JPS59179797A - Surface treatment of aluminum and alloy thereof - Google Patents
Surface treatment of aluminum and alloy thereofInfo
- Publication number
- JPS59179797A JPS59179797A JP5244783A JP5244783A JPS59179797A JP S59179797 A JPS59179797 A JP S59179797A JP 5244783 A JP5244783 A JP 5244783A JP 5244783 A JP5244783 A JP 5244783A JP S59179797 A JPS59179797 A JP S59179797A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- zinc
- treatment
- oxide film
- alloys
- 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.)
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Links
Landscapes
- Electrochemical Coating By Surface Reaction (AREA)
- Chemical Treatment Of Metals (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は耐食性のすぐれたアルミ製品會得るためのアル
ミニラL及びその合金の衣1m処理方法に関するもので
ちる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing aluminum oxide L and its alloy in a thickness of 1 m in order to obtain aluminum products with excellent corrosion resistance.
アルミニウム及びその合金(以下アルミ)は軽く、又適
当な表面処理ゲ施せは耐食性が向上し、電気及び熱伝達
性能にも6(れているため、建築用材、航空機用材はも
とより重工業製品、一般家庭用品などに汎用されている
のは周知の通りでちる。特に優れた熱伝達と軽量という
特性は、製品の重量減少につながり、省エネルギにもな
るので、今後益々そのオリ10分野が拡大される気運に
ある。Aluminum and its alloys (hereinafter referred to as "aluminum") are light, and with appropriate surface treatment, corrosion resistance is improved, and their electrical and heat transfer performance is also excellent.As a result, they are used not only as construction materials and aircraft materials, but also as heavy industrial products and for general household use. As is well known, it is widely used in supplies and other products.In particular, its excellent heat transfer and light weight properties lead to reduced product weight and energy savings, so its applications will continue to expand in the future. I'm in a good mood.
現在5この種のアルミ製品の防食ケ目的とした表面処理
の種類は非常に多く、それぞれの分野で実用化されてい
る。その具体例ケ挙げると次のようなものがある。Currently, there are a large number of types of surface treatments for the purpose of corrosion prevention of this type of aluminum products, and these are being put to practical use in each field. Specific examples include the following.
(1)重クロム酸塩又はクロム酸塩を含む化学処理液に
よる化成処理、
(2) 硫酸、蓚酸、クロム酸水浴液中において陽極
酸化処理音節し、その表面に外Q性の酸化皮膜全形成さ
せる。(1) Chemical conversion treatment using dichromate or a chemical treatment solution containing chromate; (2) Anodization treatment in sulfuric acid, oxalic acid, or chromic acid water bath solution, and an external Q-type oxide film is completely formed on the surface. let
(3) (11及び(2)の処理後、適当な塗装を施
す、(4) +2)の処理後、沸騰水中に浸漬したり
、水蒸気中に曝して多孔質な酸化皮膜内にアルミ水和物
ケ生成させて、細孔全室ぐことによって、耐食性ケ向上
させる(シーリング処理と称するもの)、
(5ン アルミの表面に亜鉛全数%〜10チ程度の濃
度で拡散浸透させ、その犠牲陽極作用によってアルミ全
防食する、等である。(3) (After the treatment in 11 and (2), apply an appropriate coating. (4) After the treatment in +2), immerse it in boiling water or expose it to steam to hydrate the aluminum inside the porous oxide film. The corrosion resistance is improved by forming a substance and filling all the pores (referred to as sealing treatment). This action completely protects aluminum from corrosion.
本発明は、(5)の処理の技術分野に属するものであシ
、次に示すよりな(5ンの処理の欠点全改善するもので
ある。The present invention belongs to the technical field of processing (5), and is intended to improve all the drawbacks of processing (5) as shown below.
すなわち、(5)の方法では亜鉛の犠牲陽極作用に依存
しているため、必然的に基材のアルミより早く腐食する
現象がある。このため本処理を施したアルミの表面はむ
しろ無処理のものに比べても早く白さびを発生して腐食
するので、外観が甚しく劣化する欠点がある。ただ亜鉛
が存在している間は、この腐食はその表層部に限定され
るため、内部へ深く侵入することはないが、曲鉛が消耗
し終れば、やがて腐食は内部へ侵入し大きな摺傷を与え
るアルミ特有の腐食現象が発生する。したがって、亜鉛
の効果を長時間に亘って維持するKは、その効果を利用
しながら亜鉛の消耗を極力小さくすることが大切である
が、現在のところ、この方法は開発さilでいない。That is, since the method (5) relies on the sacrificial anode action of zinc, it inevitably corrodes faster than the aluminum base material. For this reason, the surface of aluminum treated with this treatment develops white rust and corrodes more quickly than that of untreated aluminum, which has the disadvantage of severely deteriorating its appearance. However, while zinc is present, this corrosion is limited to its surface layer and does not penetrate deeply into the interior. However, once the bent lead is worn out, corrosion will eventually invade the interior and cause large scratches. A corrosion phenomenon peculiar to aluminum occurs. Therefore, it is important to use K to maintain the effect of zinc over a long period of time while minimizing the consumption of zinc as much as possible, but this method has not yet been developed.
