CN1332269A - Chemical bismuth plating process - Google Patents
Chemical bismuth plating process Download PDFInfo
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- CN1332269A CN1332269A CN 01127615 CN01127615A CN1332269A CN 1332269 A CN1332269 A CN 1332269A CN 01127615 CN01127615 CN 01127615 CN 01127615 A CN01127615 A CN 01127615A CN 1332269 A CN1332269 A CN 1332269A
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- bismuth
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Abstract
The chemical Bi plating process includes compounding the plating liquid comprising dimethyl sulfoxide as solvent, Bi salt as main salt, tartaric acid or citric acid as complexing agent, polyglycol or mannitol as stabilizer and inorganic salt of Fe, Co and Ni as sensitizer; and chemically plating of pre-treated substrate in the plating liquid. The chemical plating process in organic system can deposit silverly bright and compact Bi plating. Using the said process to replace electroplating can decrease pollution caused by Cr ions greatly and reduce cost.
Description
The present invention relates to a kind of method of metallic matrix chemical bismuth plating.
Compare with plating, chemistry is coated with following significant advantage: (1) has covering power widely, can obtain uniform coating for each position of complex part; (2) have than electroplating much good degree of depth ability, can reduce plating piece blind hole, the interior no coating phenomenon of deep hole widely.
Because the toxicity of bismuth is less, environmentally safe; The electrochemistry tagmeme of bismuth is insoluble to rare hydrochloric acid, the rare sulfuric acid or the vitriol oil between hydrogen and copper, its good corrosion resistance receives some environmental protection and electrochemist's concern in recent years, wants to replace chromium coating with plating bismuth layer.In addition, bismuth also is used for semiconductor element refrigeration.
The salt of bismuth is easy to generate alkaline bismuth salt in the aqueous solution, form precipitation, causes the bismuth metal ion significantly to descend in solution, certainly will will strengthen the acidity of plating bath, suppresses the generation of alkaline bismuth salt usually with hydrochloric acid or perchloric acid.If at the aqueous solution deposition bismuth, coating is influenced seriously by liberation of hydrogen, and the plating bath instability with electrochemical method.And adopt chemical plating method plating bismuth to yet there are no report.
The method that the purpose of this invention is to provide a kind of chemical bismuth plating, this method does not generate bismuth oxide compound and liberation of hydrogen, and bath stability, electroplates the existing the problems referred to above of bismuth thereby solve.
Chemical bismuth plating method of the present invention may further comprise the steps:
(1) pre-treatment of matrix: the pretreatment process of matrix (unplated piece) is identical with conventional plating or electroless plating, through polishing, pickling, washing, skimming treatment.
(2) preparation of plating bath: with organic solvent dimethyl sulfoxide (DMSO) (DMSO) is solvent, with bismuth salt is main salt, tartrate or citric acid are complexing agent, polyoxyethylene glycol or N.F,USP MANNITOL are stablizer, the inorganic salt of the 8th family's iron, cobalt, nickel are mixed with chemical plating bath with main salt, complexing agent, stablizer and sensitizing agent by following concentration ratio and solvent DMSO as sensitizing agent: bismuth salt 20～40gL
-1, complexing agent 15～25gL
-1, stablizer 20～25gL
-1, sensitizing agent 12.5～18gL
-1
(3) implement electroless plating: will place above-mentioned chemical plating bath plating to get final product through pretreated matrix; Service temperature (bath temperature) is controlled at 18～35 ℃ usually, and plating time is generally 5-720 minutes.
Organic solvent DMSO used in the aforesaid method preferably uses 4A activated molecular sieve drying earlier, and the compound of other band crystal water is preferably also handled through vacuum hydro-extraction earlier, is used further to prepare plating bath.
Above-mentioned said bismuth salt is generally the inorganic salt that Bismuth trinitrate, bismuth perchlorate, bismuth chloride etc. are simple, be easy to get, and is preferably Bismuth trinitrate; Said sensitizing agent is generally nickelous chloride, cobalt chloride, iron protochloride, single nickel salt, rose vitriol and ferrous sulfate etc., is preferably nickelous chloride.
