosphate treatment - Google Patents
Aluminum alloy material for zinc phosphate treatmentInfo
- Publication number
- JP3217768B2 JP3217768B2 JP19346799A JP19346799A JP3217768B2 JP 3217768 B2 JP3217768 B2 JP 3217768B2 JP 19346799 A JP19346799 A JP 19346799A JP 19346799 A JP19346799 A JP 19346799A JP 3217768 B2 JP3217768 B2 JP 3217768B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- hydrated oxide
- alloy material
- zinc phosphate
- phosphate treatment
- 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.)
- Expired - Fee Related
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リン酸亜鉛処理に
おけるアルミニウムの溶出を防止したAl合金材に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Al alloy material in which aluminum is prevented from being eluted during zinc phosphate treatment.
【０００２】[0002]
【従来の技術】近年、排気ガス等による地球環境問題に
対し、車両、船舶、航空機、自動二輪あるいは自動車な
どの輸送機車体の軽量化による燃費の向上が追求されて
いる。このため、輸送機車体の構造材やパネル、フレー
ム材などへのアルミニウム合金材 (以下、アルミニウム
を単にAlと言う) の使用も増加しつつある。2. Description of the Related Art In recent years, with respect to global environmental problems due to exhaust gas and the like, improvement in fuel efficiency by reducing the weight of transport vehicles such as vehicles, ships, aircraft, motorcycles, and automobiles has been pursued. For this reason, the use of aluminum alloy materials (hereinafter, aluminum is simply referred to as Al) for structural materials, panels, frame materials, and the like of transport vehicle bodies is also increasing.
【０００３】Al合金は、鋼に比してその比重が1/3 であ
ること、優れたエネルギー吸収性を有すること、更には
断面形状の自由度が高いという特性を有する。したがっ
て、車体重量を増加させずに、安全基準への対応や車体
性能を向上させることが可能となる。[0003] An Al alloy has the characteristics that its specific gravity is one-third that of steel, that it has excellent energy absorption, and that it has a high degree of freedom in its cross-sectional shape. Therefore, it is possible to comply with safety standards and improve vehicle performance without increasing the vehicle weight.
【０００４】このため、自動車のドア補強用部材として
のドアビームやサイドメンバー、バンパーやバンパース
テイなどの車体補強部材 (車体保護部材) 等に、Al-Mg-
Si系のAA 6000 系Al合金や、Al-Zn-Mg系のAA 7000 系Al
合金などの押出形材が使用されている。For this reason, Al-Mg-based materials are used for door beams and side members as vehicle door reinforcing members, body reinforcing members (vehicle protection members) such as bumpers and bumper stays, and the like.
Si-based AA 6000 series Al alloy, Al-Zn-Mg-based AA 7000 series Al
Extruded shapes such as alloys are used.
【０００５】また、自動二輪や自動車のホイールやナッ
クル、ロアアーム、アッパーアーム等のサスペンション
部品などの、複雑な形状や厚肉部を有する構造材には、
安価でかつ必要な強度や靱性を有することから、Al合金
の鋳造材や鍛造材 (本発明ではこれらを総称して鋳鍛材
と言う) が使用されている。鋳造材としては、Siを6.5
〜7.5% (質量% 、以下同じ) 含む、AA AC4CHなどの Al-
Si-Mg 系Al合金が代表的である。また、鍛造材として
は、時効硬化性やリサイクル性に優れたAl-Si-Mg系のAA
6000 系Al合金などが代表的である。In addition, structural materials having complicated shapes and thick portions, such as motorcycles, automobile wheels, suspension parts such as knuckles, lower arms, and upper arms, include:
Since it is inexpensive and has the necessary strength and toughness, cast materials and forged materials of Al alloy (these are collectively referred to as cast forged materials in the present invention) are used. As casting material, 6.5
~ 7.5% (mass%, the same applies hereinafter), including Al- such as AA AC4CH
A typical example is a Si-Mg-based Al alloy. In addition, Al-Si-Mg based AA with excellent age hardening and recyclability
A typical example is a 6000 series Al alloy.
【０００６】更に、自動車のドアやフェンダーあるいは
ボンネットなどのパネル材或いはホイール等の自動車用
部材については、Al-Si-Mg系のAA 6000 系Al合金などが
代表的である。AA 6000 系Al合金は、プレス成形加工時
には低耐力として成形加工性を確保でき、プレス成形後
の焼付塗装時に時効硬化して耐力が向上し、パネル材と
して必要な強度を確保できる。また、スクラップをAl合
金溶解原料として再利用する際に、比較的合金量が少な
く、元の6000系Al合金鋳塊を得やすい利点もある。[0006] Further, as a member for a vehicle such as a panel material such as a door, a fender or a bonnet of an automobile, or a wheel, an Al-Si-Mg-based AA6000-based Al alloy or the like is representative. The AA 6000 series Al alloy has low proof stress during press forming and can secure the formability, age hardens during baking coating after press forming, improves proof stress, and can secure the strength required for panel materials. Further, when scrap is reused as a raw material for dissolving an Al alloy, there is an advantage that the alloy amount is relatively small and an original 6000 series Al alloy ingot can be easily obtained.
【０００７】しかし、例えば自動車車体にAl合金材が使
用される場合、オールアルミ車などの一部を除いて、大
部分の自動車車体は従来からの鋼板などの鋼材とAl合金
材とが複合化されて用いられる。例えば鋼板製からなる
ドアの部材とAl合金形材製のドアビームとが複合材料の
ドア部材として車体に取り付けられる。However, for example, when an Al alloy material is used for an automobile body, most of the automobile body except for a part of an all-aluminum vehicle or the like is a composite of a conventional steel material such as a steel plate and an Al alloy material. It is used. For example, a door member made of a steel plate and a door beam made of an Al alloy profile are attached to a vehicle body as a door member made of a composite material.
【０００８】通常、自動車の製造ラインにおいて、成
形、組み立て後の車体は、リン酸亜鉛処理およびカチオ
ン電着塗装処理などの塗装下地処理を施された後、焼付
け硬化する中塗り、上塗りなどの塗装を施される。そし
て、この製造ラインにおける各工程条件は基本的に、こ
れまで使用されている鋼材の条件に見合ったものとなっ
ている。したがって、自動車車体に使用されるAl合金材
は、従来の鋼材とともに、言い換えると、鋼材と同じ条
件で表面にリン酸亜鉛処理およびカチオン電着塗装処理
などの塗装下地処理が施されることになる。[0008] Usually, in a car production line, a car body after being formed and assembled is subjected to a coating base treatment such as a zinc phosphate treatment and a cationic electrodeposition coating treatment and then to a baking-hardened coating such as a middle coat or a top coat. Is given. Each process condition in this production line basically matches the condition of the steel material used so far. Therefore, the Al alloy material used for the automobile body is subjected to a coating base treatment such as a zinc phosphate treatment and a cationic electrodeposition coating treatment on the surface together with the conventional steel material, in other words, under the same conditions as the steel material. .
