JPH0426748A - Flux for hot dip zn-al alloy plating - Google Patents
Flux for hot dip zn-al alloy platingInfo
- Publication number
- JPH0426748A JPH0426748A JP12696690A JP12696690A JPH0426748A JP H0426748 A JPH0426748 A JP H0426748A JP 12696690 A JP12696690 A JP 12696690A JP 12696690 A JP12696690 A JP 12696690A JP H0426748 A JPH0426748 A JP H0426748A
- Authority
- JP
- Japan
- Prior art keywords
- flux
- alloy plating
- plating
- hot dip
- test
- 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 37
- 230000004907 flux Effects 0.000 title claims abstract description 24
- 229910000838 Al alloy Inorganic materials 0.000 title 1
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 229910007570 Zn-Al Inorganic materials 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 6
- 239000010959 steel Substances 0.000 abstract description 6
- 238000011282 treatment Methods 0.000 abstract description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 2
- 235000019270 ammonium chloride Nutrition 0.000 abstract 2
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Coating With Molten Metal (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、鉄鋼材料等に溶融Ｚｎ−Ａｊ！合金めっき処
理を施す際に用いるめっき用フラックスに関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides molten Zn-Aj! This invention relates to a plating flux used when performing alloy plating treatment.
従来、鉄鋼材料等の腐食を防止することを目的として、
その表面に溶融亜鉛めっき並びに電気亜鉛めっきを施す
ことが知られている。Traditionally, for the purpose of preventing corrosion of steel materials,
It is known to apply hot-dip galvanizing and electrogalvanizing to the surface.
また最近では、亜鉛めっき処理を下地として、更にその
上に表面処理、例えば塗装・加工等の後処理を加味する
ことによって、市場には新しく付加価値の高い商品が数
多く進出するようになり、これ等の商品に対する利用者
の選択も益々多様化してきている。Recently, many new products with high added value have entered the market by using zinc plating as a base and adding surface treatments such as painting and finishing. Users' choices regarding products such as these are becoming increasingly diverse.
これらの要求を満足させるため溶融亜鉛めっき処理品に
ついても、そのめっき浴組成としての添加元素と添加量
の選択により、めっき層の特性向上を図ることがかなり
行われてきた。In order to satisfy these demands, considerable efforts have been made to improve the properties of the galvanized layer by selecting the additive elements and amounts added in the plating bath composition for hot-dip galvanized products.
とりわけ、めっき層の耐食性を確保するために、ｉを０
．１〜２０重量％程度添加しためっき浴が知られている
。このめっき浴は、通常、鉄鋼部品等の被処理物にそれ
を７０℃程度のＺｎＣＥ ２水溶液中に浸漬するなどに
よりフラックス処理をした後、使用されている。In particular, in order to ensure the corrosion resistance of the plating layer, i is set to 0.
．． Plating baths containing about 1 to 20% by weight of C are known. This plating bath is usually used after subjecting objects to be treated, such as steel parts, to flux treatment by immersing them in an aqueous ZnCE 2 solution at about 70°C.
ところが、このようにして製造されるめっき処理品には
、めっき層がのらず不めっきを生じ易い。However, the plated product manufactured in this way does not have a plating layer and is likely to be unplated.
この不めっきの問題を解消するために、従来、（１）ア
ンモニウム塩を含まず、フン化物を主成分とするフラッ
クス（特開昭６０−１２５３６１号、特開昭５８１８５
７５６号など）や（２１ＡＡ’より活性なアルカリ土属
の塩化物などを主成分としたり、有機酸のアンモニウム
塩を主成分とするフラックス（特開昭５８１３６７５９
号、特開平１−２８３３５３号）などが提案されている
。In order to solve this problem of non-plating, (1) a flux containing no ammonium salt and containing fluoride as a main component (JP-A-60-125361, JP-A-58185
No. 756, etc.), fluxes containing alkaline earth chlorides more active than 21AA' as main components, or fluxes containing ammonium salts of organic acids as main components (JP-A-58136759).
No. 1-283353), etc. have been proposed.
しかしながら、これらのフラックスのうち、（１）のも
のは、含有されるフン化物の強い腐食性のために、フラ
ックス槽の材質に高価なものが要求され、設備やその維
持にコストがかかるのみならず、非常に有害なガスが発
生するので作業環境に対する対策が必要となる。また、
（２）のものは、上記不めっきの問題を充分解消し得な
い。However, among these fluxes, (1) requires an expensive material for the flux tank due to the strong corrosivity of the fluoride it contains, and the equipment and maintenance costs are high. First, extremely harmful gases are generated, so measures must be taken to protect the working environment. Also,
The method (2) cannot sufficiently solve the problem of non-plating.