In the above-mentioned technology, the optimum concentration range of bismuth salt is 25～35gL
-1The optimum concentration range of complexing agent is 15～25gL
-1The optimum concentration range of stablizer is 20～25gL
-1The optimum concentration range of sensitizing agent is 15～18gL
-1The optimum operating temperature scope is 25～30 ℃.Plating time is preferably 10-45 minutes.
The preferred solution composition proportioning of the present invention (solvent is DMSO) as shown in table 1.
Table 1
| Solution composition | Each constituent concentration (gL in the plating bath -1) | |
| Plating bath 1 | Plating bath 2 | |
| Bismuth trinitrate | ????25～35 | ????25～35 |
| Tartrate | ????15～25 | |
| Citric acid | ????15～25 | |
| Polyoxyethylene glycol | ????20～25 | |
| N.F,USP MANNITOL | ????20～25 | |
| ????NiCl 2 | ????15～18 | ????15～18 |
The present invention adopts organic system to carry out chemical bismuth plating, because of anhydrous, thus can avoid generating bismuth oxide compound and liberation of hydrogen, and bath stability.Can go out the fine and close coating of silvery white light at the plating piece surface deposition, coated metal bismuth particle is tiny, is evenly distributed.The plating bismuth of the most suitable iron of the present invention, copper matrix.The mechanism of electroless plating of the present invention (is example with the copper matrix): under the sensitizing agent effect, provide electronics by copper earlier, bismuth autocatalysis then thickens coating.
By the content of metal in Oxford ISIS 300 energy dispersive spectrometry (EDAX) the analysis coating, wherein the content of copper occupies 25%, is from matrix copper.Bismuth accounts for 75%.Do not have other metal eutectoid to go out, have only bismuth metal in the coating.
The coating of above-mentioned bismuth metal amplifies 15000 times with Hitachi S-520 scanning electronic microscope and observes sedimental configuration of surface, as shown in Figure 2.The metallic particles of coating surface bismuth is heaped tightr, and distribution uniform, particle apparent size are 200～300nm.
Analyze above-mentioned coating thing with the D/MAX-3A X-ray diffractometer and constitute mutually, as shown in Figure 3.By the d value of six main diffraction peaks among the Analysis of X RD figure, the experiment d value at first three peak is 3.3091 , 2.3767 , and 2.2872 , by the powdery diffractometry card deck (PDF) of retrieval JCPDS, the data of bismuth are 3.28
x, 2.37
4, 2.27
4 contrasts two groups of d values as can be known, and there is bismuth really in the surface of copper and is to separate out with the form of Metallic Solids.The median size of bismuth is 38nm in the coating.
Because environment goes from bad to worse, the human space of more and more paying close attention to existence.Replace existing plating chromium method with the inventive method, can significantly reduce trivalent and hexavalent chromium to the harm of human body and to the pollution of environment.The bath stability of the inventive method only needs to replenish bismuth salt, recycle, and cost is low, and is pollution-free, has remarkable economic efficiency and social benefit.
The invention will be further described below by way of embodiments and drawings.
Fig. 1 is a content energy spectrogram of analyzing metal in the coating by Oxford ISIS 300 energy dispersive spectrometry (EDAX).Wherein the content of copper occupies 25%, is from matrix copper.Bismuth accounts for 75%.Do not have other metal eutectoid to go out, have only bismuth metal in the coating.
Fig. 2 is with the sedimental surface topography map of Hitachi S-520 sem observation.After amplifying 15000 times, the metallic particles heap that can be observed the coating surface bismuth is tightr, and distribution uniform, particle apparent size are 200～300nm.
Fig. 3 is a ray powder diffraction pattern.Analyze the coating thing with the D/MAX-3A X-ray diffractometer and constitute mutually, by the d value of six main diffraction peaks among the Analysis of X RD figure, the experiment d value at first three peak is 3.3091 , 2.3767 , 2.2872 , by the powdery diffractometry card deck (PDF) of retrieval JCPDS, the data of bismuth are 3.28
x, 2.37
4, 2.27
4 contrasts two groups of d values as can be known, and there is bismuth really in the surface of copper and is to separate out with the form of Metallic Solids.The average crystal grain size (D) of bismuth can be used the halfwidth B of the strongest diffraction peak face in the coating, utilization Scherrer Equation for Calculating:
In D=K λ/(Bcos θ) formula, K is the Scherrer constant, and when B was halfwidth, K=0.89, λ were the incident wavelength of X ray.The median size that gets the bismuth metal particle according to this Equation for Calculating is 38nm.
