JPH11264088A - Pretreating method of surface treatment of aluminum alloy member - Google Patents

Pretreating method of surface treatment of aluminum alloy member

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Publication number
JPH11264088A
JPH11264088A JP8809398A JP8809398A JPH11264088A JP H11264088 A JPH11264088 A JP H11264088A JP 8809398 A JP8809398 A JP 8809398A JP 8809398 A JP8809398 A JP 8809398A JP H11264088 A JPH11264088 A JP H11264088A
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treatment
aluminum alloy
alloy member
surface
mass
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Japanese (ja)
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Kendou So
Shinobu Suzuki
建堂 蘇
忍 鈴木
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Sumitomo Light Metal Ind Ltd
住友軽金属工業株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a pretreating method for a surface treatment of a Si- containing aluminum alloy capable of reducing to the utmost a generation of a gaseous NOx and also capable of a short time treatment at normal temp. and capable of increasing a washing effect and capable of improving operating property and productivity.
SOLUTION: As the pretreatment of the surface treatment such as anodic oxidation treatment, plating treatment, chemical conversion treatment of the silicon-containing aluminum alloy, the treatment with a washing agent soln. consisting of three components of nitric acid (60% HNO3), ammonium bifluoride (NH4F-HF) and acetic acid (CH3COOH) and consisting of a mixed soln. prepared so that a concn. of ≥50 mass% nitric acid (60% HNO3), ≥10 mass% ammonium bifluoride and 5-20 mass% acetic acid is obtained is adopted.
COPYRIGHT: (C)1999,JPO

Description

【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【発明の属する分野】本発明は、Siを含有するアルミニウム合金部材の表面処理の前処理方法、とくに、Si The present invention FIELD OF THE INVENTION, pretreatment method for the surface treatment of aluminum alloy member containing Si, in particular, Si
を含有するアルミニウム合金の鋳造品、ダイカスト品、 Casting of aluminum alloy containing, die cast product,
もしくは粉末合金製品を対象とし、これらのアルミニウム部材に対して陽極酸化皮膜、めっき皮膜あるいはいは化成皮膜を均一に生成するための前処理方法に関する。 Or a powdered alloy products intended, the anodized film to these aluminum members, plating film Aruiwai relates pretreatment method for uniformly generating a conversion coating.

【0002】 [0002]

【従来技術の説明】自動車およびコンピーター関連部材として用いられるアルミニウム合金の鋳造品、ダイカスト品または粉末合金製品においては、鋳造性の改善や材料強度の向上のため、Siが合金成分として添加されている。 BACKGROUND Description of the casting automotive and con Peter associated member aluminum alloy used as in the die cast product or powder alloy products, for the improvement of improvement and material strength of castability, Si is added as an alloying element there. Siの添加量は、鋳造品及びダイカスト品では1 The addition amount of Si is 1 in casting and die casting
2mass%以下、粉末合金製品では30mass%以下であるが、これらのアルミニウム部材に陽極酸酸化処理などの表面処理を行うに先立って、通常の酸性またはアルカリ性洗浄液で前処理を施すと、Siはアルミニウムより溶解・酸化されにくいため、材料表面にSiが濃縮してその後の表面処理性が劣化し、均一な表面処理皮膜が得られないという問題がある。 2mass% or less, in the powder alloy products is less than 30 mass%, prior to performing the surface treatment such as anodized oxidation treatment to these aluminum members, when pretreated in the usual acidic or alkaline washing solution, Si aluminum more because hardly dissolved and oxidized, then the surface treatment property deteriorates and Si are concentrated on the surface of the material, there is a problem that uniform surface treatment film can not be obtained.

【0003】この問題を解決するために、アルミニウム合金部材の表面層に存在するSiを前処理という形で選択除去してから表面処理を施すことによって、表面処理皮膜を均一に生成させる手法が採られている。 [0003] In order to solve this problem, by performing the surface treatment of Si existing on the surface layer of the aluminum alloy member after selecting removed in the form of pre-treatment, adopted is a method of uniformly generating a surface treatment film It is. この手法に従い、Siを含有するアルミニウム合金の鋳造品、ダイカスト品、粉末合金製品に陽極酸化処理、めっき処理、化成処理を施すに際し、前処理の手法でこれらの製品の表面層に存在するSiを選択除去することにより、 In accordance with this technique, casting the aluminum alloy containing Si, die cast, anodized in powder alloy products, plating, upon performing chemical conversion treatment, the Si existing on the surface layer of these products in the pretreatment method by selective removal,
陽極酸化皮膜、めっき皮膜あるいは化成皮膜を均一に生成することが可能となる。 Anodized film, plated film or the chemical conversion film makes it possible to uniformly generate.