本発明は上記亜鉛の犠牲陽極作用を利用したアルミの防
食法における欠点全改善し得る方法を開発することを目
的としたもので、亜鉛全アルミ表面に拡散浸透後、その
表面を陽極酸化処理することKよって、上記目的に達成
したものである。The purpose of the present invention is to develop a method that can overcome all the drawbacks of the above-mentioned aluminum corrosion prevention method that utilizes the sacrificial anode action of zinc. After zinc has diffused into the entire aluminum surface, the surface is anodized. Therefore, the above objective has been achieved.
本発明はアルミ基材の表面拠亜鉛を拡散浸透させ、その
表面を陽極酸化処理することによって亜鉛拡散層の上に
、亜鉛を含むアルミの酸化皮膜を形成させるものである
。すなわち本発明はアルミニウム及びその合金に亜鉛拡
散浸透処理を施し′fr:、後、その表面に陽極酸化処
理を施して、一部の亜鉛を溶出させると共にアルミニウ
ムを主成分とする酸化皮膜全形成させることによって、
拡散亜鉛濃度を制御することを特徴とする、アルミニウ
ム及びその合金の表面処理方法に関するものである。こ
の方法は、次に示すような特徴がある。In the present invention, zinc is diffused into the surface of an aluminum base material, and the surface is anodized to form an aluminum oxide film containing zinc on the zinc diffusion layer. That is, in the present invention, aluminum and its alloys are subjected to a zinc diffusion and penetration treatment, and then the surface is subjected to an anodizing treatment to elute some zinc and form an entire oxide film containing aluminum as the main component. By this,
The present invention relates to a method for surface treatment of aluminum and its alloys, which is characterized by controlling the concentration of diffused zinc. This method has the following characteristics.
(1) 亜鉛拡散を施したアルミ基材の断面における
亜鉛の濃度は、拡散条件(温度一時間)Kよって異なる
が、通常行なわれている、亜鉛を含む苛性ソーダ溶液中
にアルミを浸漬してその表面に亜鉛を析出させ、水洗後
これ全加熱して内部へ拡散浸透させる方法では表面に析
出する亜鉛の量が必らずしも−°定とならない欠点があ
る。このため、一定温度と時間で拡散処理すると、アル
ミ基材中への亜鉛の拡散浸透深さは制御できるが、最表
層部の亜鉛濃度は付着量が大なる場合は高く、付着量が
小なる場合は低くなることとなる。この現象が亜鉛の防
食作用に大きな影響を与える。(1) The concentration of zinc in a cross section of an aluminum base material subjected to zinc diffusion differs depending on the diffusion conditions (temperature for 1 hour), but the concentration of zinc in a cross section of an aluminum base material that has been subjected to zinc diffusion differs depending on the diffusion conditions (temperature for 1 hour). A method in which zinc is deposited on the surface, washed with water, and thoroughly heated to diffuse into the interior has the disadvantage that the amount of zinc deposited on the surface is not necessarily constant. Therefore, if diffusion treatment is performed at a constant temperature and time, the depth of zinc diffusion into the aluminum base material can be controlled, but the concentration of zinc in the outermost layer will be high when the amount of adhesion is large, and the amount of adhesion will be small. In this case, it will be lower. This phenomenon greatly affects the anticorrosion effect of zinc.
本発明では、上記のような状態のものでも・例えば蓚酸
中で陽極酸化処理を施すと、高濃度の亜鉛は酸化処理中
でも溶液中へ浴解し、亜鉛濃度が低下しである濃度に達
するとはじめてアルミの酸化皮膜が生成しはじめ、これ
に伴って亜鉛の溶出がとまり、それによって次のような
効果が奏せられる。In the present invention, even in the above state, for example, when anodized in oxalic acid, high-concentration zinc is dissolved into the solution even during the oxidation treatment, and the zinc concentration decreases until it reaches a certain concentration. For the first time, an oxide film on aluminum begins to form, and along with this, the elution of zinc is stopped, resulting in the following effects.
(イ) アルミ基材の亜鉛濃度をほぼ一定に保つことが
できる。(a) The zinc concentration of the aluminum base material can be kept almost constant.
(ロン その表面に形成されるアルミの酸化皮膜中に亜
鉛が含まれることとなるので、これが酸化皮膜の耐食性
向上に効果音発揮する。(Ron) Since zinc is contained in the aluminum oxide film formed on the surface, this has a sound effect in improving the corrosion resistance of the oxide film.
(ハ) アルミ製品として使用中、酸化皮膜が腐食され
ても、その直下のアルミ基材には拡散浸透した亜鉛が存
在しているため、内部へ深く侵入することはなく、亜鉛
の犠牲陽極作用は有効に利用できる。(c) Even if the oxide film is corroded during use as an aluminum product, the zinc that has diffused and penetrated into the aluminum base material directly below it will not penetrate deeply into the interior, and the sacrificial anode effect of zinc will continue. can be used effectively.
四 酸化皮膜は従来の方法によって、シーリングするこ
とが可能であるので、不発明は耐食性にすぐれた陽極酸
化皮膜と亜鉛拡散処理の両者の効果を利用することがで
きる。Since the tetraoxide film can be sealed by conventional methods, the invention can utilize the effects of both the anodic oxide film, which has excellent corrosion resistance, and the zinc diffusion treatment.