The solution composition of the embodiment of the invention 1-15 is formed and the content proportioning, and operational condition is as shown in table 2.
Table 2
| Embodiment | Each constituent concentration (gL in the plating bath -1) | Operational condition | ||||||||
| Bismuth trinitrate | Tartrate | Citric acid | Polyoxyethylene glycol | N.F,USP MANNITOL | Nickelous chloride | Cobalt chloride | Iron protochloride | Temperature (℃) | Time (min) | |
| ?1 | ????32 | ????25 | ????25 | ??12.5 | ????25 | ????10 | ||||
| ?2 | ????32 | ????15 | ????20 | ??12.5 | ????25 | ????10 | ||||
| ?3 | ????40 | ????25 | ????25 | ???18 | ????25 | ????5 | ||||
| ?4 | ????40 | ????15 | ????22 | ???18 | ????25 | ????5 | ||||
| ?5 | ????20 | ????20 | ????20 | ???15 | ????25 | ????45 | ||||
| ?6 | ????20 | ????20 | ????25 | ???15 | ????25 | ????30 | ||||
| ?7 | ????32 | ????25 | ????20 | ??12.5 | ????28 | ????15 | ||||
| ?8 | ????32 | ????15 | ????25 | ??12.5 | ????28 | ????15 | ||||
| ?9 | ????32 | ????15 | ????25 | ????18 | ????35 | ????12 | ||||
| ?10 | ????32 | ????15 | ????20 | ????18 | ????35 | ????12 | ||||
| ?11 | ????20 | ????25 | ????25 | ????18 | ????28 | ????720 | ||||
| ?12 | ????20 | ????15 | ????22 | ????18 | ????28 | ????30 | ||||
| ?13 | ????28 | ????20 | ????20 | ????15 | ????30 | ????20 | ||||
| ?14 | ????28 | ????15 | ????22 | ????15 | ????30 | ????20 | ||||
| ?15 | ????40 | ????20 | ????25 | ????15 | ????18 | ????10 | ||||
The processing step of each embodiment is as follows:
1. the pre-treatment of reagent: used organic solvent DMSO 4A activated molecular sieve drying; The compound of band crystal water is handled through vacuum hydro-extraction.
2. the pre-treatment of matrix: identical with the substrate pretreated method of routine plating or electroless plating, be specially: metallic matrix → abrasive paper for metallograph mechanical polishing → chemical rightenning → pickling → washing → degreasing → pickling → washing → acetone is washed
3. press table 2 condition preparation plating bath.
4. will place plating bath through pretreated matrix by table 2 operational condition, can form bismuth metal coating at matrix surface.
The bismuth salt concn is high more in the plating bath, and the formation of bismuth coating is fast more; Along with the formation of bismuth coating, the bismuth salt concn can reduce in the plating bath, at this moment only needs to add bismuth salt in plating bath, makes it remain on the desired concn scope and gets final product.Plating bath can recycle continuously.
Claims (10)
1. the method for a chemical bismuth plating may further comprise the steps:
(1) pre-treatment of matrix: matrix is according to a conventional method through polishing, pickling, washing, skimming treatment;
(2) preparation of plating bath: with organic solvent DMSO is solvent, with bismuth salt is main salt, tartrate or citric acid are complexing agent, polyoxyethylene glycol or N.F,USP MANNITOL are stablizer, the inorganic salt of iron, cobalt or nickel are as sensitizing agent, main salt, complexing agent, stablizer and sensitizing agent are added among the solvent DMSO by following concentration ratio, be mixed with chemical plating bath: bismuth salt 20～40gL
-1, complexing agent 15～25gL
-1, stablizer 20～25gL
-1, sensitizing agent 12.5～18gL
-1
(3) implement electroless plating: will place above-mentioned chemical plating bath plating to get final product through pretreated matrix; Service temperature is controlled at 18～35 ℃, and plating time is 5-720 minutes.
