JPH04259393A - Zinc-nickel alloy coating bath and method for preventing precipitation of black on material to be coated - Google Patents
Zinc-nickel alloy coating bath and method for preventing precipitation of black on material to be coatedInfo
- Publication number
- JPH04259393A JPH04259393A JP2005091A JP2005091A JPH04259393A JP H04259393 A JPH04259393 A JP H04259393A JP 2005091 A JP2005091 A JP 2005091A JP 2005091 A JP2005091 A JP 2005091A JP H04259393 A JPH04259393 A JP H04259393A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- plating
- nickel
- nickel alloy
- black
- 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.)
- Granted
Links
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 25
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001556 precipitation Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 title abstract description 8
- 239000011248 coating agent Substances 0.000 title abstract 4
- 238000000576 coating method Methods 0.000 title abstract 4
- 239000000463 material Substances 0.000 title abstract 3
- -1 aliphatic amines Chemical class 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 238000007747 plating Methods 0.000 claims description 79
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 abstract description 13
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 4
- 229910007567 Zn-Ni Inorganic materials 0.000 abstract description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 abstract description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 59
- 229910052759 nickel Inorganic materials 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000011701 zinc Substances 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002526 disodium citrate Substances 0.000 description 1
- 235000019262 disodium citrate Nutrition 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- KXUSQYGLNZFMTE-UHFFFAOYSA-N hex-2-yne-1,1-diol Chemical compound CCCC#CC(O)O KXUSQYGLNZFMTE-UHFFFAOYSA-N 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、シアン化合物を含有し
ないアルカリ性めっき液を用いる亜鉛−ニッケル合金め
っき浴に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc-nickel alloy plating bath using an alkaline plating solution containing no cyanide.
【0002】0002
【従来の技術】鉄鋼製品の優れた耐蝕性を確保するため
に、表面に亜鉛−ニッケル合金めっきを施すことは公知
であり、従来の亜鉛−ニッケル合金めっき技術において
は、硫酸浴、塩酸浴、スルファミン酸浴等の酸性の電解
浴、または中性の電解浴を用いてめっきを行うのが一般
的であった。[Prior Art] It is known that zinc-nickel alloy plating is applied to the surface of steel products in order to ensure excellent corrosion resistance. Conventional zinc-nickel alloy plating techniques include sulfuric acid bath, hydrochloric acid bath, It has been common practice to perform plating using an acidic electrolytic bath such as a sulfamic acid bath or a neutral electrolytic bath.
【0003】さらに、腐食性の少ない電解液を使用する
ため、めっき設備のコスト面で酸性浴、中性浴に比べて
有利なアルカリ性浴を用いて、亜鉛−ニッケル合金めっ
きを行う方法が開発され、特開昭51−28533号公
報に開示されたが、このアルカリ性浴は、極めて毒性の
高いシアン化合物を含有するため、特別の排水処理を行
う必要が生ずるとともに、作業環境が悪化するという問
題があった。Furthermore, in order to use a less corrosive electrolyte, a method has been developed for zinc-nickel alloy plating using an alkaline bath, which is more advantageous than acidic or neutral baths in terms of the cost of plating equipment. , was disclosed in Japanese Patent Application Laid-Open No. 51-28533, but since this alkaline bath contains highly toxic cyanide, it requires special wastewater treatment and also poses problems such as deterioration of the working environment. there were.
【0004】そこで、本願発明者は、かかるアルカリ性
浴の欠点を改良し、浴の安定性に優れかつ、腐食性が低
くしかも、有毒のシアン化合物を含有しないアルカリ性
めっき液を使用して、鉄鋼製品表面に形成される合金め
っき被膜の合金比率および膜厚の優れた均一性を確保す
ることができるとともに、良好な光沢性を有する亜鉛−
ニッケル合金めっきを行うことができるめっき浴に関し
、特願昭第61−129447号(特開昭第62−28
7092号)を出願した。[0004] Therefore, the inventor of the present application improved the drawbacks of such an alkaline bath, and used an alkaline plating solution that has excellent bath stability, low corrosiveness, and does not contain toxic cyanide compounds to produce steel products. It is possible to ensure excellent uniformity in the alloy ratio and film thickness of the alloy plating film formed on the surface, and it also has good gloss.