【0004】従来、Siを選択除去するための前処理技術としては、濃硝酸(例えば60%HNO 3 )にフッ酸(例えば約40g/l)またはフッ化物を添加した2元系溶液中に浸漬処理を行う方法がよく知られている。 Conventionally, as a pre-treatment technique for selectively removing the Si, concentrated nitric acid (e.g., 60% HNO 3) in hydrofluoric acid (e.g., about 40 g / l) or immersion fluoride binary system solution was added how to do the processing is well known.
(特開平9−1319号公報など) (Such as JP-A 9-1319 Patent Publication)

【0005】しかしながら、この方法を使用した場合には、まず、硝酸とアルミニウムの反応による有毒ガスN However, when using this method, firstly, toxic gas by the reaction of nitric acid and aluminum N
Oxの大量発生が避けられないという難点があり、さらに、フッ酸によるSiの溶解反応には大きな放熱を伴うため、溶解時に局所的な液温上昇が生じ、これによって不均一なエッチングが起こり、洗浄後の材料表面は凹凸となって、このままの表面に陽極酸化処理、めっき処理あるいは化成処理を行うと、均一な皮膜が得られないという問題が生じる。 There is a drawback that outbreak of Ox is unavoidable, furthermore, since with a large heat dissipation in the dissolution reaction of Si with hydrofluoric acid, topical liquid temperature rise occurs at the time of dissolution, thereby occur uneven etching, material surface after washing becomes uneven, anodizing the surface of the left, when the plating treatment or chemical treatment, a problem that uniform film can not be obtained.

【0006】上記の問題を解決するために、本発明者らは、NOxガスの発生を避け且つ表面処理性を向上させるアルミニウム合金部材の表面洗浄剤について鋭意研究を行った結果、硝酸に添加されるフッ化物としてフッ化水素アンモニウムを採用し、さらに酢酸を添加することにより、発生したNOxガスがアンモニアによって無害のN 2ガスに還元されること、並びに、酢酸の添加によって表面温度を均一に保つことができるというシリコンウェハーの表面平滑化処理に関する分野で得られた知見が、とくに一定条件下でアルミニウム合金部材の前処理洗浄に効果的に応用することができることを見出した。 [0006] In order to solve the above problems, the present inventors have found that intensive were studied surface cleaners of the aluminum alloy member to improve the avoiding and surface treatment of the generation of NOx gas, is added to the nitric acid that the ammonium hydrogen fluoride was used as the fluoride, by further addition of acetic acid, the generated NOx gas is reduced to harmless N 2 gas with ammonia, as well as to keep the surface temperature uniform by the addition of acetic acid it findings of field of surface smoothing treatment of silicon wafers that can be found that can be effectively applied to pre-treatment cleaning of the aluminum alloy member, especially under certain conditions.

【0007】 [0007]

【発明が解決しようとする課題】本発明は、上記の知見に基づいてなされたものであり、その目的は、硝酸とフッ酸またはフッ化物の2元系溶液を用いた従来の前処理方法に代わり、生産現場で問題なく採用することができるアルミニウム合金部材の表面処理の前処理方法、詳しくは、NOxガスの発生を極力低減するとともに、常温での短時間処理を可能にし、これによって洗浄効果の向上及び操業性並びに生産性の改善を図ることを可能とするSi含有アルミニウム合金部材の表面処理の前処理方法を提供することにある。 [SUMMARY OF THE INVENTION The present invention has been made based on the above findings, and its object is to conventional pretreatment method using the binary solution of nitric acid and hydrofluoric acid or fluoride Alternatively, the pretreatment method for the surface treatment of aluminum alloy member can be employed without problems in the manufacturing site, details, as well as reduced as much as possible generation of NOx gas, to allow short treatment at normal temperature, whereby the cleaning effect to provide a pretreatment method for surface treatment improved and workability as well as possible to improve the productivity and to Si-containing aluminum alloy member.

【0008】 [0008]

【課題を解決するための手段】本発明によれば、以下のようなアルミニウム合金部材の表面処理の前処理方法が提供される。 According to the present invention SUMMARY OF], preprocessing method for the surface treatment of aluminum alloy member described below is provided. 本発明において、アルミニウム部材とは、 In the present invention, the aluminum member,
素材形状のもの、半製品形状のもの、製品形状のものを含む。 Those of the material shape, the semi-finished product shape ones, including those of the product shape. (1)Siを含有するアルミニウム合金部材の表面処理に先立って、アルミニウム合金部材の表面を硝酸、フッ化水素アンモニウム、酢酸を含む溶液により洗浄処理するアルミニウム合金部材の表面処理の前処理方法。 (1) Prior to the surface treatment of the aluminum alloy member containing Si, nitric surface of the aluminum alloy member, ammonium bifluoride, pretreatment method for the surface treatment of aluminum alloy member to washing treatment with a solution comprising acetic acid.

【0009】(2)洗浄処理溶液が、硝酸(60%HN [0009] (2) washing treatment solution, nitric acid (60% HN
3 )、フッ化水素アンモニウム(NH 4 F・HF)、 O 3), ammonium hydrogen fluoride (NH 4 F · HF),
及び酢酸(CH 3 COOH)の3成分を含有してなり、 And it contains the three components of acetic acid (CH 3 COOH),
硝酸(60%HNO 3 )が50mass%以上、フッ化水素アンモニウムが10mass%以上、及び酢酸が5 Nitric acid (60% HNO 3) is 50 mass% or more, ammonium bifluoride is 10 mass% or more, and acetic acid 5
〜20mass%の濃度になるように調製された混合溶液であるアルミニウム合金部材の表面処理の前処理方法。 Pretreatment method for the surface treatment of aluminum alloy member is a mixed solution prepared to a concentration of ~20mass%.

