CN1051584C - bronze plating solution and preparation method and application thereof - Google Patents
bronze plating solution and preparation method and application thereof Download PDFInfo
- Publication number
- CN1051584C CN1051584C CN95112538A CN95112538A CN1051584C CN 1051584 C CN1051584 C CN 1051584C CN 95112538 A CN95112538 A CN 95112538A CN 95112538 A CN95112538 A CN 95112538A CN 1051584 C CN1051584 C CN 1051584C
- Authority
- CN
- China
- Prior art keywords
- grams per
- per liter
- plating bath
- bronze
- naf
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000007747 plating Methods 0.000 title claims abstract description 22
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 18
- 239000010974 bronze Substances 0.000 title claims abstract description 18
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 4
- 238000007772 electroless plating Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003788 bath preparation Substances 0.000 claims 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 235000011150 stannous chloride Nutrition 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000001119 stannous chloride Substances 0.000 abstract 1
- 238000000280 densification Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
A bronze plating liquid for plating on metal surface is prepared from copper sulfate and stannous chloride as main salts through respectively adding EDTA as copper salt complexing agent, NaF as tin salt complexing agent, nitrilotriacetic acid and distilled water, mixing, adding citric acid as additive and peregal O. The invention can be prepared and used at normal temperature, has stable performance, does not pollute the environment, has simple process, saves energy, can plate the inner surface and the outer surface of a workpiece, can carry out chemical plating and electroplate, has bright and compact plating layer which is silvery white, resists the corrosion of dilute acid and alkali and has wide application.
Description
A kind of metallic surface coating gunmetal solution and preparation method thereof.
Conventional chemical plating fluid poor stability, the operational condition harshness, the temperature height causes metal plating procurement cost height, and big energy-consuming also has the exhaust emission environment.
Conventional plating high-tin bronze solution contains prussiate, also has the service temperature height, and big energy-consuming is to human body and the bigger defective of environmental hazard.
The purpose of this invention is to provide a kind of bronze plating bath and preparation method thereof, accomplish can to prepare and use under the normal temperature, save energy, free from environmental pollution both can electroless plating, also can electroplate.
The present invention is to be main salt with tin protochloride and copper sulfate, adds complexing agent and additive and forms, and the proportioning of each component is as follows:
Tin protochloride SnCl
22H
2O 15～40 grams per liters
Pink salt complexing agent NaF (or NH
4HF
2Or NH
4F) 10～30 grams per liters
Nitrilotriacetic acid(NTA) N (CH
2COOH)
35～20 grams per liters
Copper sulfate CuSO45H
2O 10～30 grams per liters
Mantoquita complexing agent EDTA is C
10H
14N
2O
8Na
22H
2O 10～45 grams per liters
Additive: citric acid C
6H
8O
72H
2O 3～10 grams per liters
Polyoxyethylene aliphatic alcohol ether (peregal 0) 0.2～2 grams per liter
All the other are deionized water or distilled water, PH=2～2.5.
Preparation method of the present invention is as follows:
A, pour into part distilled water or deionized water in plastic channel, Pei Zhi volume (as follows) adds mantoquita complexing agent edta salt by 10～45 grams per liters as required, constantly be stirred to dissolving fully after, add mantoquita CuSO by 10～30 grams per liters
45H
2O dissolves complexing.
B, be equipped with nitrilotriacetic acid(NTA) N (CH by 5～20 grams per liters
2COOH)
3, pack that another has in the water plastic tank and with strong aqua or sodium hydroxide and adjusts to PH=4～5 into, add pink salt complexing agent NaF (or NH by 10～30 grams per liters then
4HF
2Or NH
4F), be stirred to dissolving fully, add pink salt SnCl by 15～40 grams per liters
22H
2O, dissolve complexing after, add citric acid by 3～10 grams per liters again and after the dissolving, all pour in the plastic channel and mix in the bucket.
C, to be equipped with polyoxyethylene aliphatic alcohol ether by 0.2～2 grams per liter be peregal 0, with pouring in the plastic channel behind the hot water dissolving.
