阅读说明：本技术 基于edta多元配位体系的无氰电刷镀溶液及其制备方法 (Based on the more first coordination systems of EDTA without cyanogen brush plating liquor and preparation method thereof ) 是由 李新梅 张忠文 索帅 杜宝帅 乔亚霞 邓化凌 张�浩 张�杰 罗宏建 张广成 步 于 2019-08-06 设计创作，主要内容包括：本发明公开了一种基于EDTA多元配位体系的无氰电刷镀溶液及其制备方法,至少包括可溶性银盐和EDTA多元配位体系,该EDTA多元配位体系包括主配位剂和辅助配位剂,其中,主配位剂为EDTA,辅助配位剂为5,5-二甲基乙内酰脲和焦磷酸钾。该电刷镀银溶液比较稳定,形成的镀银质量较好,镀银层性能满足标准对高压隔离开关触指镀银层的要求,能够实现清洁、高效、安全无氰电刷银技术修复。(The invention discloses a kind of based on the more first coordination systems of EDTA without cyanogen brush plating liquor and preparation method thereof, including at least the more first coordination systems of soluble silver salt and EDTA, the EDTA is more, and first coordination system includes main complexant and auxiliary complexing agent, wherein, main complexant is EDTA, auxiliary complexing agent is 5,5- dimethyl hydantoin and potassium pyrophosphate.The silver brush plating solution is more stable, and the silver-plated quality of formation is preferable, and silver coating performance meets requirement of the standard to high voltage isolator fingertip silver coating, can be realized cleaning, efficient, safety without cyanogen brush silver technology reparation.)

1. it is a kind of based on the more first coordination systems of EDTA without cyanogen brush plating liquor, it is characterised in that: include at least soluble silver salt With the more first coordination systems of EDTA, the EDTA is more, and first coordination system includes main complexant and auxiliary complexing agent, wherein main complexant is EDTA, auxiliary complexing agent 5,5- dimethyl hydantoin and potassium pyrophosphate.

2. it is according to claim 1 based on the more first coordination systems of EDTA without cyanogen brush plating liquor, it is characterised in that: EDTA Concentration be 100-200g/L, the concentration of 5,5- dimethyl hydantoins is 40-160g/L, and the concentration of potassium pyrophosphate is 40- 120g/L。

3. it is according to claim 1 based on the more first coordination systems of EDTA without cyanogen brush plating liquor, it is characterised in that: it is described Soluble silver salt is silver nitrate, and the concentration of silver nitrate is 80-160g/L.

4. it is according to claim 1 based on the more first coordination systems of EDTA without cyanogen brush plating liquor, it is characterised in that: also wrap Include conductive salt, auxiliary complexing agent, buffer, additive and brightener；

Further, the conductive salt is potassium carbonate, and the concentration of potassium carbonate is 10-80g/L；

Further, the auxiliary complexing agent is potassium pyrophosphate, concentration 40-120g/L；

Further, the buffer is ammonium acetate, concentration 10-50g/L；

Further, the additive is bismuth nitrate and Amcide Ammate, and the concentration of bismuth nitrate is 1-3g/L, Amcide Ammate Concentration is 50-200g/L；

Further, the brightener is bipyridyl and gelatin, and the concentration of bipyridyl is 0.5-0.8g/L, and the concentration of gelatin is 0.8-1.2g/L。

5. it is according to claim 1 based on the more first coordination systems of EDTA without cyanogen brush plating liquor, it is characterised in that: its pH Value is 8.5-10；

Further, the no cyanogen brush plating liquor adjusts pH value using potassium hydroxide.

6. any preparation method without cyanogen brush plating liquor based on the more first coordination systems of EDTA of claim 1-5, It is characterized in that: including the following steps:

EDTA and 5,5- dimethyl hydantoin are added into alkali fusion liquid, dissolution completely, obtains mixed liquor；

Under stirring condition, silver nitrate solution is added in Xiang Suoshu mixed liquor, adds potassium pyrophosphate and sulfamic acid ammonia, stirring makes It is completely dissolved, and adjusts the pH value of solution, obtains the second mixed liquor；

Potassium carbonate, ammonium acetate, bipyridyl and gelatin are added into the second mixed liquor, after mixing, water is added to be adjusted to setting volume, adjusts Save solution pH value to get.

7. the preparation method without cyanogen brush plating liquor according to claim 6 based on the more first coordination systems of EDTA, special Sign is: temperature when preparation is 15-35 DEG C.

8. the preparation method without cyanogen brush plating liquor according to claim 6 based on the more first coordination systems of EDTA, special Sign is: water used in process for preparation is high purity water；

Further, alkali used in process for preparation is potassium hydroxide.