Regarding a plating bath capable of performing nickel alloy plating, Japanese Patent Application No. 61-129447 (Japanese Unexamined Patent Publication No. 62-28
No. 7092) was filed.
【0005】しかしながら、このシアンを含まないアル
カリ性Zn−Ni合金めっき浴は、浴中金属濃度および
該アミン濃度を維持しながらめっき作業を行なっている
と、低電流密度(0.5A/dm2 以下)部分に黒色
析出が生じるという欠点があることがわかった。この原
因は、アルカリ性のめっき浴中でアミンが酸化され、又
は分解されて、その生成物が影響を及ぼしていると推定
される。However, this cyan-free alkaline Zn-Ni alloy plating bath has a low current density (0.5 A/dm2 or less) when plating is performed while maintaining the metal concentration and the amine concentration in the bath. It was found that there is a drawback that black deposits occur in some areas. The cause of this is presumed to be that the amine is oxidized or decomposed in the alkaline plating bath, and the products thereof have an effect.
【0006】この低電流密度部分の黒色析出の発生時期
は、浴中の金属成分濃度・アミンの種類や濃度・アルカ
リ濃度・アルカリ塩濃度・めっき温度・めっき作業電流
密度・陽極の種類などにより異なるが、一般にめっき開
始から作業電気量負荷が50〜300AH/l(1AH
/l=3600クーロン/l)の時点である。黒色析出
は、金属成分中のニッケル比率、アルカリ濃度・アルカ
リ塩濃度が多いほど、めっき温度・めっき作業電気量負
荷が高いほど、陽極に不溶解性のものが多いほど発生が
早まる傾向にある。[0006] The timing of occurrence of black precipitation in this low current density area varies depending on the metal component concentration in the bath, the type and concentration of amine, the alkali concentration, the alkali salt concentration, the plating temperature, the plating current density, the type of anode, etc. However, in general, the working electricity load is 50 to 300 AH/l (1 AH) from the start of plating.
/l=3600 coulombs/l). Black precipitation tends to occur more quickly as the nickel ratio, alkali concentration, and alkali salt concentration in the metal components increases, as the plating temperature and electrical load of plating work increase, and as the amount of insoluble material in the anode increases.
【0007】なお、黒色析出を一時的に解消する手段と
して、該アミンを増量する方法はあるが、さらにめっき
作業電気量が増加すると5〜30AH/l後には再び黒
色析出が発生し、これを繰り返すと最終的に、50〜2
00AH/l後には該アミンの溶解度が限界に達し、解
消不能となる。こうなると、めっき浴を新しくしないと
低電流密度部分に光沢のあるZn−Ni合金めっきが得
られなくなる。[0007] Although there is a method of increasing the amount of the amine as a means of temporarily eliminating black precipitation, if the amount of electricity used in plating work increases further, black precipitation will occur again after 5 to 30 AH/l. If you repeat it, you will finally get 50-2
After 00 AH/l, the solubility of the amine reaches its limit and cannot be resolved. In this case, unless the plating bath is renewed, a shiny Zn-Ni alloy plating cannot be obtained in the low current density area.
【0008】[0008]
【発明が解決しようとする課題】本発明は、シアンを含
まないアルカリ性Zn−Ni合金めっき浴が、低電流密
度部分において黒色析出を生じるという上記欠点を防止
することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to prevent the above-mentioned drawback that a cyan-free alkaline Zn--Ni alloy plating bath causes black precipitation in low current density areas.
【0009】[0009]
【課題を解決するための手段】本願発明者は、アセチレ
ンアルコール化合物をこのめっき浴で併用することによ
り、低電流密度部分の黒色析出の発生を無くすことがで
きることを発見し、本発明に至った。本発明のめっき浴
は、少なくとも一種類の脂肪族アミンまたはこれらのポ
リマーを含有し、pH11以上である亜鉛−ニッケル合
金めっき浴であって、アセチレンアルコール化合物を含
有することを特徴とするものである。[Means for Solving the Problems] The inventors of the present invention have discovered that by using an acetylene alcohol compound in this plating bath, it is possible to eliminate the occurrence of black precipitation in low current density areas, and have arrived at the present invention. . The plating bath of the present invention is a zinc-nickel alloy plating bath containing at least one type of aliphatic amine or a polymer thereof and having a pH of 11 or more, and is characterized by containing an acetylene alcohol compound. .