【０００９】しかし、Al合金材の場合、鋼材よりもリン
酸亜鉛処理性が劣るため、Al合金材表面に、均一で適当
量のリン酸亜鉛の皮膜が確保されにくいという問題があ
る。仮にリン酸亜鉛処理性が悪いと、その後に塗装によ
り形成される塗膜の密着性が低下する。そしてこの結
果、塗装後に糸錆状の腐食や塗膜のふくれが生じ、自動
車としての耐食性や外観性を低下させるという問題があ
る。However, in the case of the Al alloy material, the zinc phosphate treatment property is inferior to that of the steel material, so that there is a problem that it is difficult to secure a uniform and appropriate amount of zinc phosphate film on the surface of the Al alloy material. If the zinc phosphate treatment property is poor, the adhesion of a coating film formed by coating thereafter will be reduced. As a result, there is a problem that rust-like corrosion and swelling of the coating film occur after coating, and the corrosion resistance and appearance of the automobile are deteriorated.
【００１０】このため、Al合金材のリン酸亜鉛処理性を
改善するために、従来からリン酸亜鉛処理浴の側を改善
することが行われている。例えば、その代表例として
は、リン酸亜鉛処理浴に数十〜数百ppm 程度の高濃度の
フリーフッ素(F) イオンを添加することが行われてい
る。[0010] Therefore, in order to improve the zinc phosphate treatability of the Al alloy material, the zinc phosphate treatment bath has conventionally been improved. For example, as a typical example, a high concentration of free fluorine (F) ions of about several tens to several hundreds ppm is added to a zinc phosphate treatment bath.
【００１１】[0011]
【発明が解決しようとする課題】このフリーフッ素(F)
イオンの添加によって、Al合金材のリン酸亜鉛処理性は
改善される。しかし、Al合金材表面へのリン酸亜鉛皮膜
の形成は、Al合金材表面からのAlイオンの溶出によって
促進されるため、Al合金材のリン酸亜鉛処理性がよくな
るほど、Al合金材表面からのAlイオンの溶出量が多くな
る。そして、このAlイオンの溶出が多くなると、肝心の
鋼材の方のリン酸亜鉛処理性を阻害するという新たな問
題を生じる。SUMMARY OF THE INVENTION This free fluorine (F)
The addition of ions improves the zinc phosphate treatability of the Al alloy material. However, the formation of a zinc phosphate film on the surface of the Al alloy material is promoted by the elution of Al ions from the surface of the Al alloy material. Eluted amount of Al ions increases. When the elution of this Al ion increases, a new problem arises in that the essential steel material is inhibited from being treated with zinc phosphate.
【００１２】勿論、リン酸亜鉛処理浴より、蓄積したAl
イオンを除去してやれば良いが、除去に伴うリン酸亜鉛
浴のロス分や、処理設備のコストが大きく、省エネや効
率化が厳しく追求される自動車の製造ラインからする
と、コストアップにつながってしまう結果となる。[0012] Of course, the accumulated Al from the zinc phosphate treatment bath.
It is good to remove the ions, but the loss of the zinc phosphate bath due to the removal and the cost of the processing equipment are large, and the cost of the automobile production line, where energy saving and efficiency are strictly pursued, leads to an increase in cost. Becomes
【００１３】本発明はこの様な事情に着目してなされた
ものであって、その目的は、従来のリン酸亜鉛処理の問
題点をAl合金材の側から解決し、リン酸亜鉛処理されて
も、また、特に鋼材とともに同一のラインでリン酸亜鉛
処理されても、更に、リン酸亜鉛処理浴にフリーフッ素
イオンが添加されたとしても、Al合金材表面からのAlイ
オンの溶出を抑えることのできるAl合金材を提供しよう
とするものである。The present invention has been made in view of such circumstances, and an object of the present invention is to solve the problems of the conventional zinc phosphate treatment from the side of the Al alloy material, and to perform the zinc phosphate treatment. In addition, even if zinc phosphate treatment is carried out in the same line with steel material, and even if free fluorine ions are added to the zinc phosphate treatment bath, elution of Al ions from the surface of the Al alloy material is suppressed. The purpose of the present invention is to provide an Al alloy material that can be used.
【００１４】[0014]
【課題を解決するための手段】この目的を達成するため
に、本発明リン酸亜鉛処理用Al合金材の要旨は、リン酸
亜鉛処理される際に、Alの溶出を防止したAl合金材であ
って、表面にAlの水和酸化物皮膜が設けられるととも
に、該皮膜を有するAl合金材のリン酸亜鉛処理液中にお
ける自然電位が、同一条件で測定した、Alの水和酸化物
皮膜を設けないAl合金材の最も低い自然電位よりも、10
0mV 以上高いことである (但し、Al合金材の自然電位
は、液中のフリーフッ素イオン濃度50ppm 、液温42℃の
リン酸亜鉛処理液に2 分浸漬後に測定したもの) 。In order to achieve this object, the gist of the Al alloy material for zinc phosphate treatment of the present invention is to provide an Al alloy material which prevents the elution of Al during zinc phosphate treatment. Then, while a hydrated oxide film of Al is provided on the surface, the natural potential of the Al alloy material having the film in the zinc phosphate treatment solution was measured under the same conditions. 10 lower than the lowest spontaneous potential of the Al alloy material without
It is higher than 0 mV (however, the spontaneous potential of the Al alloy material was measured after immersion in a zinc phosphate treatment solution at a free fluorine ion concentration of 50 ppm and a solution temperature of 42 ° C. for 2 minutes).
【００１５】本発明者らは、先に、特願平10-227758 号
等により、現行のリン酸亜鉛処理およびカチオン電着塗
装処理などの塗装下地処理に代わる下地処理として、Al
合金材の表面にAlの水和酸化物皮膜を設けることを提案
した。The inventors of the present invention have previously disclosed, in Japanese Patent Application No. 10-227758, Al as an undercoating treatment which can replace the existing coating treatments such as zinc phosphate treatment and cationic electrodeposition coating treatment.
It was proposed to provide a hydrated oxide film of Al on the surface of the alloy material.
【００１６】そして、今回、更に、このAlの水和酸化物
皮膜が、Al合金材がリン酸亜鉛処理される場合に、Al合
金材表面からのAlイオンの溶出を抑えることができるの
ではないかと検討した。And, this time, this hydrated oxide film of Al cannot suppress the elution of Al ions from the surface of the Al alloy material when the Al alloy material is treated with zinc phosphate. I considered.
【００１７】しかし、単に、Al合金材にAlの水和酸化物
皮膜を設けただけでは、酸性の強いリン酸亜鉛処理浴に
浸漬されると、例え、短時間であっても、Alの水和酸化
物皮膜自体がリン酸亜鉛処理浴に反応し、甚だしき場合
は、Alの水和酸化物皮膜自体が変質乃至消滅すること、
および、そこまでいかずとも、Alの水和酸化物皮膜自体
にこの種薄膜としては、比較的大きな割れ (クラック)
が多数入り、甚だしき場合は、生地のAl合金材から剥離
する可能性があること等を知見した。However, simply by providing a hydrated oxide film of Al on an Al alloy material, if the aluminum alloy material is immersed in a strongly acidic zinc phosphate treatment bath, even if it is for a short time, the water content of Al is reduced. The hydrated oxide film itself reacts with the zinc phosphate treatment bath, and if severe, the hydrated oxide film itself of Al deteriorates or disappears,
And even if not so, the hydrated oxide film of Al itself has relatively large cracks as this kind of thin film.
