CN110284128A - The method of chemical plating metal ruthenium - Google Patents
The method of chemical plating metal ruthenium Download PDFInfo
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- CN110284128A CN110284128A CN201910686760.5A CN201910686760A CN110284128A CN 110284128 A CN110284128 A CN 110284128A CN 201910686760 A CN201910686760 A CN 201910686760A CN 110284128 A CN110284128 A CN 110284128A
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- Prior art keywords
- metal
- plating
- ruthenium
- chemical plating
- stoste
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
The invention belongs to chemical plating fields, more particularly to a kind of method of chemical plating metal ruthenium, include the following steps: a) preparing metal ruthenium stoste: adding water to mix soluble ruthenium salt, sodium nitrite and hydrochloric acid, after solid content is completely dissolved, ammonium hydroxide is added to be uniformly mixed, metal Ru stoste is obtained, is sealed spare；B) it prepares and prepares liquid: taking metal Ru stoste obtained by step a), adjust pH value to 12~13 with strong alkali solution, obtain metal Ru and prepare liquid；C) plating: preparing liquid for the metal Ru that step b) is prepared and be added in the plating container for being placed with workpiece to be plated, and reducing agent is added thereto and starts plating, workpiece surface to be plated gradually forms metal Ru coating.Using the above scheme, preparing metal ruthenium stoste can save for a long time, on-demand, eliminate now with most times needed for chemical plating fluid, substantially increase the process efficiency of chemical plating, and prepare liquid using strong basicity and carry out plating, coating more it is fine and close more evenly.
Description
Technical field
The invention belongs to chemical plating fields, and in particular to a kind of method of chemical plating metal ruthenium.
Background technique
Chemical plating is a kind of novel metal surface treatment technology, also referred to as electroless plating or autocatalytic plating, is in nothing
By suitable reducing agent in the case where applying power, metal ion in plating solution is set to be reduced into metal, and deposit to piece surface
A kind of coating method.The technology is increasingly subject to the concern of people with its simple process, energy-saving and environmental protection.Chemical plating use scope
It is very wide, coating uniformly, good decorative property.In terms of protective, the corrosion resistance and service life of product can be improved；In functionality side
Face can improve the specific functions such as wear-resistant conductive, the greasy property of workpiece.Since country focuses on environmental protection, and industrial development
Requirements at the higher level are proposed to Treatment of Metal Surface, so that electroless plating technology development speed is constantly accelerated, development prospect attracts attention.
In the prior art, chemical plating is first to configure chemical plating fluid, such as chemical plating ruthenium, including soluble ruthenium salt, complexing agent,
The additives such as reducing agent, and other pH adjusting agents, buffer.It is first that all preparation of reagents other than reducing agent are molten at mixing
Liquid is put into workpiece to be plated, adds reducing agent and starts plating.
Such as: application No. is " 201510125066.8 ", entitled " the chemical plating ruthenium solution for PCB surface processing
With PCB surface processing method " patent of invention disclose the circuit board chemical plating ruthenium in a kind of chemical nickel plating gold-leaching technology
Solution, including soluble ruthenium salt, main complexing agent, auxiliary complex-former, reducing agent and pH adjusting agent, the method increase chemical plating fluids
Stability, solution " service life " can be kept in 20 days, but in 20 days effective standing times, plating effect is still big
Amplitude reduction is significantly exactly most in identical plating time, and thickness of coating significantly reduces, it is seen then that can protect described in it
Holding bath life not being is that real effect is constant, and in the identical situation of material utilization amount, plating effect difference is so big, for
For enterprise, this scheme is just very undesirable.
In fact, although water can be dissolved in, solution rate is very slow for soluble ruthenium salt, generally continuously stirring
Need at least six or seven hour that can just be completely dissolved in the case of mixing, when workpiece to be plated needs plating metal ruthenium, being reconfigured plating solution is needed
The time to be waited is longer, seriously affects working efficiency.