【0010】本発明の好ましい態様では、前記めっき浴
はさらに少なくとも一種類の芳香族アルデヒドを含有す
る。また、本発明の黒色析出を防止する方法は、少なく
とも一種類の脂肪族アミンまたはこれらのポリマーを含
有し、pH11以上である亜鉛−ニッケル合金めっき浴
にアセチレンアルコール化合物を添加することにより、
被めっき物上の黒色析出を防止することを特徴とする方
法である。In a preferred embodiment of the present invention, the plating bath further contains at least one aromatic aldehyde. Further, the method of preventing black precipitation of the present invention includes adding an acetylene alcohol compound to a zinc-nickel alloy plating bath containing at least one type of aliphatic amine or a polymer thereof and having a pH of 11 or higher.
This method is characterized by preventing black precipitation on the object to be plated.
【0011】本発明に使用される電解液は、電解物質と
して、 NaOH 、 KOH、 Na2CO3 、
K2CO3等を1〜300g/lの範囲で適量を含んで
いる。さらに、本発明の電解液は、ZnO 、 Zn
SO4 ・ 7H2O 、ZnCO3 、Zn(CH3
COO)2 等の亜鉛成分含有化合物と、NiCl・6
H2O、NiSO4 ・6H2O、NiCO3 、(N
H4)2Ni(SO4)2・6H2O等のニッケル成分
含有化合物を含んでいる。この場合これらの亜鉛成分含
有化合物とニッケル成分含有化合物は電解液中の亜鉛濃
度が1〜70g/l、好ましくは1〜50g/l、ニッ
ケル濃度が0.1〜118g/l、好ましくは0.1〜
10g/l、になるように、添加量を調整するのが好ま
しい。[0011] The electrolytic solution used in the present invention contains NaOH, KOH, Na2CO3,
Contains an appropriate amount of K2CO3 etc. in the range of 1 to 300 g/l. Furthermore, the electrolytic solution of the present invention contains ZnO, Zn
SO4 ・7H2O, ZnCO3, Zn(CH3
Zinc component-containing compounds such as COO)2 and NiCl.6
H2O, NiSO4 ・6H2O, NiCO3, (N
Contains a nickel component-containing compound such as H4)2Ni(SO4)2.6H2O. In this case, these zinc component-containing compounds and nickel component-containing compounds have a zinc concentration in the electrolyte of 1 to 70 g/l, preferably 1 to 50 g/l, and a nickel concentration of 0.1 to 118 g/l, preferably 0. 1~
It is preferable to adjust the amount added so that it becomes 10 g/l.
【0012】また、めっき液中の脂肪族アミンまたは、
これらのポリマーは、ニッケル成分モル濃度の等モル以
上の濃度、好ましくは5〜100g/lで添加する。ア
ミン種を2種以上添加する場合は、合算したモル濃度で
添加量を決定すれば良い。電解液に添加される脂肪族ア
ミンとしてはモノエタノールアミン、ジエタノールアミ
ン、トリエタノールアミン、エチレンジアミン、ジエチ
レントリアミン、イミノビスプロピルアミン、トリエチ
レンテトラミン、テトラエチレンペンタミン、ヘキサメ
チレンジアミン、N,N′−ビス−(3アミノプロピル
)エチレンジアミン、1,18−ジアミノ−4,8,1
1,15,−テトラアゾオクタデカン等が挙げられまた
脂肪族アミンポリマーとしては、バディッシュ社から提
供される商標名「ポリエチレンイミンG−35」、日本
触媒化学工業(株)社製の「エポミンSP、エポミンP
−1000」等のポリエチレンイミンあるいは、下記の
構造式(1)で表される3級アミンポリマー及び構造式
(2)で表される4級アミンポリマー等が挙げられる。[0012] Furthermore, an aliphatic amine in the plating solution or
These polymers are added at a concentration equal to or higher than the molar concentration of the nickel component, preferably from 5 to 100 g/l. When two or more types of amines are added, the amount to be added may be determined based on the total molar concentration. Aliphatic amines added to the electrolyte include monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, iminobispropylamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, N,N'-bis- (3aminopropyl)ethylenediamine, 1,18-diamino-4,8,1
Examples of aliphatic amine polymers include ``Polyethyleneimine G-35'' provided by Budish Co., Ltd., and ``Epomin SP'' manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd. , Epomin P
-1000'', a tertiary amine polymer represented by the following structural formula (1), a quaternary amine polymer represented by the structural formula (2), and the like.