It was found that there is a possibility of peeling off from the Al alloy material of the fabric when it is extremely large.
【００１８】Alの水和酸化物皮膜のリン酸亜鉛処理浴に
よるこれら損傷乃至変質( 以下、単に劣化と言う) の問
題は、塗装皮膜の塗装性や密着性、或いは耐蝕性を阻害
することにつながるとともに、塗装下地処理としての信
頼性を大幅に低下させる。The problem of such damage or alteration (hereinafter simply referred to as deterioration) of the hydrated oxide film of Al due to the zinc phosphate treatment bath is caused by impairing the paintability, adhesion, or corrosion resistance of the coating film. In addition, it greatly reduces the reliability of the paint base treatment.
【００１９】そこで、更に、Alの水和酸化物皮膜の改良
について検討を重ねた結果、ベーマイトなどのAl2O3 ・
XH2Oで表されるAlの水和酸化物皮膜のリン酸亜鉛処理浴
中の自然電位 (実際には表面にAlの水和酸化物皮膜を設
けたAl合金材の自然電位で測定) が、Alの水和酸化物皮
膜のリン酸亜鉛処理浴による耐劣化性に大きく影響する
ことを知見した。Therefore, as a result of further study on improvement of the hydrated oxide film of Al, Al 2 O 3.
The natural potential of a hydrated oxide film of Al represented by XH 2 O in a zinc phosphate treatment bath (actually measured by the natural potential of an Al alloy material with a hydrated oxide film of Al on the surface) It was also found that the hydrated oxide film of Al had a great influence on the resistance to deterioration by the zinc phosphate treatment bath.
【００２０】即ち、Alの水和酸化物皮膜のリン酸亜鉛処
理浴における自然電位が高いほど、アノード分極を低下
させて、リン酸亜鉛処理浴に対する皮膜の耐劣化性や耐
反応性を向上させ、皮膜の耐久性を向上させる。That is, the higher the spontaneous potential of the hydrated oxide film of Al in the zinc phosphate treatment bath, the lower the anodic polarization and the better the deterioration resistance and reaction resistance of the film to the zinc phosphate treatment bath. And improve the durability of the film.
【００２１】これは、Alの水和酸化物皮膜のリン酸亜鉛
処理浴における自然電位が高いほど、Alの水和酸化物皮
膜の緻密さと厚みが増して、リン酸亜鉛処理浴に対する
皮膜の耐劣化性や耐反応性を向上させ、皮膜の耐久性を
向上させるものと推考される。This is because the higher the spontaneous potential of the Al hydrated oxide film in the zinc phosphate treatment bath, the greater the density and thickness of the Al hydrated oxide film, and the more resistant the film is to the zinc phosphate treatment bath. It is supposed that this improves the deterioration and reaction resistance, and improves the durability of the film.
【００２２】ただ、このAlの水和酸化物皮膜の、特に緻
密さは直接定量化することは困難である。したがって、
本発明では、Alの水和酸化物皮膜の緻密さと相関を有す
るAlの水和酸化物皮膜のリン酸亜鉛処理浴における自然
電位で特定する。更に、水和酸化物皮膜 (薄膜) 自体の
自然電位の測定は困難であるので、実際の自然電位の測
定は表面にAlの水和酸化物皮膜を設けたAl合金材の自然
電位で測定) で特定する。そして、この測定自然電位量
に再現性を持たせるために、Alの水和酸化物皮膜を設け
ない、同じAl合金材の同じリン酸亜鉛処理浴における自
然電位量を規準とし、これとの差で、自然電位量を規定
している。However, it is difficult to directly quantify the density of the hydrated oxide film of Al in particular. Therefore,
In the present invention, the hydrated oxide film of Al having a correlation with the density of the hydrated oxide film of Al is specified by the natural potential in the zinc phosphate treatment bath. Furthermore, since the measurement of the natural potential of the hydrated oxide film (thin film) itself is difficult, the actual measurement of the natural potential is performed using the natural potential of an Al alloy material having an Al hydrated oxide film on the surface.) To specify. Then, in order to give reproducibility to the measured natural potential, the natural potential in the same zinc phosphate treatment bath of the same Al alloy material without the hydrated oxide film of Al was used as a reference, and the difference from this was considered. Defines the amount of spontaneous potential.
【００２３】一方、Alの水和酸化物皮膜のリン酸亜鉛処
理浴における自然電位は、Al合金材の化学成分やAlの水
和酸化物皮膜の形成条件に大きく影響される。例えば、
同じ、Alの水和酸化物皮膜の形成条件であったとして
も、Al合金材の特にCu、Mg、Zn等の含有量の違いなどに
によっても、前記自然電位は大きく異なる。このこと
は、Alの水和酸化物皮膜の緻密さが、Al合金材の化学成
分やAlの水和酸化物皮膜の形成条件に大きく影響される
ことを示している。そして、本発明におけるリン酸亜鉛
処理浴におけるAlの溶出を防止する効果を再現性良く保
証するためには、Alの水和酸化物皮膜のリン酸亜鉛処理
浴における自然電位という指標が必要となることも示し
ている。On the other hand, the natural potential of the hydrated oxide film of Al in the zinc phosphate treatment bath is greatly affected by the chemical composition of the Al alloy material and the conditions for forming the hydrated oxide film of Al. For example,
Even under the same conditions for forming the hydrated oxide film of Al, the above-mentioned spontaneous potential greatly differs depending on the difference in the content of Al, particularly Cu, Mg, Zn and the like. This indicates that the density of the Al hydrated oxide film is greatly affected by the chemical composition of the Al alloy material and the conditions for forming the Al hydrated oxide film. In order to ensure the effect of preventing the elution of Al in the zinc phosphate treatment bath of the present invention with good reproducibility, an index called the natural potential in the zinc phosphate treatment bath of the hydrated oxide film of Al is required. It also shows that.
【００２４】[0024]
【発明の実施の形態】(Alの水和酸化物皮膜)本発明にお
ける、Alの水和酸化物皮膜とは、一般式、Al2O3 ・XH2O
で表され、Alの酸化物の水和反応により生成したAlの水
和酸化物の皮膜を言う。そして、本発明におけるAlの水
和酸化物とは、水和の程度(Xの値) などによる水和酸化
物の種類や、形態、結晶構造や結晶度などに特に限定さ
れるものではない。ただ、Alの水和酸化物の中でも、前
記X の値が約1.5 〜1.9 である擬似ベーマイトのもの
は、ベーマイト皮膜と一般的に総称されている。BEST MODE FOR CARRYING OUT THE INVENTION (Hydrated oxide film of Al) In the present invention, the hydrated oxide film of Al is represented by the general formula: Al 2 O 3 .XH 2 O
And a film of a hydrated oxide of Al formed by a hydration reaction of an oxide of Al. The hydrated oxide of Al in the present invention is not particularly limited to the type, form, crystal structure, crystallinity, etc. of the hydrated oxide depending on the degree of hydration (the value of X). However, among the hydrated oxides of Al, those of pseudo-boehmite in which the value of X is about 1.5 to 1.9 are generally referred to as boehmite films.