9. a kind of coating, it is characterised in that: by claim 1-5 it is any it is described based on the more first coordination systems of EDTA without cyanogen brush Plating liquor is prepared on conducting base by Brush Plating mode.

10. coating according to claim 9, it is characterised in that: the conducting base is copper.

Technical field

The invention belongs to Brush Electroplating Technique fields, and in particular to it is a kind of based on the more first coordination systems of EDTA without cyanogen Brush Plating Solution and preparation method thereof.

Background technique

Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art Art.

High voltage isolator is most important, high-voltage electrical equipment that usage amount is most in electric system power transmission and transforming equipment, with Transmission line of electricity capacity and distance it is increasingly longer, higher want also proposed to reliability and the service life of high-voltage switch gear It asks.Significant points of the contact as high-voltage switch gear, due to mechanical collision, friction, corrosion and burning in disjunction and closing course Erosion etc. be easy to cause contact erosion damage, and switch fever or trip accident happen occasionally caused by failing because of contact, wherein touching Head silver coating quality decline problem is most commonly seen.At present for underproof switch contact, field service personnel is being destroyed Coating surface applies vaseline or conductive paste with anti-oxidation, run vaseline or conductive paste after a period of time harden, dusting meeting Guiding discharge phenomenon occurs, and ultimately causes equipment damage；At present other than taking substitute mode, scene is all made of the brush of plating solution containing cyanogen Silver-coating method is repaired, so that thickness be made to meet the requirements of the standard.But the cyanide content of cyanide silver plating solution is high, toxicity is big, Seriously endanger ecological environment and human health.For many years, the scholar of countries in the world has done deep and long-term research work, opens Non-cyanide silver coating technical research is opened up, is dedicated to finding more effective complexing agent and additive, adjuvant, control silver is in the heavy of copper surface Product speed.Therefore, studying without cyanogen brush plating liquor is the difficult point of high-voltage switch contact re-manufacturing technology and the place of key, is had Very important realistic meaning.

Currently used cyanideless electro-plating silver process mainly has that thiosulfate is silver-plated, imino-diacetic sulfonic acid (NS) is silver-plated, cigarette Acid is silver-plated, imidazoles-aminosalicylic acid is silver-plated, succimide is silver-plated etc., wherein thiosulfate bath stability, but quality of coating It is not good enough；Imino-diacetic sulfonic acid plating solution performance is silver-plated close to cyanogen system, but the volatilization of plating liquefied ammonia and copper material chemolysis are more tight Weight, plating solution are more sensitive to impurity；Nicotinic acid silver plating and the silver-plated performance of imidazoles-aminosalicylic acid are silver-plated close to cyanogen system, but its Price is more expensive, it is difficult to popularize in an all-round way and use；It polarizes when succimide plating solution silver electro-deposition larger, the pH wider range used, Being not required to leaching silver can directly be electroplated, the problem is that succimide facile hydrolysis, easily jaundice discoloration after coating is shelved.So by Larger in non-cyanide silver coating technical difficulty, each system, which more or less has problem, influences cyanide-free silver plating process engineering application.

Summary of the invention

For above-mentioned the technical problems existing in the prior art, the object of the present invention is to provide one kind to be based on the more members of EDTA Coordination system without cyanogen brush plating liquor and preparation method thereof.The silver brush plating solution is more stable, the silver-plated quality of formation compared with Good, silver coating performance meets requirement of the standard to high voltage isolator fingertip silver coating, can be realized cleaning, efficient, safe nothing Cyanogen brush silver technology reparation.

In order to solve the above technical problems, the technical solution of the present invention is as follows:

The first purpose of the invention is to provide a kind of based on the more first coordination systems of EDTA without cyanogen brush plating liquor, at least Including the more first coordination systems of soluble silver salt and EDTA, the more first coordination systems of the EDTA include main complexant and auxiliary complexing agent, Wherein, main complexant is EDTA, auxiliary complexing agent 5,5- dimethyl hydantoin and potassium pyrophosphate.

Determining according to the selection of the stability of the complexing power of complexant and complex.Ethylenediamine tetra-acetic acid (EDTA) contains There is the chelating agent of hydroxyl and amino, there is multiple tooth coordination structure, anion Y^4-Tool there are two amino and four hydroxyls, can with silver from Son occurs complex reaction and forms cyclic annular complexing body, i.e. chelate.EDTA and silver ion form negative coordination ion, and complex is stablized Constant log β₁It is 7.32, is directly coordinated with silver ion as stable complex in alkaline environment, so based on EDTA is selected Complexant.