本発明は、上記従来の問題点に鑑み、フン化物を含有し
ないで、不めっきを生ぜしめない溶融Ｚｎ−Ａ１合金め
っき用フラックスを提供することを目的とする。In view of the above conventional problems, an object of the present invention is to provide a flux for hot-dip Zn-A1 alloy plating that does not contain fluorides and does not cause non-plating.
〔課題を解決するための手段〕
上記目的を達成するために、本発明者等は種々研究を重
ねた結果、旧Ｃβ３および従来、めっき浴中の八βと反
応して、フラックス作用を低減するのみならず、不めっ
きを生じ易いとされていたＮＨ４，ＣＡが鉄鋼部品等の
被処理物へのＺｎ−Ａｊｌ！合金の密着性を向上させ得
ることを見出したものである。[Means for Solving the Problems] In order to achieve the above object, the present inventors have conducted various studies and found that the former Cβ3 reacts with the octaβ in the conventional plating bath to reduce the flux effect. Not only that, but NH4 and CA, which are thought to easily cause unplating, can be applied to Zn-Ajl! on workpieces such as steel parts! It has been discovered that the adhesion of the alloy can be improved.
即ち、本発明の熔融Ｚｎ−Ａｌ合金めっき用フラックス
は、０．０１〜２５重量％のＢｉＣｊ２．および残部Ｎ
Ｈ，，Ｃ１からなるものである。That is, the flux for molten Zn-Al alloy plating of the present invention contains 0.01 to 25% by weight of BiCj2. and remainder N
It consists of H,,C1.
また、本発明は、溶融Ｚｎ−Ａ７＋合金めっき用フラッ
クスとして、前記本発明フラックスを水に溶解して水溶
液としたものでもある。この水溶液中の前記本発明フラ
ックスの濃度は、好ましくは２５０〜１０００ ｇ ／
Ａである。この水溶液には、その作成時易溶性とする
ため塩酸などが適宜添加されてもよい。The present invention also provides an aqueous solution by dissolving the above-mentioned flux of the present invention in water as a flux for molten Zn-A7+ alloy plating. The concentration of the flux of the present invention in this aqueous solution is preferably 250 to 1000 g/
It is A. Hydrochloric acid or the like may be appropriately added to this aqueous solution to make it easily soluble during preparation.
本発明のフラックスの用途を溶融７．ｎ−Ａ１合金めっ
きとし、亜鉛めっき浴中にＡβを含有せしめたのは、め
っき層の耐食性を維持するためである。7. Melting uses of the flux of the present invention. The reason for using n-A1 alloy plating and containing Aβ in the zinc plating bath is to maintain the corrosion resistance of the plating layer.
そのＡｌ量は０．１〜２０重量％が好ましい。０．１重
量％未満では上記の耐食性を維持する効果が少なく、ま
たＡｌの含有量が２０重量％を超えても耐食性のより一
層の向上が得られ難くなると共に、めっき浴の融点が上
昇するため作業性が悪くなるからである。The amount of Al is preferably 0.1 to 20% by weight. If the Al content is less than 0.1% by weight, the effect of maintaining the above-mentioned corrosion resistance will be small, and if the Al content exceeds 20% by weight, it will be difficult to further improve the corrosion resistance, and the melting point of the plating bath will increase. This is because workability deteriorates.
本発明のフラックス中にＢｉ（Ｊ！＋とＮｌ＋４（ｌを
含有せしめることにより、これらの作用が相俟ってＺｎ
−Ａ １合金めっき層と鉄鋼部品等の被処理物との密着
性を改善せしめる。By including Bi(J!+ and Nl+4(l) in the flux of the present invention, these effects work together to reduce Zn.
-A 1 Improves the adhesion between the alloy plating layer and the workpiece such as steel parts.
ＢｉＣｌ３は、被処理物表面上で
２Ｂｉ” ＋３Ｆｅ’−”２Ｂｉ’ ＋３Ｆｅ”なる
反応を起し、析出して該表面を覆ったビスマス層がＺｎ
−Ａｊ！合金めっき浴の被処理物への濡れ性を向上させ
るものと考えられる。上記反応は、比較的低温でも十分
に進み、常温下でも短時間でフラックス処理が可能であ
る。ＢｉＣｌ３の含有量が０．０１重量％未満では、上
記作用が十分利用できず、一方、２５重量％を超えると
、含有されるＮＨ，ＣＡの量が少量に過ぎ、この作用（
後記）が十分利用できない。BiCl3 causes a reaction of 2Bi"+3Fe'-"2Bi'+3Fe" on the surface of the workpiece, and the bismuth layer that precipitates and covers the surface becomes Zn.