【００２５】そして、これらの皮膜構造の同定は、前記
走査型電子顕微鏡による形態的な観察の他に、入射角75
度の平行偏光使用によるFTIR (フーリエ変換式赤外分光
光度計) 分析で行うことができる。即ち、FTIRにより、
水酸基のスペクトルを吸光度表示した際の、3000〜3700
cm-1 (カイザー) 付近に認められるAlO ←→H の伸縮振
動による吸収スペクトル、および1000〜1050cm-1付近に
認められるAl←→OHの伸縮振動による吸収スペクトル、
更に800 〜600cm -1付近に認められるOAl ←→O の伸縮
振動による吸収スペクトルの、いずれか一つ以上が認め
られることにより、本発明のAlの水和酸化物皮膜の存在
が確認される。また、Alの水和酸化物皮膜と、塗膜の区
別および膜厚の測定は、Al合金材の破面 (例えばAl合金
材の180°曲げによる破面) を前記した走査型電子顕微
鏡による2 万倍以上の観察で行うことができる。なお、
この倍率は、Alの水和酸化物の膜厚が薄くなるに従い、
より高倍率とする必要がある。また、この他、X 線回折
によってもAlの水和酸化物皮膜の同定が可能であり、透
過型電子顕微鏡によっても形態的な観察が可能である。The identification of these film structures was carried out by morphological observation using a scanning electron microscope and the incident angle 75
It can be performed by FTIR (Fourier transform infrared spectrophotometer) analysis using parallel polarized light. That is, by FTIR,
3000 to 3700 when the absorbance of the hydroxyl group spectrum is displayed
cm -1 (Kaiser) AlO found in the vicinity ← → absorption spectrum due to stretching vibration of H, and 1000~1050cm are found in the vicinity of -1 Al ← → absorption spectrum due to stretching vibrations of OH,
Further, the presence of any one or more of the absorption spectra due to the stretching vibration of OAl ← → O observed near 800 to 600 cm −1 confirms the presence of the Al hydrated oxide film of the present invention. Further, the hydrated oxide film of Al and the distinction of the coating film and the measurement of the film thickness were obtained by scanning the fracture surface of the Al alloy material (for example, the fracture surface of the Al alloy material by bending at 180 °) with the scanning electron microscope described above. It can be performed with more than 10,000 times observation. In addition,
This magnification, as the thickness of the hydrated oxide of Al becomes thinner,
Higher magnification is required. In addition, the hydrated oxide film of Al can be identified by X-ray diffraction, and morphological observation can be performed by a transmission electron microscope.
【００２６】また、Alの水和酸化物皮膜中の、Alの自然
電位よりも電位的に卑な金属化合物についても、実施例
にて詳述するX 線光電子分析法(XPS法) による、各々の
金属元素の結合エネルギー (各々の金属元素のXPS スペ
クトル強度) の測定により、これら元素のAlの水和酸化
物皮膜中の同定や含有量の測定が可能である。或いはX
線回折法によってもこれらの測定が可能である。The metal compounds in the hydrated oxide film of Al that are lower in potential than the natural potential of Al were also measured by X-ray photoelectron analysis (XPS method) described in detail in Examples. By measuring the binding energies of the metal elements (the XPS spectral intensities of the respective metal elements), it is possible to identify and measure the content of these elements in the hydrated oxide film of Al. Or X
These measurements are also possible by the line diffraction method.
【００２７】(Alの水和酸化物皮膜の膜厚)更に、本発明
におけるAlの水和酸化物皮膜の膜厚は、100 〜10000 Å
とするのが好ましい。膜厚が100 Å未満では、膜厚の絶
対量が不足して、リン酸塩処理浴やED塗装に対する劣化
性を向上させる( 劣化を抑制させる) ことができない。
一方、膜厚が10000 Åを越えると、Alの水和酸化物皮膜
のAl合金材との密着性が低下して、膜厚が薄い場合と同
様に、却って、リン酸塩処理浴に対する劣化性を向上さ
せることができない。(Film thickness of hydrated oxide film of Al) Further, the film thickness of the hydrated oxide film of Al in the present invention is 100 to 10000100.
It is preferred that If the film thickness is less than 100 mm, the absolute amount of the film thickness will be insufficient, and it will not be possible to improve (suppress the deterioration) deterioration of the phosphating bath or ED coating.
On the other hand, when the film thickness exceeds 10,000 mm, the adhesion of the hydrated oxide film of Al to the Al alloy material is reduced, and as in the case of the thin film, the deterioration in the phosphating bath is rather increased. Can not be improved.
【００２８】(Alの水和酸化物皮膜の自然電位)次に、本
発明におけるAlの水和酸化物皮膜の自然電位 (以下、単
に電位と言う) について説明する。まず、Alの水和酸化
物皮膜の電位の測定方法について、薄膜であるAlの水和
酸化物皮膜自体の電位を直接測定することは、実質的に
困難である。一方、測定可能なAlの水和酸化物皮膜を設
けたAl合金材の電位と、このAlの水和酸化物皮膜を設け
ないAl合金材との電位の差をとれば、Alの水和酸化物皮
膜自体の電位を、正確に、しかも再現性良く測定するこ
とが可能である。したがって、本発明では、Alの水和酸
化物皮膜の電位を、Alの水和酸化物皮膜を設けたAl合金
材の電位として測定し、しかも、Alの水和酸化物皮膜を
設けないAl合金材との電位量の差で表している。(Spontaneous potential of hydrated oxide film of Al) Next, the natural potential of the hydrated oxide film of Al in the present invention (hereinafter, simply referred to as potential) will be described. First, regarding the method of measuring the potential of the hydrated oxide film of Al, it is substantially difficult to directly measure the potential of the hydrated oxide film of Al itself, which is a thin film. On the other hand, the difference between the potential of the Al alloy material provided with the measurable Al hydrated oxide film and the potential of the Al alloy material not provided with the Al hydrated oxide film can be calculated as the hydrated oxidation of Al. It is possible to measure the potential of the object film itself accurately and with good reproducibility. Therefore, in the present invention, the potential of the Al hydrated oxide film is measured as the potential of the Al alloy material provided with the Al hydrated oxide film, and the Al alloy without the Al hydrated oxide film is provided. It is represented by the difference in the amount of potential with the material.