(ホ)表面の亜鉛濃度を一定に保つことができるので、
亜鉛會含む陽極酸化皮膜の質も一定に保ち得ることとな
り、品質管理75;容易で、常に良好な皮膜を得ること
が可能である。(e) Since the zinc concentration on the surface can be kept constant,
The quality of the anodic oxide film containing zinc can also be kept constant, making quality control easy and always possible to obtain a good film.
(2)本発明全実施した部材は真空容器中でカロ熱する
ような加工を加えても、亜鉛が蒸発揮散することがない
ので、その効果はカロエ上のfft[I約がない(亜鉛
拡散処理材全真空容器中でカロ熱すると、蒸気圧の高い
亜鉛が揮散するため従来はこの種の加工が実施できない
欠点力;あった)。(2) Even if a member in which the present invention is fully implemented is subjected to processing such as heating in a vacuum container, zinc does not evaporate or transpire, so the effect is that there is no fft [I approximately (zinc diffusion) When the material to be treated is heated in a fully vacuum container, zinc with a high vapor pressure evaporates, making this type of processing impossible in the past.
以上のように本発明は(1) アルミニウム及びその
合金に亜鉛拡散浸透処理を施した後、その表面に陽極酸
化処理を施して、一部の亜鉛全溶出させると共に、アル
ミニウムを主成分とする酸化皮膜全形成させることによ
って、拡散亜鉛濃度を制御することを特徴とするアルミ
ニウム及びその合金の表面処理方法に関するものである
が、不発明では、−1,た(2) 上記(1)の陽極
酸イヒ処理後、沸騰水中に浸漬しfCシ、水蒸気中に曝
すことによって酸化皮膜中に推鉛とアルミニウムの水和
物を生成させ1、その耐食性ケ向上させることもできる
。As described above, the present invention (1) performs zinc diffusion and penetration treatment on aluminum and its alloys, and then performs anodization treatment on the surface to completely elute some of the zinc, and at the same time The present invention relates to a surface treatment method for aluminum and its alloys, which is characterized by controlling the concentration of diffused zinc by forming a film on the entire surface. After the dipping treatment, hydrates of lead and aluminum can be generated in the oxide film by immersing it in boiling water and exposing it to steam, thereby improving its corrosion resistance.
更に不発明では(3) +11の処理?実施した後、
重クロム酸あるいはクロム酸ケ含む化成液中に浸漬する
ことによって酸化皮膜中の亜鉛全不溶性のクロム酸亜鉛
に変化させると共に酸化皮膜そのもの全不働態化させる
ことによって、その耐食性全向上させることもできるし
、(41(21の処理を施した後、(3)の重クロム酸
あるいはクロム酸液処理を行ない、その耐食性な向上さ
せたり、(5) (1)の処理を施した後、硅素化合
物を含む溶液中に浸漬して、酸化皮膜中に亜鉛(拡散浸
透した亜鉛の一部)、アルミニウム(酸化皮膜及び基材
の一部)、珪素化合物(珪素浸透したもの)全充填させ
、これケ沸騰水シール処理、水蒸気シール処理あるいは
重クロム酸塩などを含む化成処理液中に浸漬することに
よって、その耐食性を向上させることもできる。Furthermore, in non-invention (3) +11 processing? After implementing
By immersing the zinc in dichromic acid or a chemical solution containing chromic acid, the zinc in the oxide film is completely transformed into insoluble zinc chromate, and the oxide film itself is completely passivated, thereby improving its corrosion resistance. (41 (After performing the treatment in 21, dichromic acid or chromic acid solution treatment in (3) is performed to improve its corrosion resistance, and (5) After performing the treatment in (1), silicon compound The oxide film is completely filled with zinc (part of the diffused zinc), aluminum (the oxide film and part of the base material), and the silicon compound (silicon permeated). The corrosion resistance can also be improved by boiling water sealing treatment, steam sealing treatment, or immersion in a chemical conversion treatment solution containing dichromate or the like.
本発明における亜鉛拡散処理、陽極酸化処理等測々の処
理方法は知られており、通常行なわれる条件を採用し得
るが一般的に述べると次のようである。Various treatment methods such as zinc diffusion treatment and anodic oxidation treatment in the present invention are known, and commonly used conditions can be employed, but generally speaking, they are as follows.
(1)亜鉛置換法
アルミ及びその合金の表面を水洗した後、アルカリ(苛
性ソーダ10%)中に30秒浸漬し7CJ)、あるいは
濃硝酸(60wt%)中に2〜5秒程度浸漬し、水洗後
下記のアルカリ性液中に50秒から2分程度浸漬する。(1) Zinc substitution method After washing the surface of aluminum and its alloy with water, immerse it in alkali (caustic soda 10%) for 30 seconds (7 CJ) or in concentrated nitric acid (60 wt%) for about 2 to 5 seconds, and then wash it with water. Then, immerse it in the following alkaline solution for about 50 seconds to 2 minutes.
この操作によって、アルミ及びその合金の一部はアルカ
リに溶解するがこれに代って液中の亜鉛がアルミ及びそ
の合金の表面に析出する。Through this operation, part of the aluminum and its alloy is dissolved in the alkali, but instead, zinc in the liquid is deposited on the surface of the aluminum and its alloy.