Summary of the invention
The purpose of the present invention is to provide a kind of method of chemical plating metal ruthenium, chemical plating fluid is configured to semi-finished product, solution
Stablize, can store for a long time, when plating can be used at any time, and greatly improve the efficiency of chemical plating ruthenium.
To achieve the above object, the technical solution adopted by the present invention are as follows: a kind of preparation method of metal Ru chemical plating fluid, packet
Include following steps:
A) preparing metal ruthenium stoste: water is added to mix soluble ruthenium salt, sodium nitrite and hydrochloric acid, solid content is completely dissolved
Afterwards, ammonium hydroxide is added to be uniformly mixed, obtains metal Ru stoste, is sealed spare；
B) it prepares and prepares liquid: taking metal Ru stoste obtained by step a), adjust pH value to 12~13 with strong alkali solution, obtain
Metal Ru prepares liquid；
C) plating: preparing liquid for the metal Ru that step b) is prepared and be added in the plating container for being placed with workpiece to be plated, to
Reducing agent is wherein added and starts plating, workpiece surface to be plated gradually forms metal Ru coating.
Using the above scheme, first configuration metal Ru stoste is spare, and sodium nitrite and salt is added as ruthenium source in soluble ruthenium salt
Acid can not only promote ruthenium salt to be dissolved in water, but also can play coordination, add ammonium hydroxide, under mutual cooperation, can make molten
Liquid forms stable complex status, can store for a long time after sealing, on-demand, when needing chemical plating ruthenium, directly takes out metal Ru
Stoste, after adjusting pH value with strong alkali solution, reducing agent, which is added, can carry out chemical plating ruthenium, be greatly saved now with needed for solution
Time improves the process efficiency of chemical plating, and the pH value of plating liquid wants high compared to conventional chemical plating, in this strong basicity ring
Under border, coating more it is fine and close more evenly.
Specifically, in the step a), first water is added to mix soluble ruthenium salt and sodium nitrite, then that hydrochloric acid is slowly added dropwise is molten
Mixed solution is heated to 100 DEG C by liquid, and stirring to solid content is completely dissolved, and adds ammonium hydroxide after cooling；It, will after ammonium hydroxide is added
After mixed liquor is heated to 100 DEG C and keeps 5~8min, stop heating and natural cooling.Wherein, ruthenium content in soluble ruthenium salt,
The molar ratio of the content of ammonia is 1:(3.0-3.2 in hydrogen chloride content and ammonium hydroxide in sodium nitrite, hydrochloric acid solution): (4.0-4.2):
(160-180)。
In the step b), strong alkali solution is sodium hydroxide solution or potassium hydroxide solution.
In the step c), plating is carried out under the conditions of 50~65 DEG C, before plating, first respectively by workpiece to be plated and plating
Container, metal Ru prepare liquid and reducing agent preheats under the conditions of 50~65 DEG C.Wherein, the reducing agent is hydrazine hydrate, is used
It is preceding to be first configured to N2H4Concentration is the aqueous solution of 0.5~1.0M；Reducing agent effective component and metal Ru prepare rubbing for ruthenium content in liquid
You are than being (6.1-6.3): 1.
Through inventor's a large number of experiments, when the pH that metal Ru prepares liquid is lower than 11, coating compaction rate is inadequate, and with coating
The increase of thickness, compaction rate gradually decrease, until being attached to coating surface at metal powdery, gently wiping can be detached from, and have
Imitating thickness of coating is only 1~2 μm；And preparing liquid pH in 12-13, coating compaction rate greatly improves, and thickness of coating reaches 5 μm
It is still in densifie state when above.
Specific embodiment
Technical solution of the present invention is described in further detail below with reference to embodiment.