【００２９】Alの水和酸化物皮膜を設けたAl合金材の自
然電位の具体的な測定方法は、当該Alの水和酸化物皮膜
を設けた場合と設けない場合の同じ成分組成および製法
の(要は同一の) Al合金材を各々試料電極とし、液中の
フリーフッ素イオン濃度50ppm 、液温42℃としたリン酸
亜鉛処理液に2 分浸漬後という一定条件で、両者の自然
電位を測定し、自然電位の差を算出する。The specific method of measuring the natural potential of the Al alloy material provided with the Al hydrated oxide film is based on the same component composition and production method when the Al hydrated oxide film is provided and not provided. Under the constant condition of immersion for 2 minutes in a zinc phosphate treatment liquid with the Al alloy material as the sample electrode and the free fluoride ion concentration in the liquid at 50 ppm and the liquid temperature at 42 ° C, the natural potential of both was determined. Measure and calculate the difference in natural potential.
【００３０】図1 に、前記リン酸亜鉛処理液中での、水
和酸化物皮膜を設けたAl合金材の自然電位a の経時変化
と、Alの水和酸化物皮膜を設けないAl合金材の自然電位
b のの経時変化を示す。本発明における水和酸化物皮膜
を設けたAl合金材の自然電位とは、図1 において、前記
リン酸亜鉛処理液に浸漬2 分後の電位a1である。時間が
経過するほど、リン酸亜鉛処理液中でAlの水和酸化物皮
膜が溶解するため、自然電位a は次第に低下 (変化) し
ていく。このため、自然電位を特定する場合には、リン
酸亜鉛処理液の浸漬時間を特定する必要があり、本発明
では、2 分後とした。これに対し、Alの水和酸化物皮膜
を設けないAl合金材の最も低い自然電位とは、図1 にお
いて、前記リン酸亜鉛処理液に浸漬2 分後の電位の内、
電位が最も低くなる電位b1である。そして、本発明で
は、水和酸化物皮膜を設けたAl合金材の自然電位a1が、
Alの水和酸化物皮膜を設けないAl合金材の最も低い自然
電位b1とよりも、100mV 以上高いことを要旨としてい
る。なお、Alの水和酸化物皮膜を設けないAl合金材の自
然電位が電位b2等のピークをもっているのは( 図1 では
3 つのピーク) 、Alの水和酸化物皮膜を設けないAl合金
材では、表面のAl合金とリン酸亜鉛との反応が生じ、リ
ン酸亜鉛結晶の反応電位として現れているからである。FIG. 1 shows the change over time of the natural potential a of the Al alloy material provided with the hydrated oxide film and the Al alloy material not provided with the hydrated oxide film of Al in the zinc phosphate treatment liquid. Natural potential
The time course of b is shown. The natural potential of the Al alloy material having a hydrated oxide film of the present invention, in FIG. 1, the potential a 1 soaking after 2 minutes to the zinc phosphate treatment solution. As time elapses, the hydrated oxide film of Al dissolves in the zinc phosphate treatment liquid, so that the natural potential a gradually decreases (changes). For this reason, when specifying the spontaneous potential, it is necessary to specify the immersion time of the zinc phosphate treatment solution, and in the present invention, it is set to 2 minutes. On the other hand, the lowest spontaneous potential of the Al alloy material not provided with the hydrated oxide film of Al is the potential after two minutes of immersion in the zinc phosphate treatment liquid in FIG.
The potential b 1 potential is the lowest. And in the present invention, the natural potential a 1 of the Al alloy material provided with the hydrated oxide film,
Than the lowest natural potential b 1 Metropolitan of Al alloy material without the hydrated oxide film of Al, it is summarized as higher than 100 mV. Incidentally, the self-potential of the Al alloy material without the hydrated oxide film of Al has a peak of equipotential b 2 is in (Figure 1
This is because, in an Al alloy material having no hydrated oxide film of Al, a reaction between the Al alloy on the surface and zinc phosphate occurs and appears as a reaction potential of zinc phosphate crystals.
【００３１】そして、この自然電位の差 (以下、この自
然電位の差を単にAlの水和酸化物皮膜の自然電位と言
う) を100mV 以上とするのは、リン酸塩処理浴やED塗装
に対するAlの水和酸化物皮膜の耐劣化性を向上させるた
めである。Alの水和酸化物皮膜の自然電位差が100mV 未
満であると、Alの水和酸化物皮膜の、リン酸塩処理浴や
ED塗装に対する劣化性を向上させることができず、Alの
溶出量を抑制することが出来なくなる。また、これと同
時に、Alの水和酸化物皮膜の劣化によって、前記Alの水
和酸化物皮膜の優れた耐食性などが発揮できなくなる。The difference in the natural potential (hereinafter, this difference in the natural potential is simply referred to as the natural potential of the hydrated oxide film of Al) is set to 100 mV or more because of the difference between the phosphating bath and the ED coating. This is for improving the deterioration resistance of the hydrated oxide film of Al. If the natural potential difference of the hydrated oxide film of Al is less than 100 mV, the hydrated oxide film of Al
Deterioration to ED coating cannot be improved, and the elution amount of Al cannot be suppressed. At the same time, due to the deterioration of the hydrated oxide film of Al, the excellent corrosion resistance and the like of the hydrated oxide film of Al cannot be exhibited.
【００３２】(Alの水和酸化物皮膜の作製方法)本発明に
おけるAlの水和酸化物皮膜の高自然電位化の手段は、Al
の水和酸化物皮膜の緻密化の手段と対応する。(Method for Producing Al Hydrated Oxide Film) The means for increasing the spontaneous potential of the Al hydrated oxide film in the present invention is as follows.
Corresponds to the means for densification of the hydrated oxide film.
【００３３】即ち、Alの水和酸化物皮膜の作製方法は、
Al合金材を輸送機用に成形および溶接接合した後、成形
材のAl合金表面を、有機溶剤やアリカリ性溶液により、
脱脂乃至洗浄する前処理を行った後に、高温水や水蒸気
に直接接触させる方法、あるいは成形材のAl合金表面に
Alの酸化物層を設けた後で水和反応によりAlの水和酸化
物皮膜に変換する方法、更に、これらAlの水和酸化物皮
膜を設けた後に、加熱により水和量を調節する方法など
が適宜選択されて良い。That is, the method for producing the hydrated oxide film of Al is as follows.
After forming and welding-joining the Al alloy material for the transport machine, the Al alloy surface of the formed material is treated with an organic solvent or an alkaline solution.
After performing pretreatment for degreasing or cleaning, it is directly contacted with high-temperature water or steam, or on the Al alloy surface of the molding material.
A method of converting to an Al hydrated oxide film by a hydration reaction after providing an Al oxide layer, and a method of adjusting the hydration amount by heating after providing these Al hydrated oxide films May be appropriately selected.
【００３４】このAlの水和酸化物皮膜の作製に使用され
る水なり水分は、中性または弱アルカリ性浴、より具体
的には、水道水、純水、あるいはトリエタノールアミン
やアンモニアなどの水溶液が用いられる。The water used for producing the hydrated oxide film of Al is a neutral or weak alkaline bath, more specifically, tap water, pure water, or an aqueous solution of triethanolamine or ammonia. Is used.