酸化亜鉛 70〜100 t/l 液温 25℃
苛性ソーダ 400〜500 t/1
(2)亜鉛拡散処理
(11の処理を行なった後、水洗して余分なアルカリ性
液中する。この場合析出した亜鉛はアルミ上に残存して
いるので、これを電気炉中に入れて加熱すると亜鉛がア
ルミ基材中に拡散浸透する。この温度条件は目的によっ
て変化するが、一般的には、亜鉛の融点(約420℃)
以Fで行なわれる。Zinc oxide 70-100 t/l Liquid temperature 25℃
Caustic soda 400-500 t/1 (2) Zinc diffusion treatment (after performing the treatment in step 11, wash with water and soak in excess alkaline solution. In this case, the deposited zinc remains on the aluminum, so it is heated with electricity. When placed in a furnace and heated, zinc diffuses into the aluminum base material.The temperature conditions vary depending on the purpose, but in general, the melting point of zinc (approximately 420°C)
This will be done in F.
(3) 陽4′f1.酸化処理
アルミ及びその合金全陽極として、下記電解液中で電気
を流す。(3) Positive 4'f1. Oxidized aluminum and its alloys are used as anodes and electricity is applied in the following electrolyte.
蓚酸法 硫酸法 クロム酸法
(4)沸騰水、水蒸気処理
沸騰水:脱イオン水を80〜100℃とし、その中に1
0〜60分浸漬
水蒸気処理:120〜150℃の水蒸気中に20〜60
分放置
(5)重クロム酸塩、クロム酸塩
通常は重クロム酸カリ又は重クロム酸ナトリウムを用い
るが、クロム酸カリ、クロム酸ナトリウムも効果がある
。Oxalic acid method Sulfuric acid method Chromic acid method (4) Boiling water, steam-treated boiling water: Deionized water is heated to 80-100℃, and 1
0-60 minutes immersion steam treatment: 20-60 minutes in steam at 120-150℃
(5) Dichromate, Chromate Potassium dichromate or sodium dichromate is usually used, but potassium chromate and sodium chromate are also effective.
2〜4%に溶解した液に5〜20分 80〜100℃浸
漬
(6)硅素処理化合物
硫酸ナトリウムが主であるがメチルシリケート金柑いる
こともできる
不発明における亜鉛拡散処理温度とアルミ基材内部の亜
鉛濃度の分布例を第1図に示す。Immersion at 80-100℃ for 5-20 minutes in a solution dissolved at 2-4% (6) The silicon treatment compound is mainly sodium sulfate, but methyl silicate kumquat can also be used. Zinc diffusion treatment temperature and inside of aluminum substrate in the invention An example of the distribution of zinc concentration is shown in Figure 1.
図中、A、B、Cは各々300℃、40(]℃、500
℃のときの亜鉛拡散処理したときの表面の亜鉛濃度で、
温度によって相当異なる。Dは陽極酸化処理時に溶解す
る亜鉛拡散層、Eは陽極酸化皮膜の層であり、この酸化
皮膜中に亜鉛化合物が含まれている。A’、B’、G’
は上記各温度における亜鉛拡散後、陽極醸化処理したと
きの亜鉛濃度で、温度による差が小さくなっている。こ
の酸化皮膜表面の亜鉛濃度は低下しているが、アルミ基
材の腐食を防止するには十分な濃度が残っている。In the figure, A, B, and C are 300°C, 40(]°C, and 500°C, respectively.
Zinc concentration on the surface after zinc diffusion treatment at ℃,
It varies considerably depending on the temperature. D is a zinc diffusion layer that dissolves during anodizing treatment, and E is an anodic oxide film layer, and this oxide film contains a zinc compound. A', B', G'
is the zinc concentration when subjected to anodic fermentation treatment after zinc diffusion at each of the above temperatures, and the differences due to temperature are small. Although the zinc concentration on the surface of this oxide film has decreased, it remains at a sufficient concentration to prevent corrosion of the aluminum base material.
図から判るように、アルミ表面の亜鉛濃度は拡散温度(
正確には時間も影響する)によって変化する。このため
この状態ではその耐食性に差が出る(亜鉛濃度が高いと
亜鉛が早く腐食し白さびの発生原因となるj。しかし、
その後陽極酸化処理するとこの高濃度亜鉛層が溶解し、
ある程度の亜鉛濃度に低下した段階からアルミの酸化皮
膜が生成し、その後の亜鉛の溶出を防止する。このため
、不発明の陽極酸化膜と亜鉛拡散層から成る処理層が形
成される。しかも、この陽極酸化皮膜中には、亜鉛が含
まれているので、その耐食性は一層向上する。As can be seen from the figure, the zinc concentration on the aluminum surface increases at the diffusion temperature (
To be precise, it changes depending on the time (also influenced by time). Therefore, there is a difference in corrosion resistance in this state (high zinc concentration causes zinc to corrode quickly and cause white rust. However,
This highly concentrated zinc layer is then dissolved when anodized.