【0010】(3)アルミニウム合金部材が、鋳造品、 [0010] (3) aluminum alloy member, castings,
ダイカスト品、または粉末合金製品であるアルミニウム合金部材の表面処理の前処理方法。 Pretreatment method for the surface treatment of aluminum alloy member is a die casting or powder alloy products.

【0011】(4)アルミニウム合金部材の表面処理が、陽極酸化処理、めっき処理または化成処理であるアルミニウム合金部材の表面処理の前処理方法。 [0011] (4) the surface treatment of aluminum alloy member, anodizing pretreatment method for the surface treatment of aluminum alloy member is a plating process or chemical conversion process.

【0012】 [0012]

【発明の実施の形態】本発明に係る前処理方法の処理対象材となるアルミニウム合金部材は、Siを含有するアルミニウム合金部材、とくに高Siアルミニウム合金部材であり、例えば、JIS H8603で3種(b)に分類されているSi8%以上を含有する鋳造材(AC4 Processed material to become aluminum alloy member of the pretreatment method according to the embodiment of the present invention is an aluminum alloy member containing Si, a particularly high Si aluminum alloy member, for example, three in JIS H8603 ( cast material containing Si8% or more are classified into b) (AC4
A、AC4B、AC4C、AC8A、AC8B、AC8 A, AC4B, AC4C, AC8A, AC8B, AC8
C)、ダイカスト材(ADC10、ADC12)、及びSi20%〜40%を含有するAl−Si系粉末合金材等である。 C), die-cast material (ADC10, ADC12), and a Al-Si system powder alloy material or the like containing Si20% to 40%.

【0013】シリコンウェハーの表面平滑化処理に関する分野では、酢酸の添加によってフッ化水素酸によるS [0013] In the field related to surface smoothing treatment of silicon wafers, S with hydrofluoric acid by the addition of acetic acid
iの溶解放熱が奪われ、外気中に放出されやすくなるため、10℃〜30℃で処理してもシリコンウェハーの表面温度を均一に保つことができるという知見が得られている。 i dissolution heat radiation is deprived, it becomes more likely to be released into the outside air, it has been obtained findings that it is possible to maintain the surface temperature of the silicon wafer be treated at 10 ° C. to 30 ° C. uniform. 硝酸、フッ化水素アンモニウム、酢酸を含む溶液によるSiを含むアルミニウム合金部材の処理において、本発明者らは、とくに一定条件下でアルミニウム合金部材の表面処理の前処理洗浄に効果的に応用することができることを見出したが、Siの選択除去を行うためには、まず酢酸添加の場合の処理条件を適切に調整することが好ましく、そのためには、硝酸に対するフッ化水素アンモニウムの濃度比を適切にする必要がある。 Nitrate, ammonium bifluoride, in treatment of aluminum alloy member containing Si with a solution containing acetic acid, the present inventors have effectively applied to the pre-treatment cleaning of the surface treatment of aluminum alloy member, especially under certain conditions Although found that it is, in order to perform the selective removal of Si is preferably appropriately adjusting the process conditions in the case of first acid addition. for this purpose, appropriately concentration ratio of ammonium bifluoride for nitrate There is a need to.

【0014】例えば、硝酸に対するフッ化水素アンモニウムの濃度比が大きすぎると、硝酸によるアルミニウムの不働態化反応よりもフッ化イオンによるアルミニウムの溶解反応のほうが激しくなるため、洗浄処理後の材料表面には、除去されたSiの周辺にアルミニウムの溶解と思われる大きな穴が存在することになる。 [0014] For example, when the concentration ratio of ammonium bifluoride for nitrate is too large, than the passivation reaction of the aluminum with nitric acid is towards the dissolution reaction of aluminum fluoride in ion intensified, the material surface after cleaning It would have a large hole seems to dissolution of aluminum present in the periphery of the Si removed.

【0015】このままの表面に陽極酸化皮膜、めっき皮膜あるいは化成皮膜を均一に生成させるには、さらに化学研磨、ショットブラスト、バレル研磨等の手段による表面の平滑化処理が必要となるが、本発明によれば、硝酸に対するフッ化水素アンモニウムの濃度比を適切に調整することにより、除去されたSiの周辺に大きな穴があくこと自体が防止できる。 The anodic oxide film on the surface of the left, in order to uniformly generate a plating film or the chemical conversion film further chemical polishing, shot blasting, smoothing of the surface by means of barrel polishing or the like but is required, the present invention According to, by properly adjusting the concentration ratio of ammonium bifluoride for nitrate prevents itself significant pitting it around the Si which is removed. 従って、本発明を採用した場合には、化学研磨またはショットブラスト、バレル研磨などの表面平滑化処理が不要となり、前処理洗浄だけでも均一な陽極酸化皮膜、めっき皮膜あるいは化成皮膜が簡易に得られることになる。 Therefore, in the case of employing the present invention, chemical polishing or shot blasting, surface smoothing treatment such as barrel polishing becomes unnecessary, pre-treatment cleaning alone uniform anodized film, plated film or conversion coating can be obtained in a simple It will be.