【００３５】この際、Alの水和酸化物皮膜の形成温度を
高温とし、更に長時間とするほど、Alの水和酸化物皮膜
が緻密となって、Alの水和酸化物皮膜が高自然電位化す
る。例えば、Al合金材の化学成分やAlの水和酸化物皮膜
の処理液によっても異なるが、70℃未満の処理温度や10
分以内の短時間処理では、Alの水和酸化物皮膜を緻密化
および高自然電位化できない。At this time, the higher the temperature at which the hydrated oxide film of Al is formed and the longer the temperature, the denser the hydrated oxide film of Al, and the more natural the hydrated oxide film of Al becomes. Potential is set. For example, depending on the chemical composition of the Al alloy material and the treatment liquid for the hydrated oxide film of Al, the treatment temperature of less than 70 ° C.
If the treatment is performed for a short time of less than one minute, the hydrated oxide film of Al cannot be densified and the self-potential cannot be increased.
【００３６】ただ、前記した通り、Alの水和酸化物皮膜
のリン酸亜鉛処理浴における自然電位は、Al合金材の化
学成分やAlの水和酸化物皮膜の形成条件に大きく影響さ
れるので、同じAlの水和酸化物皮膜の形成条件であった
としても、同じAl合金材の化学成分であったとしても、
同じ自然電位( 緻密さ) のAlの水和酸化物皮膜が得られ
るとは限らない。また、Alの水和酸化物皮膜の形成温度
を高温とし、更に長時間としても、高い自然電位 (緻密
さ) のAlの水和酸化物皮膜が得られるとは限らない。し
たがって、同じAlの水和酸化物皮膜の形成条件で、同じ
Al合金材の化学成分であったとしても、また、Alの水和
酸化物皮膜の形成温度を高温とし、更に長時間として
も、Alの水和酸化物皮膜の自然電位を測定して、本発明
範囲の自然電位を有するか否か検証する必要がある。However, as described above, the natural potential of the hydrated oxide film of Al in the zinc phosphate treatment bath is greatly affected by the chemical composition of the Al alloy material and the conditions for forming the hydrated oxide film of Al. Even if it is the same condition for forming the hydrated oxide film of Al, even if it is the same chemical composition of the Al alloy material,
It is not always possible to obtain a hydrated oxide film of Al having the same spontaneous potential (density). In addition, even if the formation temperature of the hydrated oxide film of Al is set to a high temperature, and even for a long time, a hydrated oxide film of Al having a high spontaneous potential (density) is not always obtained. Therefore, under the same Al hydrated oxide film formation conditions,
Even if it is a chemical component of the Al alloy material, the formation temperature of the Al hydrated oxide film is set to a high temperature, and even for a long time, the natural potential of the Al hydrated oxide film is measured, It is necessary to verify whether or not it has a spontaneous potential within the scope of the invention.
【００３７】Alの水和酸化物皮膜をAl合金材表面に形成
する場合、板材や形材や鍛造材などの素材の段階で形成
しても良く、Al合金材を例えば輸送機用に成形および溶
接接合した後で、リン酸塩処理前に、成形材のAl合金表
面にAlの水和酸化物皮膜を設けても良い。When the hydrated oxide film of Al is formed on the surface of the Al alloy material, it may be formed at the stage of a material such as a plate material, a shape material or a forged material. After welding and before the phosphate treatment, a hydrated oxide film of Al may be provided on the surface of the Al alloy of the molded material.
【００３８】次に、本発明における適用対象Al合金は、
AA乃至JIS 3000系、 5000 系、 6000 系、7000系の成分
規格のAl合金が適宜使用可能である。しかし、このJIS
規格以外のAl合金でも、用途の要求特性を満足するAl合
金は、全て本発明の適用対象となる。Next, the Al alloy to be applied in the present invention is:
AA to JIS 3000 series, 5000 series, 6000 series, and 7000 series component alloys can be used as appropriate. However, this JIS
The present invention is applicable to all Al alloys that meet the required characteristics of the application, even if they are non-standard.
【００３９】自動車、船舶などの輸送機材や構造材ある
いは部品用の内、特に自動車のパネル材やフレーム材と
しては、合金元素が少なくリサイクル性に優れることが
好ましい。また、基本的な特性として、引張強度が200N
/mm2以上および耐力で 90N/mm2以上を有してプレス成形
性に優れることや、プレス成形後の塗装焼付後には、好
ましくは200N/mm2以上の高い耐力となる焼付硬化性など
の特性に優れていることが必要である。It is preferable that the materials for transportation equipment such as automobiles and ships, structural materials and parts, especially for automobile panel materials and frame materials, contain few alloying elements and have excellent recyclability. Also, as a basic characteristic, the tensile strength is 200N
/ In mm 2 or more and yield strength have a 90 N / mm 2 or more and is excellent in press formability, after paint baking following press forming, preferably, such as bake hardenability to be 200 N / mm 2 or more high yield strength It must have excellent characteristics.
【００４０】したがって、本発明Al合金の化学成分組成
は、前記諸特性を満足するために、Al-Mg-Si系のJIS 60
00系Al合金の成分規格 (JIS 6101、6003、6151、6061、
6N01、6063など) に相当するものとして、Si:0.2〜1.8%
(質量% 、以下同じ) 、Mg:0.2〜1.6%を基本的に含有
し、その他、Fe:1.0以下、Cu:1.5% 以下、Mn:1.0% 以
下、Cr:1.0以下、Zn:1.0% 以下、Ti:0.15%以下、B:300p
pm以下などを必要により選択的に含むAl合金とすること
が好ましい。Therefore, the chemical composition of the Al alloy of the present invention must be in accordance with JIS 60 of Al-Mg-Si system in order to satisfy the above-mentioned properties.
00 series Al alloy component standard (JIS 6101, 6003, 6151, 6061,
6N01, 6063 etc.), Si: 0.2-1.8%
(Mass%, the same applies hereinafter), Mg: basically 0.2 to 1.6%, other: Fe: 1.0 or less, Cu: 1.5% or less, Mn: 1.0% or less, Cr: 1.0 or less, Zn: 1.0% or less , Ti: 0.15% or less, B: 300p
It is preferable to use an Al alloy that selectively contains pm or less as necessary.
【００４１】また、JIS 6000系Al合金の各成分規格通り
にならずとも、前記基本的な特性を有してさえいれば、
更なる特性の向上や他の特性を付加するための、適宜成
分組成の変更は許容される。この点、上記元素の成分範
囲の変更や、より具体的な用途および要求特性に応じ
て、その他、Ni、V 、Zr、Sc、Agなどの他の元素やH 等
の不純物を適宜含むことは許容される。Further, even if the basic characteristics are not satisfied as long as they do not conform to the respective component standards of JIS 6000 series Al alloy,
It is permissible to appropriately change the component composition to further improve the characteristics or add other characteristics. In this regard, it is not possible to change the component range of the above-described elements, or to appropriately include other elements such as Ni, V, Zr, Sc, and Ag and impurities such as H according to more specific applications and required characteristics. Permissible.