-Aj! It is thought that this improves the wettability of the alloy plating bath to the workpiece. The above reaction proceeds satisfactorily even at a relatively low temperature, and flux treatment can be carried out in a short time even at room temperature. If the content of BiCl3 is less than 0.01% by weight, the above effect cannot be fully utilized. On the other hand, if it exceeds 25% by weight, the amount of NH and CA contained is too small, and this effect (
(see below) are not fully available.
また、ＮＨ，（Ｊは、被処理物表面上でＮＨ４（Ｊ！
→ＮＨｆｆ ＋ ）Ｉｃ ｆｆなる反応で分解したり
、被処理物上に生じるスケール・スマットとの
Ｆｅ、、Ｏｎ ＋ ８ＮＨａ、Ｃ１２＋ Ｆｅ−４Ｆｅ
ＮＨ３ＣＥ ｚ ＋ ４ Ｎｌ＋３ ＋ ４Ｈ２０Ｆｅ
Ｃｊ！ ２ ・ＦｅＯ＋２ＮＨ，ＣＡ −２ＦｅＮＨ３
ＣＡ ２ ＋）１２０なる反応で低沸点の錯塩が生成し
たりして、起った沸騰と発泡および不めっきを生じさせ
ていたスケール・スマットの分解がＺｎ−Ａｊｌ！合金
めっき浴と被処理物との接触を良好ならしめるものと考
えられる。In addition, NH, (J is NH4 (J!
→NHff + ) Ic ff Fe decomposes through the reaction, and with scale and smut generated on the treated object, On + 8NHa, C12+ Fe-4Fe
NH3CE z + 4 Nl+3 + 4H20Fe
Cj! 2 ・FeO+2NH, CA -2FeNH3
The decomposition of scale and smut that caused boiling, foaming, and non-plating was caused by the formation of complex salts with low boiling points in the reaction CA 2 +) 120, which caused Zn-Ajl! This is thought to improve contact between the alloy plating bath and the workpiece.
〔実施例〕
実施例、比較例
ＪＩＳ ）１２１０７の規定による蒸溜亜鉛地金（一種
）および純度９９．９重量％以上のアルミニウム地金を
用いて、第１表に示す量のＡｊ！！を含有し、残部Ｚｎ
および不可避不純物からなる組成の溶融亜鉛めっき浴を
２０番の黒鉛坩堝中で電気炉を用いて５２０℃にて溶製
した。[Example] Example, Comparative Example Using a distilled zinc ingot (type) according to the provisions of JIS) 12107 and an aluminum ingot with a purity of 99.9% by weight or more, Aj! in the amount shown in Table 1 was used. ! with the remainder being Zn
A hot-dip galvanizing bath having a composition consisting of and unavoidable impurities was melted at 520° C. in a No. 20 graphite crucible using an electric furnace.
一方、板厚３．２ｆｉの一般構造用圧延鋼板より板幅７
５ｍｍ、板長１５０ 富＊の試験片を切り出し、その試
験片の表面を加熱した水酸化ナトリウムの１０重重量水
溶液で脱脂した後、１２重量％の塩酸溶液中に３０分間
浸漬することにより試験片の表面を酸洗し、更に、７０
°Ｃ（但し、試験階３および１２は１５℃）に加熱した
、第１表に示す組成および濃度のフランクス水溶液中に
９０秒間（但し、試験隘８は５秒間）浸漬して引上げる
ことによってフラックス処理を施し、最後に２００℃に
保持された恒温槽中で５分乾燥することによって溶融亜
鉛めっき処理品に対する不めっきの度合を評価するため
の試験片を準備した。On the other hand, the plate width is 7.
A test piece with a thickness of 5 mm and a plate length of 150 mm was cut out, the surface of the test piece was degreased with a heated 10 weight aqueous solution of sodium hydroxide, and then the test piece was immersed in a 12 weight % hydrochloric acid solution for 30 minutes. Pickle the surface of
By immersing it in a Franks aqueous solution with the composition and concentration shown in Table 1 heated to 15°C for test floors 3 and 12 for 90 seconds (5 seconds for test floor 8) and then pulling it out. A test piece was prepared for evaluating the degree of non-plating with respect to a hot-dip galvanized product by performing flux treatment and finally drying for 5 minutes in a constant temperature bath maintained at 200°C.