【0013】[0013]
【化1】[Chemical formula 1]
【0014】側鎖及び数値は構造式(1)及び(2)に
共通である:
R1〜R2:H、CH3 、 C2H5 、 C3H7
R3 :(1) CH2−CH2−CH2(
2) CH2−C(OH)H−CH2 (3) C
H2CH2−O−CH2CH2(4) CH2−O−
CH2
(5) CH2−C(CH3)H−CH2(6)
CH2−C(OH)H−C(OH)H(7) CH2
CH2−C−C(OH)H(8) CH2−C(CH
3)H−C(OH)H X1、X2:無機陰イオン
n :10〜200
また、上記脂肪族アミンは、めっき液中に0.03モル
/1以上含有せしめるのが望ましい。Side chains and numerical values are common to structural formulas (1) and (2): R1 to R2: H, CH3, C2H5, C3H7
R3: (1) CH2-CH2-CH2(
2) CH2-C(OH)H-CH2 (3) C
H2CH2-O-CH2CH2(4) CH2-O-
CH2 (5) CH2-C(CH3)H-CH2(6)
CH2-C(OH)HC-C(OH)H(7) CH2
CH2-C-C(OH)H(8) CH2-C(CH
3) H-C(OH)H X1, X2: Inorganic anion n: 10-200 Further, it is desirable that the aliphatic amine is contained in the plating solution at 0.03 mol/1 or more.
【0015】本発明によればまず、 NaOH 、 K
OH、 Na2CO3 、 K2CO3等の電解物質お
よびZnO 、ZnSO4 ・7H2O、ZnCO3
、Zn(CH3COO)2 等の亜鉛成分含有化合物と
を溶解してジンケート液を建浴する。一方、少なくとも
一種類の脂肪族アミンまたは、これらのポリマーにNi
Cl・6H2O、 NiSO4・ 6H2O 、NiC
O3 、(NH4)2・Ni(SO4)2・6H2O等
のニッケル成分化合物を溶解して水溶液を調製し、この
水溶液と上記ジンケート液を混合して、めっき液を建浴
する。この場合ニッケル濃度および脂肪族アミンまたは
これらのポリマーの濃度は要求される合金化率に応じて
決定される。According to the present invention, first, NaOH, K
Electrolytes such as OH, Na2CO3, K2CO3 and ZnO, ZnSO4 ・7H2O, ZnCO3
, Zn(CH3COO)2 and other zinc component-containing compounds to prepare a zincate solution. On the other hand, at least one type of aliphatic amine or Ni
Cl・6H2O, NiSO4・6H2O, NiC
A nickel component compound such as O3, (NH4)2.Ni(SO4)2.6H2O is dissolved to prepare an aqueous solution, and this aqueous solution and the zincate solution are mixed to prepare a plating solution. In this case, the nickel concentration and the aliphatic amine or polymer concentration are determined depending on the required alloying ratio.
【0016】本発明のアセチレンアルコール化合物とし
ては、1,4−ブチンジオール、ブロバギルアルコール
、ヘキシンジオールなどが使用できる。アセチレンアル
コール化合物はめっき浴に最初から含有させても良いし
、めっき作業電気量がある程度増加した時点で添加して
も良い。また、めっき浴の作業電気量負荷が多くなり黒
色析出が発生した時点で添加すると大きな効果がある。
アセチレンアルコール化合物の添加はめっきの密着性を
低下させるので、添加量は0.01〜20g/l好まし
くは0.1〜10g/lとする。As the acetylene alcohol compound of the present invention, 1,4-butynediol, brobagyl alcohol, hexynediol, etc. can be used. The acetylene alcohol compound may be contained in the plating bath from the beginning, or may be added when the amount of electricity for plating work increases to a certain extent. Further, it is highly effective to add it when the working electrical load on the plating bath increases and black precipitation occurs. Since addition of an acetylene alcohol compound reduces the adhesion of plating, the amount added is 0.01 to 20 g/l, preferably 0.1 to 10 g/l.