【００４２】更に、本発明に係るAl合金材は、常法によ
る圧延加工、あるいは常法による押出加工等によって、
板材や形材 (中空断面など断面形状が長さ方向のどの位
置でも本質的に同一である形材) として製造される。即
ち、成分規格範囲内に溶解調整されたアルミ合金溶湯
を、例えば、連続鋳造圧延法、半連続鋳造法（ＤＣ鋳造
法）等の通常の溶解鋳造法を適宜選択して鋳造する。次
いで、このアルミ合金鋳塊に均質化熱処理を施し、熱間
圧延−冷間圧延−調質処理 (溶体化および焼き入れ処理
や時効硬化処理) 、押出加工−調質処理、熱間鍛造−調
質処理、あるいはこれらの組み合わせにより、板材、形
材、鍛造材等の所望の断面形状のAl合金材とする。Further, the Al alloy material according to the present invention can be rolled by a conventional method or extruded by a conventional method.
It is manufactured as a plate or a profile (a profile whose cross-sectional shape, such as a hollow cross-section, is essentially the same at any position along its length). That is, the molten aluminum alloy melt-adjusted within the component standard range is cast by appropriately selecting a normal melting casting method such as a continuous casting rolling method and a semi-continuous casting method (DC casting method). Next, the aluminum alloy ingot is subjected to a homogenizing heat treatment, and hot rolling, cold rolling, tempering treatment (solution treatment and quenching treatment and age hardening treatment), extrusion processing, tempering treatment, hot forging-tempering. An Al alloy material having a desired cross-sectional shape such as a plate material, a shape material, a forged material, or the like is obtained by a quality treatment or a combination thereof.
【００４３】[0043]
【実施例】次に、本発明の実施例を説明する。表1 に示
すA 〜E までの組成のAl合金の中空押出形材および板材
を前記常法にてを製作した (A 、B 、E が板材、C 、D
が形材) 。そして、これらから板状の試験片を採取し、
試験片のAl合金材の表面に表2 に示す条件でAlの水和酸
化物皮膜を形成した。Alの水和酸化物皮膜の形成方法
は、各試験片を40℃の30% 硝酸に2 分間浸漬して水洗
後、高温の純水および0.5%トリエタノールアミン(TEA) 水溶液中に
浸漬してAlの水和酸化物皮膜を形成するとともに、純水
およびTEA 水溶液の温度と浸漬時間等を変えて、Alの水
和酸化物の皮膜厚みを制御した。Next, an embodiment of the present invention will be described. Hollow extruded shapes and plates of Al alloys having the compositions A to E shown in Table 1 were prepared by the above-mentioned conventional method (A, B, and E were plates, C, and D, respectively).
But shaped material). Then, a plate-like test piece is collected from these,
A hydrated oxide film of Al was formed on the surface of the Al alloy material of the test piece under the conditions shown in Table 2. The method for forming the hydrated oxide film of Al is as follows: each test piece is immersed in 30% nitric acid at 40 ° C for 2 minutes, washed with water, and then immersed in hot pure water and 0.5% triethanolamine (TEA) aqueous solution. In addition to forming the hydrated oxide film of Al, the thickness of the hydrated oxide film of Al was controlled by changing the temperature and the immersion time of the pure water and the TEA aqueous solution.
【００４４】このAlの水和酸化物皮膜をFTIR法により同
定した結果、3000〜3700cm-1付近に認められるAlO ←→
H の伸縮振動による吸収スペクトル、および1050〜1100
cm-1付近に認められるAl←→OHの伸縮振動による吸収ス
ペクトルが認められることにより、Alの水和酸化物皮膜
の存在が確認された。また、Al合金試験片の表面の断面
を50000 倍 (膜厚の薄い例は150000倍) 倍の走査型電子
顕微鏡(SEM) による観察し、Alの水和酸化物皮膜である
ことを確認するとともに、Alの水和酸化物皮膜厚みを測
定した。As a result of identifying the hydrated oxide film of Al by the FTIR method, AlO observed in the vicinity of 3000 to 3700 cm −1 ← →
Absorption spectrum due to stretching vibration of H, and 1050-1100
The presence of a hydrated oxide film of Al was confirmed by an absorption spectrum due to stretching vibration of Al ← → OH observed near cm −1 . In addition, by observing the cross section of the surface of the Al alloy specimen with a scanning electron microscope (SEM) at a magnification of 50,000 times (150,000 times for a thin film), it was confirmed that it was a hydrated oxide film of Al. The thickness of the hydrated oxide film of Al was measured.
【００４５】更に、各々試験片のAlの水和酸化物皮膜の
電位を、前記測定方法により測定および計算した結果を
表2 に示す。Further, Table 2 shows the results obtained by measuring and calculating the potential of the hydrated oxide film of Al on each test piece by the above-mentioned measuring method.
【００４６】(化成処理条件) 各複合材試験片 (供試材)
をU 曲げした成形材の曲げ部分(R部分) を、塗装後の
耐蝕性試験片として採取し、表面の潤滑剤を脱脂して完
全に除去し、その後、発明例および比較例とも、リン酸
チタンのコロイド分散液コロイダル液 (コロイダルチタ
ン溶液: 日本パーカーライジング (株) 社製、商品名PB
L3020 システム、温度25℃、浸漬1 分) 処理およびリン
酸亜鉛処理 (フリーフッ素イオン量 50ppm、温度42℃、
浸漬2 分) した。この際、Al試験片からのAlの溶出量
は、リン酸亜鉛溶液中の総Alの量(mg)を原子吸光法によ
り測定し、試験片の単位面積当たり(1m2) に換算して求
めた。(Conversion conditions) Each composite material test piece (test material)
The bent part (R part) of the molded material obtained by bending the U was sampled as a corrosion resistance test piece after coating, the lubricant on the surface was degreased completely, and then the phosphoric acid in both the invention and comparative examples was Colloidal dispersion of titanium colloidal liquid (Colloidal titanium solution: Nippon Parker Rising Co., Ltd., trade name PB
L3020 system, temperature 25 ° C, immersion 1 minute) treatment and zinc phosphate treatment (free fluorine ion content 50ppm, temperature 42 ° C,
(Immersion for 2 minutes). At this time, the elution amount of Al from the Al test piece was determined by measuring the total amount (mg) of Al in the zinc phosphate solution by the atomic absorption method and converting it to the unit area of the test piece (1 m 2 ). Was.
【００４７】(塗装条件) これらの化成処理を行った
後、カチオン電着塗装を行い、しかる後に、2 コート2
ベーク塗装として、より具体的には、中塗り塗装とし
て、30μm 厚さのポリエステルメラミン系塗装皮膜を設
けた。ベークハード処理( 焼き付け硬化処理) は170 ℃
×20分とした。(Coating conditions) After performing these chemical conversion treatments, a cationic electrodeposition coating was performed.
As a bake coating, more specifically, a polyester melamine-based coating film having a thickness of 30 μm was provided as an intermediate coating. 170 ° C for bake hardening (bake hardening)
X 20 minutes.