【0016】また、本発明によれば、発生したNOxガスがアンモニアによって無害のN 2ガスに還元されるが、50〜80℃の処理温度において、処理時間が1分以上になるとアンモニアによる還元効果が小さくなる。 [0016] According to the invention, generated NOx gas is reduced to harmless N 2 gas with ammonia, at a treatment temperature of 50 to 80 ° C., the reduction with ammonia the treatment time is 1 minute or more effect It becomes smaller.
特に、処理を終了し、処理材を前処理液から引き上げる際に、高温の金属表面が空気に接触するとNOxガスが激しく発生する。 In particular, the process is terminated when the pulling up the treatment material from the pretreatment liquid, the hot metal surfaces NOx vigorous gas generated upon contact with air. 従って、フッ化水素アンモニウムを添加する場合には、常温処理を可能にするために、前処理液及び前処理条件を適切な領域に調整することが必要となる。 Therefore, in case of adding ammonium hydrogen fluoride, in order to allow for room temperature processing, it is necessary to adjust the pre-treatment liquid and pretreatment conditions in a suitable area.

【0017】好ましい前処理洗浄溶液としては、硝酸(60%HNO 3 )、フッ化水素アンモニウム(NH 4 [0017] Preferred pre-treatment cleaning solution, nitric acid (60% HNO 3), ammonium hydrogen fluoride (NH 4
F・HF)、及び酢酸(CH 3 COOH)の3成分を含有し、硝酸(60%HNO 3 )が50mass%以上、 F · HF), and contains three components of acetic acid (CH 3 COOH), nitric acid (60% HNO 3) is 50 mass% or more,
フッ化水素アンモニウムが10mass%以上、及び酢酸が5〜20mass%の濃度になるように調製された混合溶液が適用され、この溶液により10〜30℃の液温度範囲で1〜3分の処理を行うのが好ましい。 Ammonium bifluoride is 10 mass% or more, and acetic acid is applied mixed solution prepared to a concentration of 5~20Mass%, the process of 1-3 minutes at a liquid temperature range of 10 to 30 ° C. The solution preferably carried out.

【0018】上記の前処理条件に従った場合には、とくに、NOxガスの発生を低減できることに加え、常温で短時間の処理を行うことができ、これによって洗浄効果の向上及び操業性並びに生産性が改善できる。 [0018] When according to the above pretreatment conditions, particularly, in addition to being able to reduce the generation of NOx gas, the processing of short time at normal temperature can be performed, thereby improving the washing effect and operability and productivity sex can be improved.

【0019】以下、実施例により本発明を説明する。 [0019] The present invention will be described by way of examples. 実施例1 前処理液の組成、すなわち、[硝酸(60%HN The composition of Example 1 treatment solution, i.e., [nitrate (60% HN
3 ):フッ化水素アンモニウム(NH 4 F・HF): O 3): ammonium hydrogen fluoride (NH 4 F · HF):
酢酸(CH 3 COOH)]の3元系溶液の濃度は、図1 The concentration of the ternary solution of acetic acid (CH 3 COOH)], as shown in FIG. 1
の斜線に示される範囲で最適化される。 It is optimized in the range shown in the shaded. 代表例として、 As a typical example,
図2〜6に、図1の〜組成の溶液を用い、液温20 Figure 2-6, with a solution of ~ composition of FIG. 1, the liquid temperature 20
℃で、2分の洗浄処理を施したADC12ダイカスト品(Si:10.5mass%、Cu:2.5mass ℃ In, ADC 12 the die cast product was subjected to cleaning treatment for 2 minutes (Si: 10.5mass%, Cu: 2.5mass
%、残りAlおよび不純物)の表面状態を示す。 %, It shows the surface condition of the remaining Al and impurities).

【0020】組成の溶液を用いた場合と比較して、 [0020] Compared with the case of using the solution composition,
組成(酢酸<5mass%)または組成(硝酸<50 Composition (acetate <5 mass%) or composition (nitrate <50
mass%)の溶液では、アルミニウムをも激しく侵食するため、均一な洗浄表面が得られなかった。 In the solution of mass%), to severely erode even aluminum, uniform cleaning surface can not be obtained. また、 Also,
組成(酢酸>20mass%)または組成(フッ化水素アンモニウム<10mass%)の溶液を用いた場合には、Siを選択的に除去することができなかった。 Composition in the case of using the solution of (acetate> 20 mass%) or composition (ammonium hydrogen fluoride <10 mass%) were unable to selectively remove the Si. このような結果から、前処理液として使用する場合には、 From these results, when used as a pretreatment liquid,
[(硝酸>50mass%)+(フッ化水素アンモニウム>10mass%)+(5mass%<酢酸<20m [(Nitrate> 50 mass%) + (ammonium hydrogen fluoride> 10mass%) + (5mass% <acetic acid <20 m
ass%)=100mass%]の液組成が効果的なことがわかる。 ass%) = liquid composition of 100 mass%] is effective it can be seen.