【0017】このめっき液には、ヒドロキシ脂肪族カル
ボン酸またはこれらの塩を添加することができ、例えば
、酒石酸、酒石酸ナトリウム、クエン酸、クエン酸ナト
リウム、クエン酸2ナトリウム、グリコール酸、グリコ
ール酸ナトリウム等任意のものを使用することができる
。本発明のめっき浴では、この他に光沢剤として芳香族
アルデヒドや、ジメチルアミンとエピハロヒドリンとの
反応物などを一種以上単独または併用で使用できる。
なお、本発明のめっき浴に添加する光沢成分としての芳
香族アルデヒドには、バニリン、アニスアルデヒド、ピ
ペロナール、ベラトルアルデヒド、サリチルアルデヒド
、ベンズアルデヒド、P−トルアルデヒド等が含まれ、
これらのアルデヒドを一種類以上添加することが望まし
い。また、この芳香族アルデヒドは、めっき浴中に0.
02〜5g/l、好ましくは0.05〜0.5g/lと
なるよう添加する。Hydroxy aliphatic carboxylic acids or salts thereof can be added to this plating solution, such as tartaric acid, sodium tartrate, citric acid, sodium citrate, disodium citrate, glycolic acid, sodium glycolate. etc. can be used. In the plating bath of the present invention, one or more kinds of brighteners such as aromatic aldehyde and a reaction product of dimethylamine and epihalohydrin can be used alone or in combination. The aromatic aldehyde as a brightening component added to the plating bath of the present invention includes vanillin, anisaldehyde, piperonal, veratraldehyde, salicylaldehyde, benzaldehyde, P-tolualdehyde, etc.
It is desirable to add one or more of these aldehydes. Moreover, this aromatic aldehyde is present in the plating bath at 0.0%.
02 to 5 g/l, preferably 0.05 to 0.5 g/l.
【0018】[0018]
【発明の効果】本発明のめっき浴を用いれば、シアンを
含まないアルカリ性亜鉛−ニッケル合金めっき浴の欠点
であった低電流密度部分の黒色析出を解消でき、かつ、
鉄鋼製品の表面に形成された亜鉛−ニッケル合金めっき
被膜における合金比率の均一性は極めて良好であり、ま
た、そのめっき被膜は優れた均一電着性を有しており、
従ってめっき部分の全体にわたってほぼ均一な膜厚を有
しかつ光沢性の良好なめっき被膜を形成することができ
る。[Effects of the Invention] By using the plating bath of the present invention, it is possible to eliminate black precipitation in low current density areas, which was a drawback of alkaline zinc-nickel alloy plating baths that do not contain cyanide, and
The uniformity of the alloy ratio in the zinc-nickel alloy plating film formed on the surface of steel products is extremely good, and the plating film has excellent uniform electrodeposition.
Therefore, it is possible to form a plating film that has a substantially uniform thickness over the entire plating area and has good gloss.
【0019】したがって、本発明のめっき浴を使用する
ことにより、有毒なシアン化合物を加えることなく、か
つ黒色析出に妨げられることなく、めっき製品、特にプ
レス品、溶接部品、パイプ部品等の複雑な形状の製品の
品質を向上させることができる。Therefore, by using the plating bath of the present invention, it is possible to coat plated products, especially complex products such as pressed products, welded parts, pipe parts, etc., without adding toxic cyanide compounds and without being hindered by black precipitation. The shape of the product can improve its quality.