1, preparing metal ruthenium stoste:
4.82g RuCl is weighed respectively3·3H2O and 3.92g NaNO2, two kinds of powder are sufficiently mixed, are added 100ml's
Deionized water stirs 10-15 minutes at room temperature, the hydrochloric acid of 7.4ml 37% is slowly dropped under agitation, by above-mentioned mixing
Object is heated to 100 DEG C, is stirred continuously, and until all solid contents all dissolve, stopping heating, solution naturally cools to room temperature, to
The NH of 237ml 25% is slowly added in solution3·H2O, and quickly stir, then mixed liquor is warming up to 100 DEG C, and keep the temperature 5-8
Minute, then stop heating and being cooled to room temperature, by the volumetric flask constant volume of solution 1L, shakes up and be sealed spare, obtain
Metal Ru stoste.
2, it prepares and prepares liquid:
Take three parts of 112ml's to be sealed spare metal Ru stoste, being separately added into NaOH solution and adjusting pH value is 7~9
(7.8), 9~11 (10.2), 12~13 (12.7), are settled to 1L with deionized water, obtain metal Ru and prepare liquid 1., 2., 3.；
It prepares reducing agent solution: hydrazine hydrate is configured to the aqueous solution of 1.0M concentration.
3, plating:
Using stainless steel plate as workpiece to be plated, steel plate to be plated, plating container, metal Ru are first prepared into liquid and reducing agent is distinguished
It preheats under the conditions of 50 DEG C, is placed in plating container by workpiece to be plated, 500ml metal Ru is added and prepares liquid 1., 100~
Under 250rpm speed, it is slowly dropped into the prepared hydrazine hydrate solution of 15ml (being added in three times, each 5ml), metal while stirring
Ruthenium is slowly precipitated and gradually forms coating in workpiece surface to be plated, obtains plating piece 1..
Using with plating piece 1. identical plating conditions, prepare liquid with metal Ru respectively and 2., 3. same stainless steel plate applied
2. and 3. plating obtains plating piece, is monitored respectively to the plating layer formation process of three plating pieces, monitors and analyze data and be shown in Table 1.
Influence of the 1 chemical plating fluid pH value of table to ruthenium coating
4, the metal Ru stoste service life:
According to above-mentioned steps 1 record process preparing metal ruthenium stoste and be sealed, match according to the stoste recorded in table 2
Time processed takes identical the amount of the stock solution respectively, and the plating process of the plating piece recorded using above-mentioned steps 2,3 3. is respectively to identical
Workpiece to be plated carries out plating, by the thickness of coating on workpiece after plating 15min at the state of metal Ru stoste when taking liquid and 50 DEG C
It charges in table 2.
Table 2 saves the coating conditions after metal Ru stoste situation and plating after a certain period of time
By table 2 it is found that being sealed after preparing metal ruthenium stoste using the above scheme, need directly to take when plating,
After at least saving 3 years, for metal Ru stoste compared with the stoste now matched, plating effect is essentially identical, also, theoretically metal Ru
Stoste can be with persistence.
Claims (8)
1. a kind of method of chemical plating metal ruthenium, includes the following steps:
A) preparing metal ruthenium stoste: add water to mix soluble ruthenium salt, sodium nitrite and hydrochloric acid, after solid content is completely dissolved, add
Enter ammonium hydroxide to be uniformly mixed, obtains metal Ru stoste, be sealed spare；
B) it prepares and prepares liquid: taking metal Ru stoste obtained by step a), adjust pH value to 12~13 with strong alkali solution, obtain metal
Ruthenium prepares liquid；
C) plating: the metal Ru that step b) is prepared is prepared into liquid and is added in the plating container for being placed with workpiece to be plated, thereto
Reducing agent is added and starts plating, workpiece surface to be plated gradually forms metal Ru coating.
2. the method for chemical plating metal ruthenium according to claim 1, it is characterised in that:, first will be soluble in the step a)
Ruthenium salt and sodium nitrite add water to mix, then hydrochloric acid solution is slowly added dropwise, and mixed solution are heated to 100 DEG C, stirring to solid content
It is completely dissolved, adds ammonium hydroxide after cooling.