【0021】実際に、上記〜組成の溶液で前処理し、陽極酸化処理すると、では均一なアルマイト皮膜が得られるのに対し、及び液組成の場合には、アルミニウム合金が激しく侵食されるため、均一な厚膜のアルマイト皮膜が得られない。 [0021] In fact, pre-treated with a solution of the above-composition, when anodized, to the the uniform anodized aluminum film is obtained, and in the case of the liquid composition, since aluminum alloy is severely eroded, not anodized aluminum film having a uniform thick film can be obtained. また、及び液組成の場合には、Siを選択的に除去する効果が少ないために、 Moreover, and in the case of a liquid composition, for the effect of selectively removing the Si is small,
Siの偏析部にアルマイト皮膜が生成せず、均一で良質なアルマイト皮膜が得られない。 Si anodized aluminum film in segregation is not generated in the not uniform and high quality anodized aluminum film is obtained.

【0022】実施例2 実施例1と同じ組成を有するADC12ダイカスト品を[70mass%硝酸+20mass%フッ化水素アンモニウム+10mass%酢酸]の組成の溶液にて、液温20℃で、0〜5分の洗浄処理を施した後、陽極酸化処理を行った。 [0022] with a solution of the composition of Example 2 Example 1 ADC12 die cast article having the same composition [70 mass% nitric acid + 20 mass% ammonium bifluoride + 10 mass% acetic acid, at a liquid temperature 20 ° C., of 0-5 minutes was subjected to washing treatment was subjected to anodic oxidation treatment. 生成した陽極酸化皮膜の膜厚及び均一性(膜厚変動係数)を図7に示す。 Film thickness and uniformity of the resulting anodic oxide film (film thickness variation coefficient) shown in FIG. 陽極酸化皮膜の均一性については、洗浄時間1分の場合、膜厚の変動係数が最も小さいが、洗浄時間が3分以上になると膜厚の変動係数が大きくなり、皮膜の生成が不均一となる。 The uniformity of the anodic oxide film, if the cleaning time 1 minute, but the variation coefficient of the thickness of the smallest coefficient of variation of thickness when the washing time is more than 3 minutes is increased, generation of coating and non-uniform Become. 従って、 Therefore,
本発明の前処理液を使用する際、1〜3分の洗浄時間が効果的であり、優れた皮膜の均一性が得られる。 When using the pretreatment liquid of the present invention, the washing time of 1-3 minutes is effective, the resulting uniformity of the film excellent.

【0023】なお、「膜厚変動係数」は、アルマイト皮膜の膜厚をパ−マスコープ測定器にて10点測定して得られた平均値及び標準偏差値を、(標準偏差値/平均膜厚)×100%で算出することにより求められる。 [0023] Incidentally, "thickness variation coefficient" is Pa the film thickness of the anodized aluminum film - Masukopu average obtained by measuring 10 points by the measuring instrument and the standard deviation, (standard deviation / average thickness ) it is determined by calculating in × 100%.

【0024】実施例3 実施例1と同じ組成を有するADC12ダイカスト品を[70mass%硝酸+20mass%フッ化水素アンモニウム+10mass%酢酸]の組成の溶液にて、液温5〜30℃で、2分の洗浄処理を施した後、陽極酸化処理を行った。 [0024] with a solution of the composition of Example 3 Example 1 and ADC12 die cast article having the same composition [70 mass% nitric acid + 20 mass% ammonium bifluoride + 10 mass% acetic acid, at a liquid temperature of 5 to 30 ° C., 2 minutes was subjected to washing treatment was subjected to anodic oxidation treatment. 生成した陽極酸化皮膜の膜厚及び均一性(膜厚変動係数)を図8に示す。 Film thickness and uniformity of the resulting anodic oxide film (film thickness variation coefficient) shown in FIG. 8.

【0025】洗浄液の温度が10℃以上の場合、膜厚の変動係数が小さくなり、陽極酸化皮膜が均一である。 [0025] When the temperature of the cleaning liquid is above 10 ° C., a coefficient of variation of the film thickness is reduced, the anodized film is uniform. しかし、洗浄液の温度が30℃になると有毒のNOxガスが発生する。 However, toxic NOx gas is generated when the temperature of the cleaning solution is 30 ° C.. 従って、本発明の前処理液を使用する際、 Therefore, when using the treatment solution of the present invention,
10℃〜30℃の洗浄温度(液温)が効果的であり、優れた皮膜の均一性が得られる。 10 ° C. to 30 ° C. wash temperature (liquid temperature) is effective, the resulting uniformity of the film excellent.