【0020】[0020]
【実施例】次に比較例と実施例により本発明を詳細に説
明する。
比較例1
亜鉛12.0g/l、ニッケル2.0g/l、 NaO
H 100g/lに、アミンとしてペンタエチレンヘキ
サミン30g/l、光沢剤としてディップソール社製N
Z−71を6ml/l含有する亜鉛−ニッケル合金めっ
き液で、めっき条件を4A/dm2 で100AH/l
のめっき作業負荷量を行った後、次いで、0.5A/d
m2 の電流をかけたところではニッケル析出率6%の
黒色析出であった。
実施例1
亜鉛12.0g/l、ニッケル2.0g/l、 NaO
H 100g/lにアミンとしてペンタエチレンヘキサ
ミン30g/l、1,4−ブチンジオール0.5g/l
、光沢剤としてディップソール社製NZ−71を6ml
/l、含有する亜鉛−ニッケル合金めっき液で、めっき
条件を4A/dm2 で100AH/lのめっき作業負
荷量を行ったところ、0.5A/dm2 ではニッケル
析出率6%の光沢のある亜鉛−ニッケルめっきが得られ
た。
実施例2
亜鉛8.0g/l,ニッケル1.0g/l、 NaOH
150g/lにアミンとしてテトラエチレンペンタミ
ン30g/l、を含有する亜鉛−ニッケル合金めっき液
でめっき条件を5A/dm2 で200AH/lのめっ
き作業負荷量を行ったところ、0.5A/dm2 でニ
ッケル析出率10%の黒色析出亜鉛−ニッケルめっきで
あったが、この時点でプロパギルアルコールを5g/l
となるよう添加したところ、ニッケル析出率10%の光
沢のある亜鉛−ニッケルめっきが得られた。EXAMPLES Next, the present invention will be explained in detail with reference to comparative examples and examples. Comparative example 1 Zinc 12.0g/l, nickel 2.0g/l, NaO
100g/l of H, 30g/l of pentaethylenehexamine as an amine, and N manufactured by Dipsol as a brightener.
Using a zinc-nickel alloy plating solution containing 6 ml/l of Z-71, the plating conditions were 4 A/dm2 and 100 AH/l.
After performing a plating workload of 0.5A/d,
When a current of m2 was applied, black deposits occurred with a nickel deposition rate of 6%. Example 1 Zinc 12.0g/l, nickel 2.0g/l, NaO
H 100g/l, amines such as pentaethylenehexamine 30g/l, 1,4-butynediol 0.5g/l
, 6ml of Dipsol NZ-71 as a brightener
When a plating work load of 100 AH/l was carried out under plating conditions of 4 A/dm2 using a zinc-nickel alloy plating solution containing 0.5 A/dm2, a shiny zinc-nickel alloy with a nickel precipitation rate of 6% was produced at 0.5 A/dm2. A nickel plating was obtained. Example 2 Zinc 8.0g/l, Nickel 1.0g/l, NaOH
When plating was performed with a zinc-nickel alloy plating solution containing 150 g/l and 30 g/l of tetraethylenepentamine as an amine at a plating condition of 5 A/dm2 and a plating work load of 200 AH/l, the plating work load was 0.5 A/dm2. It was black precipitated zinc-nickel plating with a nickel precipitation rate of 10%, but at this point, propargyl alcohol was added to 5 g/l.
When added so as to give a bright zinc-nickel plating with a nickel precipitation rate of 10%.