An aluminum oxide film forms when the zinc concentration drops to a certain level and prevents subsequent elution of zinc. Therefore, a treated layer consisting of an inventive anodic oxide film and a zinc diffusion layer is formed. Moreover, since this anodic oxide film contains zinc, its corrosion resistance is further improved.
実施例1
使用したアルミ材料はJIS H4000(1982)
規格のI[151)、3003の2種類であp5それぞ
れ巾50X長100×厚1m寸法に仕上げた。Example 1 The aluminum material used is JIS H4000 (1982)
Two types of standard I [151) and 3003 were finished in p5 dimensions of width 50 x length 100 x thickness 1 m.
該アルミ材に次の処理を順次、施した。The aluminum material was sequentially subjected to the following treatments.
(1)前処理:+04苛性ソーダ、50℃×30秒浸漬
→水洗、
(2)亜鉛置換処理:苛性ソーダ4509/l。(1) Pretreatment: +04 caustic soda, immersion at 50°C for 30 seconds → washing with water, (2) Zinc replacement treatment: Caustic soda 4509/l.
酸化亜鉛60り/lを含む
水溶液、40℃中に3分浸
漬→水洗→乾燥、
(3)亜鉛拡散処理=350℃×5h5(4) 陽極
酸化処理=4%蓚酸、25℃中で陽極として電解0.5
時間、
(5) シーリング処理:■沸騰水中60分浸漬また
は0120℃と水蒸気
中50分処理、
(4)の処理終了後のもの及び
(5)の処理後のものについて
実施例
上記処理を施したアルミ材の耐食性全試験した。耐食性
についての評価は、塩水噴霧試験J工5Z257+に規
定されている方法で連続+oooh試験し、白さびの発
生状況を調査して判定した。この試験では比較のため無
処理のまま陽極酸化後、沸騰水浸漬、あるいは水蒸気暴
露して細孔をシーリングする既知の方法及び亜鉛拡散浸
透処理したものなどを供試した。これらの塩水噴霧試験
結果を表1に示した。Aqueous solution containing 60 l/l of zinc oxide, immersed in 40°C for 3 minutes → washed with water → dried (3) Zinc diffusion treatment = 350°C x 5h5 (4) Anodizing treatment = 4% oxalic acid, 25°C as an anode Electrolysis 0.5
Time, (5) Sealing treatment: ■ 60 minute immersion in boiling water or 50 minute treatment in steam at 0120°C. The above treatment was applied to the items after the treatment in (4) and the items after the treatment in (5). All aluminum materials were tested for corrosion resistance. Corrosion resistance was evaluated by conducting a continuous +oooh test according to the method specified in Salt Spray Test J Engineering 5Z257+, and investigating the occurrence of white rust. In this test, for comparison, we used a known method of sealing the pores by anodic oxidation without any treatment, immersion in boiling water or exposure to steam, and a method of zinc diffusion infiltration treatment. Table 1 shows the results of these salt spray tests.
この結果から明らかなように、比較品は、すべてアルミ
水和物を主成分とする白さびあるいは亜鉛とアルミの水
利物よシなる白さび〜(亜鉛拡散したもの)が全面に発
生している上、不働態化していないものでは孔食の発生
が認められた。亜鉛拡散浸透材でも不働態化していない
場合は、亜鉛が完全に消失しているところでは孔食の発
生が顕著であった。As is clear from this result, all comparative products had white rust mainly composed of aluminum hydrate or white rust (zinc diffused) caused by zinc and aluminum irrigators. On the other hand, pitting corrosion was observed in the non-passivated specimens. When zinc diffusion permeation materials were not passivated, pitting corrosion was noticeable in areas where zinc had completely disappeared.
これに対し本発明品は、化成処理ケ施さない場合は、灰
白色に変色するものの白さびの発生はなく、不働態化し
たものは、殆んど異常は認められず、良好な耐食性を示
した。なお本発明材について、その断面の亜鉛濃度をX
線マイクロアナライザによって調査した結果、陽極酸化
皮膜の細孔中には亜鉛が存在し、又、酸化皮膜の直下の
アルミ基材中にも0.5〜0.5%の亜鉛が残存してい
た。したがって、さらに長時間腐食試験を実施して酸化
皮膜が消耗しても、残存亜鉛が存在している限り、その
耐食性は維持できるものである。On the other hand, when the product of the present invention is not subjected to chemical conversion treatment, it changes to a grayish white color but no white rust occurs, and when the product is passivated, almost no abnormalities are observed and it shows good corrosion resistance. . Regarding the material of the present invention, the zinc concentration in the cross section is
As a result of investigation using a wire microanalyzer, it was found that zinc was present in the pores of the anodic oxide film, and 0.5 to 0.5% zinc remained in the aluminum base material directly under the oxide film. . Therefore, even if the oxide film is consumed by conducting a corrosion test for a longer period of time, the corrosion resistance can be maintained as long as residual zinc exists.
実施例2
アルミ+D5D材料を用い、亜鉛置換条件と拡散処理条
件ケ変えたものについて、陽極酸イヒ処理を行ない、亜
鉛の濃度と拡散深さとの関係を調べた。Example 2 Using aluminum + D5D material, anodic oxidation treatment was performed on aluminum with different zinc substitution conditions and diffusion treatment conditions, and the relationship between zinc concentration and diffusion depth was investigated.