【００４８】(塗装後耐蝕性試験) そして、これら発明
例、比較例の塗装試験片に、全て同じ条件で、耐糸さび
評価試験を行った。これらの評価結果も表4 に示す。耐
糸さび評価試験は、Al合金材と鋼材の塗装試験片の表面
に一片が7cm のクロスカットを施した後、35℃の3%HCl
水溶液に2 分間浸漬した後、次いで40℃、85%RH の恒温
恒湿の雰囲気に200 時間放置し、その後、Al合金材と鋼
材の表面 (塗装面）に発生した糸さびの最大長さL(クロ
スカットより垂直方向の距離) を測定した。そして、糸
さびの最大長さL が、L ≦3mm のものを○、L ＞3mm の
ものを×として評価した。(Corrosion Resistance Test after Painting) The coated test pieces of the invention examples and the comparative examples were all subjected to a yarn rust evaluation test under the same conditions. Table 4 also shows the results of these evaluations. The rust resistance evaluation test was performed by applying a 7 cm cross-cut to the surface of a painted test piece of Al alloy and steel, and then applying 3% HCl at 35 ° C.
After immersion in an aqueous solution for 2 minutes, then left in an atmosphere of constant temperature and humidity of 40 ° C and 85% RH for 200 hours, and then the maximum length L of thread rust generated on the surface (painted surface) of Al alloy material and steel material (The distance in the vertical direction from the cross cut) was measured. The maximum length L of the thread rust was evaluated as ○ when L ≦ 3 mm, and as X when L> 3 mm.
【００４９】表2 の結果から明らかな通り、Alの水和酸
化物皮膜の電位が、本発明の規定を満足する皮膜を有す
る発明例No.1〜10は、リン酸亜鉛処理におけるAlの溶出
量が少なく、かつ塗装後の耐糸さび性などの耐蝕性にも
優れる。As is evident from the results in Table 2, the invention examples Nos. 1 to 10 having a film in which the potential of the hydrated oxide film of Al satisfies the requirements of the present invention were the same as those of Example Nos. It has a small amount and is excellent in corrosion resistance such as thread rust resistance after painting.
【００５０】一方、これに対し、本発明の電位範囲より
はずれるAlの水和酸化物皮膜を設けた比較例No.11 〜15
は、塗装後の耐糸さび性などの耐蝕性が悪く、リン酸亜
鉛処理におけるAlの溶出量も多い。On the other hand, Comparative Examples Nos. 11 to 15 provided with a hydrated oxide film of Al which was out of the potential range of the present invention.
Has poor corrosion resistance such as thread rust resistance after coating, and has a large amount of Al eluted by zinc phosphate treatment.
【００５１】したがって、以上の事実から、本発明規定
Alの水和酸化物皮膜の電位の臨界的な意義や好ましい条
件の意義が裏付けられる。Therefore, based on the above facts, the present invention
The critical significance of the potential of the hydrated oxide film of Al and the significance of preferable conditions are supported.
【００５２】[0052]
【表１】 [Table 1]
【００５３】[0053]
【表２】 [Table 2]
【００５４】[0054]
【発明の効果】本発明によれば、リン酸亜鉛処理されて
も、また、特に鋼材とともに同一のラインでリン酸亜鉛
処理されても、更に、リン酸亜鉛処理浴にフリーフッ素
イオンが添加されたとしても、Al合金材表面からのAlイ
オンの溶出を抑えることのできるAl合金材を提供するこ
とができる。したがって、Al合金材の機能を向上させる
とともに、用途を拡げることができる点で、多大な工業
的価値を有するものである。According to the present invention, even if zinc phosphate treatment is carried out, and particularly if zinc phosphate treatment is carried out on the same line with steel, free fluorine ions are further added to the zinc phosphate treatment bath. Even so, it is possible to provide an Al alloy material capable of suppressing the elution of Al ions from the surface of the Al alloy material. Therefore, it has a great industrial value in that the function of the Al alloy material can be improved and its use can be expanded.
【図１】リン酸亜鉛処理液中での、水和酸化物皮膜を設
けたAl合金材の自然電位と、Alの水和酸化物皮膜を設け
ないAl合金材の自然電位の時間的な経緯を示す説明図で
ある。FIG. 1 shows the time course of the natural potential of an Al alloy material provided with a hydrated oxide film and the natural potential of an Al alloy material not provided with a hydrated oxide film of Al in a zinc phosphate treatment solution. FIG.
a:水和酸化物皮膜を設けたAl合金材の自然電位、b:Alの
水和酸化物皮膜を設けないAl合金材の自然電位a: Natural potential of Al alloy material provided with hydrated oxide film, b: Natural potential of Al alloy material not provided with Al hydrated oxide film
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ２５Ｄ 13/00 Ｃ２５Ｄ 13/00 Ｎ ３０８ ３０８Ｃ // Ｂ０５Ｄ 7/14 １０１ Ｂ０５Ｄ 7/14 １０１Ｚ (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 22/00 - 22/86 B05D 7/14 101 C25D 11/04 303 C25D 13/00 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI C25D 13/00 C25D 13/00 N 308 308C // B05D 7/14 101 B05D 7/14 101Z (58) Fields surveyed (Int. Cl. 7 , DB name) C23C 22/00-22/86 B05D 7/14 101 C25D 11/04 303 C25D 13/00
Claims (4)
ムの溶出を防止したアルミニウム合金材であって、表面
にアルミニウムの水和酸化物皮膜が設けられるととも
に、該皮膜を有するアルミニウム合金材のリン酸亜鉛処
理液中における自然電位が、同一条件で測定した、アル
ミニウムの水和酸化物皮膜を設けないアルミニウム合金
材の最も低い自然電位よりも、100mV 以上高いことを特
徴とするリン酸亜鉛処理用アルミニウム合金材。1. An aluminum alloy material which prevents elution of aluminum when treated with zinc phosphate, wherein a hydrated oxide film of aluminum is provided on the surface, and the aluminum alloy material having the film is phosphorous. The natural potential in the zinc oxide treatment liquid is 100 mV or more higher than the lowest natural potential of an aluminum alloy material without an aluminum hydrated oxide film, measured under the same conditions, for zinc phosphate treatment. Aluminum alloy material.
厚が100 〜10000 Åである請求項１に記載のリン酸亜鉛
処理用アルミニウム合金材。2. The aluminum alloy material for zinc phosphate treatment according to claim 1, wherein the thickness of the hydrated oxide film of aluminum is 100 to 10,000 °.
る請求項１または２に記載のリン酸亜鉛処理用アルミニ
ウム合金材。3. The aluminum alloy material for zinc phosphate treatment according to claim 1, wherein the aluminum alloy material is for a transport machine.
３のいずれか１項に記載のリン酸亜鉛処理用アルミニウ
ム合金材。4. The aluminum alloy material for zinc phosphate treatment according to claim 1, wherein the transporter is an automobile.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19346799A JP3217768B2 (en) | 1999-07-07 | 1999-07-07 | Aluminum alloy material for zinc phosphate treatment |
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