【0026】実施例4 鋳造品(Si:12mass%、Mg:1mass%、 [0026] Example 4 castings (Si: 12mass%, Mg: 1mass%,
Cu:1mass%、残りAlおよび不純物)、ADC Cu: 1 mass%, remainder Al and impurities), ADC
12ダイカスト品(Si:12mass%、Cu:2. 12 the die cast product (Si: 12mass%, Cu: 2.
5mass%、残りAlおよび不純物)、及び粉末合金(Si:30mass%、Cu:2mass%、残りA 5 mass%, remainder Al and impurities), and powdered alloy (Si: 30mass%, Cu: 2mass%, the remainder A
lおよび不純物)を用い、[70mass%硝酸+20 Using l and impurities), [70 mass% nitric acid + 20
mass%フッ化水素アンモニウム+10mass%酢酸]の組成の溶液にて、液温20℃で、2分の洗浄処理を施した後、陽極酸化処理を行った。 At mass% ammonium bifluoride + 10 mass% acetic acid] in the composition of the solution, a liquid temperature 20 ° C., was subjected to cleaning treatment for 2 minutes, was subjected to anodic oxidation treatment. 代表例として、鋳造品の陽極酸化処理前の素材表面の断面写真(×40 Representative examples, cross-sectional photograph of the material surface before the anodic oxidation treatment of the casting (× 40
0)を図9に、陽極酸化処理後の陽極酸化皮膜の断面写真(×200)を図10に示す。 0) in FIG. 9 shows cross-sectional photographs of the anodic oxide film after anodizing treatment (× 200) in FIG. 10.

【0027】図9、図10にみられるように、本発明の洗浄方法を用いることによって、素材表面は均一となり、均一な陽極酸化皮膜が得られることがわかる。 [0027] Figure 9, as seen in FIG. 10, by using the cleaning method of the present invention, the material surface becomes uniform, it is found that a uniform anodized film is obtained. ダイカスト品、粉末合金についても、鋳造品と同様の断面形態が観察され、均一な陽極酸化皮膜が形成された。 The die cast product, for the powder alloys, similar cross-sectional configuration and casting was observed, a uniform anodized film has been formed. また、陽極酸化処理以外の表面処理、たとえば、電気クロムめっき及びクロメート化成処理に対しても、同様な結果が得られる。 The surface treatment other than the anodic oxidation treatment, for example, also for electric chromium plating and chromate conversion treatment, similar results.

【0028】比較例1 鋳造品(Si:12mass%、Mg:1mass%、 [0028] Comparative Example 1 castings (Si: 12mass%, Mg: 1mass%,
Cu:1mass%、残りAlおよび不純物)を用い、 Cu: 1 mass%, with the remainder Al and impurities),
10mass%NaOH溶液にて、液温70℃で、3 At 10 mass% NaOH solution, at a liquid temperature 70 ° C., 3
分、20mass%H 2 SO 4溶液にて、液温50℃ Min at 20mass% H 2 SO 4 solution, the liquid temperature 50 ° C.
で、3分、及び[70mass%硝酸+20mass% In 3 minutes, and [70 mass% nitric acid + 20 mass%
フッ化水素アンモニウム+10mass%酢酸]の溶液にて、液温20℃で、2分の洗浄処理をそれぞれ施した後、陽極酸化処理を行った。 With a solution of ammonium bifluoride + 10 mass% acetic acid, at a liquid temperature 20 ° C., after performing the cleaning process of 2 minutes, respectively, it was subjected to anodic oxidation treatment. アルカリ洗浄液による洗浄後の素材表面の断面写真(×400)を図11に、陽極酸化処理後の陽極酸化皮膜の断面写真(×200)を図12に示す。 Photograph of a cross section of the material surface after cleaning with an alkaline washing solution (× 400) in FIG. 11 shows cross-sectional photographs of the anodic oxide film after anodizing treatment (× 200) in FIG. 12. また、酸洗浄液による洗浄後の素材表面の断面写真(×400)を図13に、陽極酸化処理後の陽極酸化皮膜の断面写真(×200)を図14に示す。 The cross-sectional photograph of the material surface after washing with acid washing solution (× 400) in FIG. 13 shows cross-sectional photographs of the anodic oxide film after anodizing treatment (× 200) in FIG. 14. いずれも、洗浄後の素材表面は不均一であり、均一な陽極酸化皮膜は得られていない。 Both the material surface after washing is uneven, uniform anodized film can not be obtained.

【0029】実施例5 ADC12ダイカスト品(Si:10.8mass%、 [0029] Example 5 ADC12 die casting (Si: 10.8mass%,
Cu:2.5mass%、残りAlおよび不純物)を[70mass%硝酸+20mass%フッ化水素アンモニウム+10mass%酢酸]の組成の5l溶液にて、液温20℃で、2分の洗浄処理を繰り返して実施した。 Cu: 2.5 mass%, carrying out the remaining Al and impurities) in [70 mass% nitric acid + 20 mass% ammonium bifluoride + 10 mass% acetic acid] 5l solution composition, a liquid temperature 20 ° C., repeat the cleaning process 2 minutes did. 図15に、前処理液1lあたりの洗浄能力、すなわち、ADC12ダイカスト品の処理面積(m 2 /l)とそのエッチング量(g/m 2 )の関係を示す。 15, the pretreatment liquid cleaning capacity per 1l, that is, the relationship between the ADC12 processing area of the die cast product (m 2 / l) and its etching amount (g / m 2). また、洗浄前、総処理面積2.5m 2 /lと3.0m 2 /lの各時点において、それぞれの表面のSi、Fe量の変化をEPMAにて分析し、その結果を表1に示す。 Also, pre-cleaning, at each time point of the total processing area 2.5 m 2 / l and 3.0 m 2 / l, and analyzed Si of each surface, the change in the amount of Fe in EPMA, and the results are shown in Table 1 .