(1) 亜鉛置換処理:苛性ソーダ 450 ?/l
。(1) Zinc replacement treatment: Caustic soda 450? /l
.
酸化亜鉛 60’j/l、
浸漬温度 25℃、50℃
(2) 亜鉛拡散処理 500℃X5h 、24h4
00℃X5h
500℃X5h
(3)陽極酸化処理 4%蓚酸、25℃中で陽極として
電解05時間
亜鉛拡散処理後及び陽極酸化皮膜俊のものについて、そ
の表面の亜鉛濃度と拡散深さ2X線マイクロアナライザ
にて調査しfc。この結果會亜鉛置換処理では、同一温
度では浸漬時間が長いほどアルミ基材表面の亜鉛濃度が
高く、又拡散処理では、温度が高いほど濃度が低くなる
。Zinc oxide 60'j/l, immersion temperature 25℃, 50℃ (2) Zinc diffusion treatment 500℃X5h, 24h4
00°C x 5h 500°C x 5h (3) Anodic oxidation treatment Zinc concentration on the surface and diffusion depth after 05 hours of zinc diffusion treatment using 4% oxalic acid as anode at 25°C and with a thin anodic oxide film. Checked with analyzer and fc. As a result, in the zinc substitution treatment, the longer the immersion time at the same temperature, the higher the zinc concentration on the surface of the aluminum substrate, and in the diffusion treatment, the higher the temperature, the lower the concentration.
しかし拡散深さは長くなる。したがって、深い亜鉛拡散
層を得るには低温の場合は長時間を要1−1作業効率が
甚しく悪くなる。高温で加熱すれば深い拡散層は得られ
るが、この場合は亜鉛の拡散がアルミ基材の結晶粒界を
主として通るので、基材が脆化するおそれがある。However, the diffusion depth becomes longer. Therefore, in order to obtain a deep zinc diffusion layer, a long time is required at low temperatures, and 1-1 working efficiency becomes extremely poor. A deep diffusion layer can be obtained by heating at a high temperature, but in this case, the diffusion of zinc mainly passes through the grain boundaries of the aluminum base material, so there is a risk that the base material will become brittle.
これに対し、陽極酸化を行なうと、アルミ基材表面の亜
鉛の一部は蓚酸液中に溶出し同時にアルミの酸化皮膜が
形成されるため、亜鉛濃度は前記処理条件の差はど大き
くならず均一化する傾向にある。ことに高温で短時間拡
散したものでは、たとえアルミ基材の結晶粒界が脆弱化
していてもその表面に酸化皮膜が形成されるため、その
弱点金補うことができるので、拡散作業時間の短縮に効
果が大である。On the other hand, when anodic oxidation is performed, some of the zinc on the surface of the aluminum base material is eluted into the oxalic acid solution and an oxide film on aluminum is formed at the same time, so the difference in zinc concentration under the above treatment conditions is not large. There is a tendency towards uniformity. In particular, when diffused at high temperatures for a short period of time, even if the grain boundaries of the aluminum base material are weakened, an oxide film is formed on the surface, which can compensate for the weak points, reducing the time required for diffusion work. It is highly effective.
なお、本発明では陽極酸化処理を蓚酸溶液中で実施した
が、その性格上明らかなようにクロム酸、硫酸などの溶
液中でも可能であり、特にクロム酸中では不働態化処理
を省略できることもある(表3参照)。In the present invention, the anodizing treatment was carried out in an oxalic acid solution, but as is clear from its nature, it is also possible in solutions of chromic acid, sulfuric acid, etc., and in particular, in chromic acid, the passivation treatment may be omitted. (See Table 3).
表6 陽極酸化処理の相違による本発明の効果〔備考〕
シーリング処理条件 不働態化処理条件及び塩水噴霧に
よる腐食試験条件は
表1の場合と同様である。Table 6 Effects of the present invention due to differences in anodizing treatment [Notes]
Sealing treatment conditions The passivation treatment conditions and the salt spray corrosion test conditions are the same as in Table 1.
硫酸の場合は、亜鉛の溶出が激しいので表面の亜鉛濃度
が低下するが処理そのものは可能である。In the case of sulfuric acid, the zinc concentration on the surface decreases due to the intense elution of zinc, but the treatment itself is possible.
アルミ合金材料としてJIS H4000(19827
規格の7075のようにすてに亜鉛ケ5〜6%含むもの
に対しても処理できることは実施例1.2の結果から明
らかであるが、この種の材料はその機械的性質が105
0.5005などとかなり相違するので、この方面から
の材料選択が大切である。JIS H4000 (19827) as an aluminum alloy material
It is clear from the results of Example 1.2 that materials containing 5 to 6% zinc oxide, such as standard 7075, can be treated; however, this type of material has mechanical properties of 105%.
0.5005, etc., so it is important to select materials from this point of view.
さらに当然のことながら、本発明を実施した後、適宜塗
装することも可能である。Furthermore, as a matter of course, it is also possible to apply appropriate coating after carrying out the present invention.