D, in the plastic channel adding distil water or deionized water to the volume that needs preparation and adjust to PH=2～2.5 with HCl or NaOH solution and get final product.
In order to make effect of the present invention better, can also in plating bath, add small amount of sodium chloride, micro-asccharin, gelatin and sea-gull washing composition.
The present invention at normal temperatures just can electroless plating low tin bronze or tinbronze as long as metal works is put into plating bath.If as anode, be negative electrode with the workpiece and pass to 0.1～0.6A/Dm with the sheet tin of different table area and copper coin
2Low-voltage DC, high-tin bronze that just can electroplating bright densification on workpiece.If after the tubular workpiece inwall penetrates aluminium wire, hang up negative electrode again, can make workpiece inwall and outside surface all plate high-tin bronze.
Compared with the prior art, the present invention has following characteristics:
1, can prepare and use at normal temperatures, stable performance, no waste gas produces, and is free from environmental pollution, do not damage human body.
2, preparation technology and using method are simple, and energy consumption is few, and the cost that obtains coating is low.
3, applied widely, can electroless plating, can electroplate again; Both the workpiece outside surface can be plated, the workpiece inwall can be plated again.
4, the densification of coating light is silvery white in color, and anti-diluted acid caustic corrosion is of many uses.
Embodiment one
The operation steps of implementing side is the same with processing step recited above, repeats no more, and its difference is the proportioning difference of each component, and the proportioning of embodiment one is as follows:
SnCl
22H
2O 40 grams per liter NaF 30 grams per liters
N (CH
2COOH)
320 grams per liter CuSO45H
2O 30 grams per liters
EDTA 45 grams per liter citric acids 10 grams per liters
Polyoxyethylene aliphatic alcohol ether 2 grams per liters
All the other are distilled water or deionized water, PH=5.5.
The proportioning of embodiment two each components is as follows:
SnCl
22H
2O 15 grams per liter NaF 10 grams per liters
N (CH
2COOH)
35 grams per liter CuSO45H
2O 10 grams per liters
EDTA 10 grams per liter citric acids 3 grams per liters
Polyoxyethylene aliphatic alcohol ether 0.2 grams per liter
All the other are distilled water or deionized water, PH=2.
The proportioning of embodiment three each components is as follows:
SnCl
22H
2O 30 grams per liter NaF 30 grams per liters
N (CH
2COOH)
315 grams per liters
CuSO45H
2O 20 grams per liters
EDTA 25 grams per liter citric acids 7 grams per liters
Polyoxyethylene aliphatic alcohol ether 1 grams per liter
All the other are distilled water or deionized water, PH=4.
The characteristics of present embodiment are that the solution long-term stability is constant, and the solution working temperature is a room temperature, change plating or adopt the acceleration electric current all not have gas to produce.When workpiece is that negative electrode passes to 0.3A/Dm
2Low-voltage DC the time, can obtain the following fine and close high-tin bronze coating of 10 micron thickness, coating imporosity, and can being plated in tube wall and the deep hole.
Claims (7)
1, a kind of metallic surface coating bronze plating bath is characterized in that the proportioning of each component is as follows: S
nCl
22H
2O 15～40 grams per liter CuSO
45H
2O 10～30 grams per liter N (CH
2COOH)
3All the other are deionized water or distilled water for 5～20 grams per liter NaF, 10～30 grams per liter citric acids, 3～10 grams per liter EDTA, 10～45 grams per liter polyoxyethylene aliphatic alcohol ethers, 0.2～2 grams per liter, PH=2～5.5.
2, bronze plating bath according to claim 1 is characterized in that pink salt complexing agent NaF can use NH
4HF
2Or NH
4F replaces.
3, bronze plating bath according to claim 1 and 2 is characterized in that the proportioning of each component is as follows: S
nCl
22H
2O 30 grams per liter CuSO
45H
2O 20 grams per liter N (CH
2COOH)
3All the other are deionized water or distilled water for 15 grams per liter NaF, 30 grams per liter citric acids, 7 grams per liter EDTA, 25 grams per liter polyoxyethylene aliphatic alcohol ethers, 1 grams per liter, PH=4.