【0030】 [0030]

【表1】 [Table 1]

【0031】洗浄前のものと比較して、総処理面積が2.5m 2 /lに達した時点、ADC12ダイカスト品中のSi及びFe量が選択除去により減少するが、総処理面積が2.5m 2 /lを越えると本発明の洗浄液の洗浄能力が低下する。 [0031] Compared to the previous cleaning, when the total processing area reaches 2.5 m 2 / l, but Si and Fe content in the ADC12 die cast product is reduced by selective removal, total processing area 2. exceeds 5 m 2 / l cleaning ability of the cleaning solution of the present invention is reduced. これに対し、洗浄液中にフッ化水素アンモニウムを補給することによって、液の洗浄能力を回復することができる。 In contrast, by replenishing ammonium hydrogen fluoride in the cleaning liquid, it is possible to recover the cleaning capability of the liquid.

【0032】 [0032]

【発明の効果】本発明によれば、アルミニウム合金部材の表面に存在するSiを均一に選択除去させることができるため、均一でかつ欠陥の少ない陽極酸化皮膜、めっき皮膜、及び化成皮膜が簡易に得られる。 According to the present invention, it is possible to uniformly select remove Si existing on the surface of the aluminum alloy member, uniform and less anodized film defective plating film, and conversion coating in a simple can get. また、常温で短時間の処理が可能であるため、生産現場の安全性、操業性、及び生産性が向上される。 Further, since it is possible to process a short time at room temperature, the safety of the production site, operability, and productivity is improved.

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

【図1】 前処理液の組成、すなわち、[硝酸(60% [1] Composition of the pretreatment liquid, i.e., [nitric acid (60%
HNO 3 ):フッ化水素アンモニウム(NH 4 F・H HNO 3): ammonium hydrogen fluoride (NH 4 F · H
F):酢酸(CH 3 COOH)]の3元系溶液の濃度を三角座標で示した相図である。 F): a phase diagram showing the concentration of ternary solution of acetic acid (CH 3 COOH)] in a triangular coordinate. 図1中、斜線で示される範囲は、条件が最適化された範囲であり、本発明の対象となる範囲である。 In Figure 1, the range shown by oblique lines is the range where conditions are optimized, a range for the present invention.

【図2】 図1中ので示される組成の溶液を用い、液温20℃で、2分の洗浄処理を施したADC12ダイカスト品の表面状態を示す電子顕微鏡写真である。 [Figure 2] solution composition using a indicated by the in FIG. 1, a liquid temperature 20 ° C., which is an electron micrograph showing the ADC12 surface condition of the die cast product was subjected to cleaning treatment for 2 minutes.

【図3】 図1中ので示される組成の溶液を用い、液温20℃で、2分の洗浄処理を施したADC12ダイカスト品の表面状態を示す電子顕微鏡写真である。 [Figure 3] solution composition using a indicated by the in FIG. 1, a liquid temperature 20 ° C., which is an electron micrograph showing the ADC12 surface condition of the die cast product was subjected to cleaning treatment for 2 minutes.

【図4】 図1中ので示される組成の溶液を用い、液温20℃で、2分の洗浄処理を施したADC12ダイカスト品の表面状態を示す電子顕微鏡写真である。 [4] solution composition using a indicated by the in FIG. 1, a liquid temperature 20 ° C., which is an electron micrograph showing the ADC12 surface condition of the die cast product was subjected to cleaning treatment for 2 minutes.

【図5】 図1中ので示される組成の溶液を用い、液温20℃で、2分の洗浄処理を施したADC12ダイカスト品の表面状態を示す電子顕微鏡写真である。 [5] The solution of the composition using a indicated by the in FIG. 1, a liquid temperature 20 ° C., which is an electron micrograph showing the ADC12 surface condition of the die cast product was subjected to cleaning treatment for 2 minutes.

【図6】 図1中ので示される組成の溶液を用い、液温20℃で、2分の洗浄処理を施したADC12ダイカスト品の表面状態を示す電子顕微鏡写真である。 [6] The solution composition using a indicated by the in FIG. 1, a liquid temperature 20 ° C., which is an electron micrograph showing the ADC12 surface condition of the die cast product was subjected to cleaning treatment for 2 minutes.

【図7】 実施例2で生成した陽極酸化皮膜の膜厚及び均一性(膜厚変動係数)を示すグラフである。 7 is a graph showing the film thickness and uniformity of the anodic oxide film produced in Example 2 (film thickness variation coefficient).

【図8】 実施例3で生成した陽極酸化皮膜の膜厚及び均一性(膜厚変動係数)を示すグラフである。 8 is a graph showing the film thickness and uniformity of the anodic oxide film produced in Example 3 (film thickness variation coefficient).

【図9】 実施例4で得られた陽極酸化処理前の鋳造品の表面状態を示す断面写真である。 9 is a cross-sectional photograph showing the surface condition of the casting before the anodizing treatment obtained in Example 4.

【図10】 実施例4で得られた陽極酸化処理後の鋳造品の陽極酸化皮膜を示す断面写真である。 10 is a cross-sectional photograph showing the anodized film casting after anodizing treatment obtained in Example 4.