実施例3
1050.6005及び5005材料を用い、実施例1
における処理(1)〜(4)ヲ行なった後、次の処理を
施し、その防食効果’1+ooohの塩水噴霧試験によ
って調査した。Example 3 Using 1050.6005 and 5005 materials, Example 1
After the treatments (1) to (4) were performed, the following treatments were performed, and the anticorrosion effect was investigated by a salt spray test of '1+oooh.
(5)3%珪酸ソーダを含む水溶液中に浸漬後引上げて
乾燥
(6)エチルシリケート溶液中に浸漬後、引上げて乾燥
(7) (5)あるいは(6〉の処理を施したものに
実施例1の(6)の不働態処理を実施。(5) Immersed in an aqueous solution containing 3% sodium silicate, then pulled up and dried. (6) Dipped in an ethyl silicate solution, pulled up and dried. (7) Examples of products treated in (5) or (6>) 1. (6) Passive treatment was carried out.
試験結果は表4に示す通りでちゃ、同条件の腐食試験を
行なっている表1の比較例に比べると格段の耐食性を発
揮している。The test results are as shown in Table 4, which shows that it exhibits much better corrosion resistance than the comparative example shown in Table 1, which was tested under the same conditions.
/
アルミ材1050と5005’(z試料として、実施例
10手順に従って、亜鉛置換処理→蓚酸中陽極酸化全行
ない、その後シーリング処理ケ行なわず、実施例1の不
動態処理金笑施した。/ Aluminum materials 1050 and 5005' (z samples were subjected to zinc substitution treatment and then anodization in oxalic acid according to the procedure of Example 10, and then subjected to the passivation treatment of Example 1 without sealing treatment.
一方、不働態処理を行なわないもの紮作製し、塩水噴霧
試験を連続+000h行なって、その耐食性を評価した
。その結果は表5に示す通りであり、不働態処理を施し
ているものには全く白さびの発生はなく良好であった。On the other hand, a ligature without passivation treatment was prepared, and a salt water spray test was conducted continuously for +000 hours to evaluate its corrosion resistance. The results are shown in Table 5, and the results were good, with no white rust occurring at all in those subjected to passivation treatment.
又、不働態処理を行なわなかったものは灰色に変色して
いたが、白さびの発生はなかった。In addition, those that were not subjected to passivation treatment were discolored to gray, but no white rust occurred.
前記表1に示したように、亜鉛拡散処理音節さなければ
陽極酸化した後、不働態化処理しても白さびの発生が認
められているので、本実施例では亜鉛拡散処理の効果と
、その後の不働態表5 不働態化処理の効果
(備考J ◎異常なし、○変色するが白さびの発生なし
実施例5
アルミ材+050.5003i供試材として実施例1の
1〜4の処理を行なった後、実施例5の5及び6の処理
を行い、その後再び実施例1の不働態化処理を行ない、
塩水噴霧試験連続tooohによって耐食性を評価した
。その結果は表6に示す通りであシ、不発明の方法を施
せばi o o ohの試験後も異常はなく、健全でAs shown in Table 1 above, if zinc diffusion treatment is not performed, white rust is observed even after anodization and passivation treatment. Therefore, in this example, the effects of zinc diffusion treatment and Subsequent passivity Table 5 Effect of passivation treatment (Note J ◎ No abnormality, ○ Discoloration but no white rust Example 5 Treatments 1 to 4 of Example 1 were applied as aluminum material + 050.5003i test material. After that, the treatments 5 and 6 of Example 5 were carried out, and then the passivation treatment of Example 1 was carried out again,
Corrosion resistance was evaluated by a continuous salt spray test. The results are as shown in Table 6. If the uninvented method is applied, there will be no abnormality after the i o o oh test, and the product will be healthy.
第1図は本発明における亜鉛拡散処理温度とアルミ基材
内部の亜鉛濃度の分布例を示す図である。
復代理人 内 1) 明
復代理人 萩 原 亮 −
第1図
表面力)らの距離FIG. 1 is a diagram showing an example of the distribution of zinc diffusion treatment temperature and zinc concentration inside an aluminum base material in the present invention. Within the sub-agent 1) Distance from the sub-agent Ryo Hagiwara - Figure 1 surface force)
Claims (6)
理を施した後、その表面に陽極酸化処理を施して、一部
の亜鉛を溶出させると共にアルミニウムを主成分とする
酸化皮膜を形成させることによって、拡散亜鉛濃度を制
御するとと全特徴とする、アルミニウム及びその合金の
表面処理方法。(1) After zinc diffusion and penetration treatment is applied to aluminum and its alloys, the surface is anodized to elute some zinc and form an oxide film containing aluminum as the main component. A method for surface treatment of aluminum and its alloys, which is characterized by controlling the zinc concentration.
理を施した後、その表面に陽極酸化処理を施して、一部
の亜鉛を溶出させると共にアルミニウムを主成分とする
酸化皮膜を形成させπ後、沸騰水中に浸漬、又は水蒸気
中に曝すことによって酸化皮膜中に亜鉛とアルミニウム
の水和物を生成させることを特徴とする、アルミニウム
及びその合金の表面処理方法。(2) After zinc diffusion and penetration treatment is applied to aluminum and its alloys, the surface is anodized to elute some zinc and form an oxide film mainly composed of aluminum. After π, boiling is performed. 1. A method for surface treatment of aluminum and aluminum alloys, the method comprising forming a hydrate of zinc and aluminum in an oxide film by immersing it in water or exposing it to steam.