4, a kind of metallic surface coating bronze plating bath preparation method is characterized in that processing step is as follows:
A, pour into part distilled water or deionized water in plastic channel, Pei Zhi volume (as follows) adds mantoquita complexing agent edta salt by 10～45 grams per liters as required, constantly be stirred to dissolving fully after, add mantoquita CuSO by 10～30 grams per liters
45H
2O dissolves complexing;
B, be equipped with nitrilotriacetic acid N (CH by 5～20 grams per liters
2COOH)
3Solution is packed into, and another has in the water plastic tank and with strong aqua or sodium hydroxide and adjusts to PH=4～5, adds pink salt complexing agent NaF by 10～30 grams per liters then, is stirred to dissolving fully, adds pink salt SnCl by 15～40 grams per liters
22H
2O dissolves complexing, adds citric acid in bucket by 3～10 grams per liters again, all pours in the plastic channel after the dissolving and mixes;
C, to be equipped with polyoxyethylene aliphatic alcohol ether by 0.2～2 grams per liter be peregal 0, with pouring into behind the hot water dissolving in the plastic channel;
D, in the plastic channel adding distil water or deionized water to the volume that needs preparation and adjust to PH=2～5.5 with HCl or NaOH solution and get final product.
5, bronze plating bath preparation method according to claim 4 is characterized in that pink salt complexing agent NaF can use NH
4HF
2Or NH
4F replaces.
6, bronze plating bath preparation method according to claim 4 is characterized in that also can adding small amount of sodium chloride, micro-asccharin, gelatin or sea-gull washing composition in plating bath.
7,, it is characterized in that electroless plating low tin bronze or middle tinbronze under the normal temperature, or pass to low-voltage DC plating high-tin bronze according to the application of the described bronze plating bath of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112538A CN1051584C (en) | 1995-11-10 | 1995-11-10 | bronze plating solution and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112538A CN1051584C (en) | 1995-11-10 | 1995-11-10 | bronze plating solution and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1150184A CN1150184A (en) | 1997-05-21 |
| CN1051584C true CN1051584C (en) | 2000-04-19 |
Family
ID=5079601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95112538A Expired - Fee Related CN1051584C (en) | 1995-11-10 | 1995-11-10 | bronze plating solution and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1051584C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5733429A (en) * | 1996-09-10 | 1998-03-31 | Enthone-Omi, Inc. | Polyacrylic acid additives for copper electrorefining and electrowinning |
| US6890758B2 (en) * | 2003-06-13 | 2005-05-10 | Eci Technology, Inc. | Measurement of complexing agent concentration in an electroless plating bath |
| CN104561959A (en) * | 2015-01-14 | 2015-04-29 | 江苏兴达钢帘线股份有限公司 | Accelerator for promoting formation of chemically tinned bronze alloy coat |
| CN107043947A (en) * | 2017-05-03 | 2017-08-15 | 上海电力学院 | A kind of tin graphene oxide composite plating solution and its preparation method and application |
| CN107630240B (en) * | 2017-10-30 | 2019-03-15 | 湖南金泰检测检验有限公司 | Electroplate liquid of steel and iron parts cyanideless electro-plating tin bronze and preparation method thereof and electro-plating method |
| CN111663126A (en) * | 2019-03-06 | 2020-09-15 | 唐文海 | Decorative plating process for chemically chromium-plated alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5672196A (en) * | 1979-11-19 | 1981-06-16 | Shimizu Shoji Kk | Bright plating bath for copper-tin alloy |
| CN1016351B (en) * | 1989-06-21 | 1992-04-22 | 福建省医学科学研究所 | Medical cotton stick glue |
-
1995
- 1995-11-10 CN CN95112538A patent/CN1051584C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5672196A (en) * | 1979-11-19 | 1981-06-16 | Shimizu Shoji Kk | Bright plating bath for copper-tin alloy |
| CN1016351B (en) * | 1989-06-21 | 1992-04-22 | 福建省医学科学研究所 | Medical cotton stick glue |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1150184A (en) | 1997-05-21 |
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