【図11】 比較例1のアルカリ洗浄液による洗浄後の鋳造品素材表面の断面写真である。 11 is a cross-sectional photograph of the casting material surface after cleaning with an alkaline cleaning solution of Comparative Example 1.

【図12】 比較例1のアルカリ洗浄液による洗浄後の陽極酸化処理により生成した陽極酸化皮膜の断面図である。 12 is a cross-sectional view of the anodized film formed by anodic oxidation treatment after cleaning with an alkaline cleaning solution of Comparative Example 1.

【図13】 比較例1の酸洗浄液による洗浄後の鋳造品素材表面の断面写真である。 13 is a cross-sectional photograph of the casting material surface after cleaning with an acid cleaning solution of Comparative Example 1.

【図14】 比較例1の酸洗浄液による洗浄後の陽極酸化処理により生成した陽極酸化皮膜の断面図である。 14 is a cross-sectional view of the formed anodic oxide film by anodic oxidation treatment after washing by acid cleaning solution of Comparative Example 1.

【図15】 実施例5における前処理液1lあたりの洗浄能力(すなわち、ADC12ダイカスト品の処理面積(m 2 /l)とそのエッチング量(g/m 2 )の関係) [15] washing capacity per pretreatment liquid 1l in Example 5 (i.e., the relationship ADC12 processing area of the die cast product (m 2 / l) and its etching amount (g / m 2))
を示すグラフである。 It is a graph showing a.

Claims (4)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】 Siを含有するアルミニウム合金部材の表面処理に先立って、アルミニウム合金部材の表面を硝酸、フッ化水素アンモニウム、酢酸を含む溶液により洗浄処理することを特徴とするアルミニウム合金部材の表面処理の前処理方法。 1. A prior to the surface treatment of the aluminum alloy member containing Si, nitric surface of the aluminum alloy member, ammonium hydrogen fluoride, the surface of the aluminum alloy member, characterized in that the washing treatment with a solution comprising acetic acid pretreatment method of processing.
  2. 【請求項2】 溶液が、硝酸(60%HNO 3 )、フッ化水素アンモニウム(NH 4 F・HF)、及び酢酸(C 2. A solution, nitric acid (60% HNO 3), ammonium hydrogen fluoride (NH 4 F · HF), and acetic acid (C
    3 COOH)の3成分を含有してなり、硝酸(60% And also contains the three components of H 3 COOH), nitric acid (60%
    HNO 3 )が50mass%以上、フッ化水素アンモニウムが10mass%以上、及び酢酸が5〜20mas HNO 3) is 50 mass% or more, ammonium bifluoride is 10 mass% or more, and acetic 5~20mas
    s%の濃度になるように調製された混合溶液であることを特徴とする請求項1記載のアルミニウム合金部材の表面処理の前処理方法。 Pretreatment method for the surface treatment of aluminum alloy member according to claim 1, wherein the s% of a mixed solution prepared to a concentration.
  3. 【請求項3】 アルミニウム合金部材が、鋳造品、ダイカスト品、または粉末合金製品であることを特徴とする請求項1または2記載のアルミニウム合金部材の表面処理の前処理方法。 Wherein the aluminum alloy member, casting, pretreatment methods of the surface treatment according to claim 1 or 2, wherein the aluminum alloy member, characterized in that a die casting or powder alloy products.
  4. 【請求項4】 アルミニウム合金部材の表面処理が、陽極酸化処理、めっき処理または化成処理であることを特徴とする請求項1〜3のいずれかに記載のアルミニウム合金部材の表面処理の前処理方法。 Surface treatment wherein the aluminum alloy member is anodized, the pretreatment method for the surface treatment of aluminum alloy member according to claim 1, characterized in that a plating process or chemical treatment .
JP8809398A 1998-03-17 1998-03-17 Pretreating method of surface treatment of aluminum alloy member Pending JPH11264088A (en)

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US7353863B2 (en) 2003-05-13 2008-04-08 Denso Corporation Method of surface treating aluminum alloy base body of heat exchanger and heat exchanger produced by the method
JP2008150644A (en) * 2006-12-14 2008-07-03 Kobe Steel Ltd Aluminum alloy for semiconductor or liquid crystal production device, and method for producing the same
US8535400B2 (en) 2008-10-20 2013-09-17 Smith International, Inc. Techniques and materials for the accelerated removal of catalyst material from diamond bodies
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JP2012001716A (en) * 2010-05-20 2012-01-05 Mitsubishi Chemicals Corp Phosphor, method for manufacturing the same, and light-emitting device using the phosphor
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US9366090B2 (en) 2011-02-10 2016-06-14 Smith International, Inc. Kerfing hybrid drill bit and other downhole cutting tools
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US8887837B2 (en) 2011-02-10 2014-11-18 Smith International, Inc. Cutting structures for fixed cutter drill bit and other downhole cutting tools
US9347275B2 (en) 2011-06-22 2016-05-24 Smith International, Inc. Fixed cutter drill bit with core fragmentation feature
JPWO2014024651A1 (en) * 2012-08-07 2016-07-25 関西ペイント株式会社 Metal surface modification fluid and metal surface modification method
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