理を施した後、その表面に陽極酸化処理を施して、一部
の亜鉛を溶出させると共にアルミニウムを主成分とする
酸化皮膜を形成させ、続いて重クロム酸塩もしくはクロ
ム酸塩を含む化成液中に浸漬することによって酸化皮膜
中の亜鉛を不溶性のクロム酸亜鉛に変化させると共に酸
化皮膜全不働態化させることを特徴とするアルミニウム
及びその合金の表面処理方法。(3) After zinc diffusion and penetration treatment is applied to aluminum and its alloys, the surface is anodized to elute some zinc and form an oxide film mainly composed of aluminum, and then A surface of aluminum and its alloy, characterized in that zinc in the oxide film is changed to insoluble zinc chromate and the oxide film is completely passivated by immersion in a chromate or a chemical solution containing the chromate. Processing method.
理を施した後、その表面に陽極酸化処理を施して、一部
の亜鉛を溶出させると共に、アルミニウムを主成分とす
る酸化皮膜を形成させ、続いて沸騰水中に浸漬、又は水
蒸気中に曝すことによって酸化皮膜中に亜鉛とアルミニ
ウムの水和物を生成させた後、重クロム酸塩もしくはク
ロム酸塩を含む化成液中に浸漬すること全特徴とするア
ルミニウム及びその合金の表面処理方法。(4) After zinc diffusion and penetration treatment is applied to aluminum and its alloys, the surface is anodized to elute some of the zinc and form an oxide film containing aluminum as the main component. All characteristics are that hydrates of zinc and aluminum are generated in the oxide film by immersion in boiling water or exposure to steam, and then immersion in dichromate or a chemical solution containing chromate. Surface treatment method for aluminum and its alloys.
理を施した後、その表面に陽極酸化処理を施して、一部
の亜鉛を溶出させると共にアルミニウムを主成分とする
酸化皮膜を形成させ、続いて、硅累化合物ヶ含む溶液中
に浸漬して酸化皮膜中に亜鉛、アルミニウム及び硅素化
合物を充填させ、更にその後、沸騰水シール処理、水蒸
気処理することを特徴とするアルミニウム及びその合金
の表面処理方法。(5) After zinc diffusion and penetration treatment is applied to aluminum and its alloys, the surface is subjected to anodic oxidation treatment to elute some zinc and form an oxide film mainly composed of aluminum, and then, A method for surface treatment of aluminum and alloys thereof, which comprises immersing the aluminum in a solution containing a silicon compound to fill the oxide film with zinc, aluminum and a silicon compound, and then subjecting the aluminum to a boiling water sealing treatment and a steam treatment.
理を施した後、その表面に陽極酸化処理ケ施して、一部
の亜鉛を溶出させると共にアルミニウム全生成分とする
酸化皮膜全形成させ、続いて硅素化合物を含む溶液中に
浸漬して酸化皮膜中に亜鉛、アルミニウム及び硅素化合
物を充填させ、更にその後重クロム酸もしくはクロムi
k含む化成液中に浸漬することを特徴とするアルミニウ
ム及びその合金の表面処理方法。(6) After zinc diffusion and penetration treatment is applied to aluminum and its alloys, the surface is subjected to anodization treatment to elute some zinc and form an oxide film that is the entire aluminum component, and then silicon Zinc, aluminum and silicon compounds are filled into the oxide film by immersion in a solution containing the compound, and then dichromic acid or chromium i
A method for surface treatment of aluminum and its alloys, characterized by immersion in a chemical conversion solution containing k.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5244783A JPS59179797A (en) | 1983-03-30 | 1983-03-30 | Surface treatment of aluminum and alloy thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5244783A JPS59179797A (en) | 1983-03-30 | 1983-03-30 | Surface treatment of aluminum and alloy thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59179797A true JPS59179797A (en) | 1984-10-12 |
JPS6320318B2 JPS6320318B2 (en) | 1988-04-27 |
Family
ID=12914977
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5244783A Granted JPS59179797A (en) | 1983-03-30 | 1983-03-30 | Surface treatment of aluminum and alloy thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59179797A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010265887A (en) * | 2009-03-17 | 2010-11-25 | Nuovo Pignone Spa | Method for producing protective coating for component of turbomachine, the component, and the machine |
WO2023229306A1 (en) * | 2022-05-25 | 2023-11-30 | 삼성전자 주식회사 | Aluminium alloy plate and electronic device comprising same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0430836U (en) * | 1990-07-04 | 1992-03-12 |
-
1983
- 1983-03-30 JP JP5244783A patent/JPS59179797A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010265887A (en) * | 2009-03-17 | 2010-11-25 | Nuovo Pignone Spa | Method for producing protective coating for component of turbomachine, the component, and the machine |
WO2023229306A1 (en) * | 2022-05-25 | 2023-11-30 | 삼성전자 주식회사 | Aluminium alloy plate and electronic device comprising same |
Also Published As
Publication number | Publication date |
---|---|
JPS6320318B2 (en) | 1988-04-27 |
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