3. the method for chemical plating metal ruthenium according to claim 1, it is characterised in that: in the step a), after ammonium hydroxide is added,
After being heated to 100 DEG C by mixed liquor and keep 5~8min, stop heating and natural cooling.
4. the method for chemical plating metal ruthenium according to claim 1, it is characterised in that: in the step a), soluble ruthenium salt
Middle ruthenium content, sodium nitrite, the molar ratio of the content of ammonia is 1:(3.0-3.2 in hydrogen chloride content and ammonium hydroxide in hydrochloric acid solution):
(4.0-4.2): (160-180).
5. the method for chemical plating metal ruthenium according to claim 1, it is characterised in that: in the step b), strong alkali solution
For sodium hydroxide solution or potassium hydroxide solution.
6. the method for chemical plating metal ruthenium according to claim 1, it is characterised in that: in the step c), the reducing agent
For hydrazine hydrate, N is first configured to using preceding2H4Concentration is the aqueous solution of 0.5~1.0M.
7. the method for chemical plating metal ruthenium according to claim 1, it is characterised in that: in the step c), plating is 50
It is carried out under the conditions of~65 DEG C, before plating, workpiece to be plated and plating container, metal Ru is first prepared into liquid and reducing agent 50 respectively
It is preheated under the conditions of~65 DEG C.
8. according to claim 1 or the method for the 5 chemical plating metal rutheniums, it is characterised in that: in the step c), reducing agent has
It imitates ingredient and metal Ru prepares the molar ratio of ruthenium content in liquid as (6.1-6.3): 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910686760.5A CN110284128A (en) | 2019-07-29 | 2019-07-29 | The method of chemical plating metal ruthenium |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910686760.5A CN110284128A (en) | 2019-07-29 | 2019-07-29 | The method of chemical plating metal ruthenium |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113106507A (en) * | 2021-04-15 | 2021-07-13 | 电子科技大学 | Ruthenium electroplating solution for filling micro-nano grooves and blind holes and preparation method |
| CN114232039A (en) * | 2022-01-14 | 2022-03-25 | 惠州市中京实业有限公司 | Environment-friendly electroplating solution and electroplating method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5980766A (en) * | 1982-10-29 | 1984-05-10 | Agency Of Ind Science & Technol | Electroless ruthenium plating bath |
| US20110229734A1 (en) * | 2010-03-22 | 2011-09-22 | Unity Semiconductor Corporation | Immersion platinum plating solution |
| JP2012012632A (en) * | 2010-06-29 | 2012-01-19 | Furuya Kinzoku:Kk | Method for hardening surface of platinum molded article and platinum molded article having hardened surface |
| CN105018908A (en) * | 2015-03-23 | 2015-11-04 | 深圳市贝加电子材料有限公司 | Chemical ruthenium plating solution for circuit board surface treatment and circuit board surface treatment method |
-
2019
- 2019-07-29 CN CN201910686760.5A patent/CN110284128A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5980766A (en) * | 1982-10-29 | 1984-05-10 | Agency Of Ind Science & Technol | Electroless ruthenium plating bath |
| US20110229734A1 (en) * | 2010-03-22 | 2011-09-22 | Unity Semiconductor Corporation | Immersion platinum plating solution |
| JP2012012632A (en) * | 2010-06-29 | 2012-01-19 | Furuya Kinzoku:Kk | Method for hardening surface of platinum molded article and platinum molded article having hardened surface |
| CN105018908A (en) * | 2015-03-23 | 2015-11-04 | 深圳市贝加电子材料有限公司 | Chemical ruthenium plating solution for circuit board surface treatment and circuit board surface treatment method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113106507A (en) * | 2021-04-15 | 2021-07-13 | 电子科技大学 | Ruthenium electroplating solution for filling micro-nano grooves and blind holes and preparation method |
| CN114232039A (en) * | 2022-01-14 | 2022-03-25 | 惠州市中京实业有限公司 | Environment-friendly electroplating solution and electroplating method thereof |
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