次いで、上記のようにあらかじめ溶製された溶融亜鉛め
っき浴の温度を第１表の浴温度に調整し、めっき浴表面
のドロスを除去し、上記のように調製された試験片をめ
っき浴中に浸漬し、再びめっき浴表面のドロスを除去し
て上記試験片をめっき浴より引上げたのち空冷すること
により、めっき処理の施された試験片を採取した。Next, the temperature of the hot-dip galvanizing bath prepared in advance as described above was adjusted to the bath temperature shown in Table 1, dross on the surface of the plating bath was removed, and the test piece prepared as above was placed in the plating bath. After removing the dross on the surface of the plating bath again, the test piece was pulled out of the plating bath and cooled in air, thereby obtaining a plated test piece.
これらの試験片の不めっきの度合を目視により観察した
。その結果、実施例の試験片（試験ｍ１〜１２）にはす
べて不めっきが認められなかったのに対して、比較例の
試験片（試験階１３〜１８）にはすべて不めっきが認め
られた。The degree of non-plating of these test pieces was visually observed. As a result, no plating was observed in any of the test pieces of the example (tests m1 to 12), whereas no plating was observed in all of the test pieces of the comparative example (test floors 13 to 18). .
また、以上の実施例の試験片（試験階１〜１２）に対し
てＪＩＳ ｌ＋ ０４０１の規定によるハンマー試験お
よびＪＩＳ Ｚ ２３７１の規定による塩水噴霧試験（
試験時間１．０００時間）を行なった。その結果、いず
れの試験片においても密着性および耐食性が良好である
ことが確認された。In addition, the test pieces of the above examples (test floors 1 to 12) were subjected to a hammer test according to the provisions of JIS l+ 0401 and a salt spray test according to the provisions of JIS Z 2371 (
Test time: 1,000 hours). As a result, it was confirmed that all the test pieces had good adhesion and corrosion resistance.
以上から明らかなように、本発明によりフッ化物を含有
せず、常温下、短時間で処理しても不めっきを生ぜしめ
ない、溶融Ｚｎ−Ａｌ合金っきに用いて好適なフラック
スを提供することができる。As is clear from the above, the present invention provides a flux suitable for use in molten Zn-Al alloy plating that does not contain fluoride and does not cause unplated surfaces even when processed at room temperature for a short time. be able to.
特許出願人 住友金属鉱山株式会社Patent applicant: Sumitomo Metal Mining Co., Ltd.
Claims (2)
Ｈ＿４Ｃｌからなる溶融Ｚｎ−Ａｌ合金めっき用フラッ
クス。1.0.01-25% by weight BiCl_3 and balance N
Flux for hot-dip Zn-Al alloy plating consisting of H_4Cl.
溶融Ｚｎ−Ａｌ合金めっき用フラックス。2. A flux for hot-dip Zn-Al alloy plating, which is an aqueous solution in which the flux according to claim 1 is dissolved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12696690A JPH0426748A (en) | 1990-05-18 | 1990-05-18 | Flux for hot dip zn-al alloy plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12696690A JPH0426748A (en) | 1990-05-18 | 1990-05-18 | Flux for hot dip zn-al alloy plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0426748A true JPH0426748A (en) | 1992-01-29 |
Family
ID=14948305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12696690A Pending JPH0426748A (en) | 1990-05-18 | 1990-05-18 | Flux for hot dip zn-al alloy plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0426748A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057940A1 (en) * | 2002-01-10 | 2003-07-17 | Umicore | Preparation of steel surfaces for single-dip aluminium-rich zinc galvanising |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58136759A (en) * | 1982-02-05 | 1983-08-13 | Mitsui Mining & Smelting Co Ltd | Flux for coating with zinc-aluminum alloy by hot dipping |
-
1990
- 1990-05-18 JP JP12696690A patent/JPH0426748A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58136759A (en) * | 1982-02-05 | 1983-08-13 | Mitsui Mining & Smelting Co Ltd | Flux for coating with zinc-aluminum alloy by hot dipping |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003057940A1 (en) * | 2002-01-10 | 2003-07-17 | Umicore | Preparation of steel surfaces for single-dip aluminium-rich zinc galvanising |
| US7160581B2 (en) | 2002-01-10 | 2007-01-09 | Umicore | Preparation of steel surfaces for single-dip aluminium-rich zinc galvanising |
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