2. in accordance with the method for claim 1, it is characterized in that used organic solvent DMSO earlier with 4A activated molecular sieve drying, the compound of other band crystal water is also handled through vacuum hydro-extraction earlier, is used further to prepare plating bath.
3. according to claim 1 or 2 described methods, it is characterized in that said bismuth salt is Bismuth trinitrate, bismuth perchlorate or bismuth chloride.
4. according to claim 1 or 2 described methods, it is characterized in that said sensitizing agent is nickelous chloride, cobalt chloride, iron protochloride, single nickel salt, rose vitriol or ferrous sulfate.
5. according to claim 1 or 2 described methods, the concentration range that it is characterized in that bismuth salt is 25～35gL
-1
6. according to claim 1 or 2 described methods, the concentration range that it is characterized in that complexing agent is 15～25gL
-1
7. according to claim 1 or 2 described methods, the concentration range that it is characterized in that sensitizing agent is 15～18gL
-1
8. according to claim 1 or 2 described methods, it is characterized in that operating temperature range is 25～30 ℃, plating time is 10-45 minutes.
9. according to claim 1 or 2 described methods, it is characterized in that solution composition is formed and concentration proportioning is: Bismuth trinitrate 25～35gL
-1, tartrate 15～25gL
-1, polyoxyethylene glycol 20～25gL
-1, NiCl
215～18gL
-1
10. according to claim 1 or 2 described methods, it is characterized in that solution composition is formed and concentration proportioning is: Bismuth trinitrate 25～35gL
-1, citric acid 15～25gL
-1, N.F,USP MANNITOL 20～25gL
-1, NiCl
215～18gL
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011276150A CN1133757C (en) | 2001-07-10 | 2001-07-10 | Chemical bismuth plating process |
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|---|---|---|---|
| CNB011276150A CN1133757C (en) | 2001-07-10 | 2001-07-10 | Chemical bismuth plating process |
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| CN1332269A true CN1332269A (en) | 2002-01-23 |
| CN1133757C CN1133757C (en) | 2004-01-07 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154632A (en) * | 2011-03-22 | 2011-08-17 | 王建朝 | Method for non-aqueous system chemical cobalt plating at room temperature |
| CN102168259A (en) * | 2011-03-22 | 2011-08-31 | 王建朝 | Chemical nickel-plating method for nonaqueous system at room temperature |
| CN104218248A (en) * | 2013-05-31 | 2014-12-17 | 中国科学院大连化学物理研究所 | Difunctional negative electrode and its application as all-vanadium redox energy storage battery negative electrode |
| CN106981650A (en) * | 2017-02-10 | 2017-07-25 | 中山大学 | A kind of preparation method of nanoscale bismuth with elementary |
| CN108269991A (en) * | 2016-12-30 | 2018-07-10 | 上海移宇科技股份有限公司 | Preparation method of zinc-bismuth alloy powder for flexible battery cathode |
-
2001
- 2001-07-10 CN CNB011276150A patent/CN1133757C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154632A (en) * | 2011-03-22 | 2011-08-17 | 王建朝 | Method for non-aqueous system chemical cobalt plating at room temperature |
| CN102168259A (en) * | 2011-03-22 | 2011-08-31 | 王建朝 | Chemical nickel-plating method for nonaqueous system at room temperature |
| CN102168259B (en) * | 2011-03-22 | 2013-04-24 | 王建朝 | Chemical nickel-plating method for nonaqueous system at room temperature |
| CN104218248A (en) * | 2013-05-31 | 2014-12-17 | 中国科学院大连化学物理研究所 | Difunctional negative electrode and its application as all-vanadium redox energy storage battery negative electrode |
| CN108269991A (en) * | 2016-12-30 | 2018-07-10 | 上海移宇科技股份有限公司 | Preparation method of zinc-bismuth alloy powder for flexible battery cathode |
| CN106981650A (en) * | 2017-02-10 | 2017-07-25 | 中山大学 | A kind of preparation method of nanoscale bismuth with elementary |
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| Publication number | Publication date |
|---|---|
| CN1133757C (en) | 2004-01-07 |
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