In some embodiments, the concentration of EDTA is 100-200g/L, and the concentration of 5,5- dimethyl hydantoins is 40- 160g/L, the concentration of potassium pyrophosphate are 40-120g/L.

In some embodiments, the soluble silver salt is silver nitrate, and the concentration of silver nitrate is 80-160g/L.

In some embodiments, the no cyanogen brush plating liquor further includes conductive salt, auxiliary complexing agent, buffer, addition Agent and brightener.

Further, the conductive salt is potassium carbonate, and the concentration of potassium carbonate is 10-80g/L.Potassium carbonate can improve plating solution Dispersibility obtains uniform coating.

Further, the auxiliary complexing agent is potassium pyrophosphate, concentration 40-120g/L.

Further, the buffer is ammonium acetate, concentration 10-50g/L.

Further, the additive is bismuth nitrate and Amcide Ammate, and the concentration of bismuth nitrate is 1-3g/L, sulfamic acid The concentration of ammonium is 50-200g/L.

Amcide Ammate plays conductive, buffer function；Bismuth nitrate is used to improve the hardness of coating.

Further, the brightener is bipyridyl and gelatin, and the concentration of bipyridyl is 0.5-0.8g/L, the concentration of gelatin For 0.8-1.2g/L.

In some embodiments, the pH value of the no cyanogen brush plating liquor is 8.5-10.

Further, the no cyanogen brush plating liquor adjusts pH value using potassium hydroxide.

A second object of the present invention is to provide the above-mentioned systems without cyanogen brush plating liquor based on the more first coordination systems of EDTA Preparation Method includes the following steps:

EDTA and 5,5- dimethyl hydantoin are added into alkali fusion liquid, dissolution completely, obtains mixed liquor；

Under stirring condition, silver nitrate solution is added in Xiang Suoshu mixed liquor, adds potassium pyrophosphate and sulfamic acid ammonia, stirs It mixes and makes it completely dissolved, adjust the pH value of solution, obtain the second mixed liquor；

Potassium carbonate, ammonium acetate, bipyridyl and gelatin are added into the second mixed liquor, after mixing, water is added to be adjusted to setting body Product, adjust the pH value of solution to get.

When different pH value EDTA that there are type bodies is different, in seven kinds of type bodies of EDTA, only Y^4-It can be direct with metal ion Complexing, the acidity of solution is lower, Y^4-Distribution than bigger.Therefore, EDTA complexing power in alkaline solution is stronger.

In some embodiments, temperature when preparing without cyanogen brush plating liquor based on the more first coordination systems of EDTA is 15-35℃。

In some embodiments, it is described based on the more first coordination systems of EDTA without used in cyanogen brush plating liquor process for preparation Water be high purity water.

High purity water refers to by the conducting medium almost all removal in water, and by the colloidal substance not dissociated in water, gas It is removed with organic matter to the water of very low degree, the salt content of high purity water is in 0.3mg/L hereinafter, conductivity is less than 0.2 μ s/cm. Brush plating liquor is prepared using high purity water, it can be with the concentration of accurate formulation wherein various salt, the matter of accurate control brush plating liquor Amount, to avoid in water salt and impurity the quality of Brush Plating is impacted.

In some embodiments, it is described based on the more first coordination systems of EDTA without used in cyanogen brush plating liquor process for preparation Alkali be potassium hydroxide.

Third object of the present invention is to provide a kind of coating, the coating is by the above-mentioned nothing based on the more first coordination systems of EDTA Cyanogen brush plating liquor is prepared on conducting base by Brush Plating mode.

In some embodiments, the conducting base is copper.

The beneficial effects of the present invention are:

Silver brush plating solution is more stable, and the silver coating quality of formation is preferable, silver coating performance meet standard to high pressure every The requirement for closing fingertip silver coating is left, can be realized fingertip cleaning, efficient, safety without cyanogen brush silver technology reparation.

Detailed description of the invention

The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.

Fig. 1 is the photo of silver coating prepared by embodiment 1；

Fig. 2 is the macrograph of silver coating prepared by embodiment 1 and matrix faying face；

Fig. 3 is the metallographic structure photo of silver coating prepared by embodiment 1；

Fig. 4 is the SEM shape appearance figure of silver coating prepared by embodiment 1；

Fig. 5 is the XRD spectrum of silver coating prepared by embodiment 1；

The photo for the silver coating that Fig. 6 is prepared for comparative example 1, × 200；

Fig. 7 is the metallographic structure photo of silver coating prepared by comparative example 1；

Fig. 8 is the photo of silver coating prepared by comparative example 2.

Specific embodiment

It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the present invention.Unless another It indicates, all technical and scientific terms used herein has usual with general technical staff of the technical field of the invention The identical meanings of understanding.

It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.