【0021】また、その後さらに300AH/lの作業
負荷量のめっきを行なったが、0.5A/dm2 でニ
ッケル析出率10%の光沢のある亜鉛−ニッケルめっき
を得ることができた。
実施例3
亜鉛15.0g/l、ニッケル3.0g/l、 NaO
H 100g/lにアミンとしてエチレンジアミンとエ
ピクロルヒドリンを90℃で1:2のモル比で反応させ
たものを20g/lを含有する液で、めっき条件を3A
/dm2 で75AH/lの作業負荷量のめっきを行っ
たところ0.5A/dm2 でニッケル析出率9%の黒
色析出であったが、1,4−ブチンジオールを2.0g
/l添加することにより、ニッケル析出率9%の光沢の
ある亜鉛−ニッケル合金めっきを得ることができた。
実施例4
亜鉛5.0g/l、ニッケル2.0g/l、 NaOH
200g/lにアミンとしてポリエチレンイミン(日
本触媒化学工業(株)製エポミンSP−103)を10
g/l、プロパギルアルコールを0.2g/l含有する
液で300AH/lの作業負荷量のめっきを行なったが
、0.5A/dm2 でニッケル析出率12%の光沢の
あるZn−Niめっきを得ることができた。
比較例2
トリエタノールアミン30g/l、亜鉛8g/l、ニッ
ケル1.0g/l、 NaOH 100g/lの亜鉛−
ニッケル合金めっき液で総電流0.5Aでハルセルを用
いて10分間めっきを行ったところ、高電流部側2cm
以上(1.5A/dm2 以上)ではニッケル析出率約
10%の白色析出、2cm未満ではニッケル析出率約2
0〜40%の青黒色〜ニッケル色析出のめっきであった
。
実施例5
比較例2の亜鉛−ニッケル合金めっき液に1,4−ブチ
ンジオールを5g/l添加し、総電流0.5Aで10分
間めっきを行ったところ、全面にニッケル析出率9〜1
1%の白色析出が得られた。
比較例3
トリエチレンテトラミン30g/l、亜鉛8g/l、ニ
ッケル1.5g/l、 NaOH 100g/lの亜鉛
−ニッケル合金めっき液で総電流0.2Aで10分間め
っきを行ったところ、高電流部側5cm以上(0.2A
/dm2 以上)ではニッケル析出率約15%の光沢析
出、5cm未満ではニッケル析出率20〜30%の青黒
色析出であった。
実施例6
比較例3の亜鉛−ニッケル合金めっき液に、プロパギル
アルコールを4g/l添加し総電流0.2Aで10分間
めっきを行ったところ、全面にニッケル析出率約15%
の光沢析出が得られた。After that, plating was further carried out at a working load of 300 AH/l, and a bright zinc-nickel plating with a nickel precipitation rate of 10% could be obtained at 0.5 A/dm2. Example 3 Zinc 15.0g/l, nickel 3.0g/l, NaO
Plating conditions were 3A using a solution containing 20 g/l of 100 g/l of H and 20 g/l of ethylenediamine and epichlorohydrin reacted as amines at 90°C in a molar ratio of 1:2.
When plating was carried out at a working load of 75AH/l at 0.5A/dm2, black precipitation with a nickel precipitation rate of 9% was performed, but 2.0g of 1,4-butynediol was used.
By adding /l, a bright zinc-nickel alloy plating with a nickel precipitation rate of 9% could be obtained. Example 4 Zinc 5.0g/l, nickel 2.0g/l, NaOH
10% of polyethyleneimine (Epomin SP-103 manufactured by Nippon Shokubai Chemical Co., Ltd.) was added to 200g/l as an amine.
plating was carried out with a working load of 300 AH/l using a solution containing 0.2 g/l of propargyl alcohol. I was able to get Comparative Example 2 Triethanolamine 30g/l, zinc 8g/l, nickel 1.0g/l, NaOH 100g/l zinc-
When plating was performed for 10 minutes using a Hull cell with a nickel alloy plating solution at a total current of 0.5 A, the area of 2 cm on the high current part side was
Above (1.5 A/dm2 or more), white precipitation with a nickel precipitation rate of about 10% occurs, and below 2 cm, a nickel precipitation rate of about 2
The plating was 0 to 40% blue-black to nickel colored precipitation. Example 5 5 g/l of 1,4-butynediol was added to the zinc-nickel alloy plating solution of Comparative Example 2, and plating was performed for 10 minutes at a total current of 0.5 A, resulting in a nickel precipitation rate of 9 to 1 on the entire surface.
A 1% white precipitate was obtained. Comparative Example 3 When plating was performed for 10 minutes at a total current of 0.2 A with a zinc-nickel alloy plating solution containing 30 g/l of triethylenetetramine, 8 g/l of zinc, 1.5 g/l of nickel, and 100 g/l of NaOH, a high current 5cm or more on the side (0.2A
/dm2 or more), the nickel precipitation rate was about 15%, and bright precipitation occurred, while below 5 cm, the nickel precipitation rate was 20 to 30%, blue-black precipitation. Example 6 When 4 g/l of propargyl alcohol was added to the zinc-nickel alloy plating solution of Comparative Example 3 and plating was performed for 10 minutes at a total current of 0.2 A, the nickel precipitation rate was approximately 15% on the entire surface.
A glossy deposit of .
【0022】[0022]
Claims (3)
はこれらのポリマーを含有し、pH11以上である亜鉛
−ニッケル合金めっき浴であって、アセチレンアルコー
ル化合物を含有することを特徴とする前記めっき浴。1. A zinc-nickel alloy plating bath containing at least one type of aliphatic amine or a polymer thereof and having a pH of 11 or more, the plating bath containing an acetylene alcohol compound.
の芳香族アルデヒドを含有する請求項1記載の亜鉛−ニ
ッケル合金めっき浴。2. The zinc-nickel alloy plating bath according to claim 1, wherein the electrolytic solution further contains at least one aromatic aldehyde.
はこれらのポリマーを含有し、pH11以上である亜鉛
−ニッケル合金めっき浴にアセチレンアルコール化合物
を添加して、被めっき物上に黒色析出が生じるのを防止
する方法。[Claim 3] Adding an acetylene alcohol compound to a zinc-nickel alloy plating bath containing at least one kind of aliphatic amine or a polymer thereof and having a pH of 11 or more to prevent black precipitation from occurring on the object to be plated. How to prevent it.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3020050A JP2997072B2 (en) | 1991-02-13 | 1991-02-13 | Zinc-nickel alloy plating bath and method for preventing black deposition on plating object |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3020050A JP2997072B2 (en) | 1991-02-13 | 1991-02-13 | Zinc-nickel alloy plating bath and method for preventing black deposition on plating object |
Publications (2)
Publication Number | Publication Date |
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JPH04259393A true JPH04259393A (en) | 1992-09-14 |
JP2997072B2 JP2997072B2 (en) | 2000-01-11 |
Family
ID=12016238
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1099780A2 (en) | 1999-11-10 | 2001-05-16 | Nihon Hyomen Kagaku Kabushiki Kaisha | Surface treating agent |
JP2002521572A (en) * | 1998-07-30 | 2002-07-16 | ヴァルター ヒレブラント ゲーエムベーハー ウント コー. ガルヴァノテヒニーク | Alkaline plating bath for zinc-nickel bath |
JP2008297621A (en) * | 2007-06-04 | 2008-12-11 | Shimadzu Corp | Zinc-nickel alloy plating solution and zinc-nickel alloy plating method |
-
1991
- 1991-02-13 JP JP3020050A patent/JP2997072B2/en not_active Expired - Lifetime
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002521572A (en) * | 1998-07-30 | 2002-07-16 | ヴァルター ヒレブラント ゲーエムベーハー ウント コー. ガルヴァノテヒニーク | Alkaline plating bath for zinc-nickel bath |
JP2008150713A (en) * | 1998-07-30 | 2008-07-03 | Walter Hillebrand Gmbh & Co Galvanotechnik | Alkaline plating bath tub for zinc-nickel bath and plating method |
US7807035B2 (en) | 1998-07-30 | 2010-10-05 | Ewh Industrieanlagen Gmbh & Co. Kg | Methods of plating zinc-containing coatings under alkaline conditions |
JP4716568B2 (en) * | 1998-07-30 | 2011-07-06 | ヴァルター ヒレブラント ゲーエムベーハー ウント コー. ガルヴァノテヒニーク | Alkaline plating bath for zinc-nickel bath |
US8486235B2 (en) | 1998-07-30 | 2013-07-16 | Ewh Industrieanlagen Gmbh & Co. Kg | Alkaline zinc-nickel bath |
EP1099780A2 (en) | 1999-11-10 | 2001-05-16 | Nihon Hyomen Kagaku Kabushiki Kaisha | Surface treating agent |
US6500886B1 (en) | 1999-11-10 | 2002-12-31 | Nihon Hyomen Kagaku Kabushiki Kaisha | Surface treating agent |
US7030183B2 (en) | 1999-11-10 | 2006-04-18 | Nihon Hyomen Kagaku Kabushiki Kaisha | Surface treating method and surface treating agent |
JP2008297621A (en) * | 2007-06-04 | 2008-12-11 | Shimadzu Corp | Zinc-nickel alloy plating solution and zinc-nickel alloy plating method |
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