CN103484839A - Metal surface treatment reagent for cyanide-free chemical plating or cyanide-free electroplating, and metal surface treatment method - Google Patents
Metal surface treatment reagent for cyanide-free chemical plating or cyanide-free electroplating, and metal surface treatment method Download PDFInfo
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- CN103484839A CN103484839A CN201310470814.7A CN201310470814A CN103484839A CN 103484839 A CN103484839 A CN 103484839A CN 201310470814 A CN201310470814 A CN 201310470814A CN 103484839 A CN103484839 A CN 103484839A
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Abstract
The invention discloses a metal surface treatment reagent for cyanide-free chemical plating or cyanide-free electroplating, and a metal surface treatment method. The metal surface treatment reagent for cyanide-free chemical plating or cyanide-free electroplating comprises nickel chloride, sodium hypophosphite, sodium tungstate and ammonium dihydrogen citrate. The use of the metal surface treatment reagent for cyanide-free chemical plating or cyanide-free electroplating to carry out the cyanide-free chemical plating or cyanide-free electroplating of a member for plating avoids the use of extremely toxic substances comprising potassium gold cyanide or gold potassium citrate in the metal surface treatment process, simplifies the treatment process and effectively reduces the production cost.
Description
Technical field
The present invention relates to the metal manufacture field, the non-cyanide plating method that is specifically related to non-cyanide plating reagent and uses this reagent, be particularly related to metal finishing reagent and the metal surface treating method without the cyanogen electroless plating that uses it without the cyanogen electroless plating, and the metal surface treating method of the metal finishing reagent of cyanideless electro-plating and the cyanideless electro-plating that uses it.
Background technology
In some field, conductivity to metal requires high, do not allow metallic surface to have zone of oxidation, yet often oxidizing reaction easily occurs in cheap high-conductivity metal, and gold waits precious metal can cause the huge of cost to increase, therefore usually need to be in metallic surface by electroless plating or electric plating method metallic surface plating one deck resistance of oxidation and conductive capability all strong metal reach the balance of Performance and Cost Modeling.
Printed circuit board (PCB) (PCB) is the cross tie part that provides electronic component to connect by the copper circuit on its insulated substrate, is the essential parts of modern electronic equipment.Yet in the making processes of PCB, due to the easy oxidation of copper circuit, cause conduction and welding property to worsen, must carry out corrosion resisting property and the welding property of surface treatment to improve copper circuit to copper circuit.Chemical nickel plating/immersion gold plating technology is that to carry out chemical replacement at the first chemical nickel plating in copper circuit surface gold-plated again, and the nickel obtained/golden combined plating can effectively prevent the oxidation of copper circuit and improve weldability, therefore in PCB manufacture field, is widely used.Chemical nickel plating in chemical nickel plating/plating by chemical displacement technology for gold be a kind of can be on the surface with catalytic activity spontaneous autocatalysis process of carrying out.Yet in the chemical nickel-plating liquid that is reductive agent at Using Sodium Hypophosphite, the oxidation that the copper surface can not catalysis Hypophosporous Acid, 50 root, therefore can't be spontaneous carry out chemical nickel plating, must introduce on the copper surface the carrying out that active site bring out chemical nickel plating by activation treatment.
The physical property of the comparatively sparse nickel of while of its coating crystal layer structure of traditional electronickelling or chemical nickel plating own is poor to the acidic substance resistance, when therefore its coating runs into acidic substance or liquid, its surface can form oxidation film layer, this oxidation film layer can affect the welding of electric appliance component and cause functional obstacle, therefore need to be protected by other coating, therefore existing conventional process techniques needs to add one coating on nickel dam again, the gold layer is protected nickel dam, the gold layer that wherein used adopts potassium auric cyanide or citric acid gold potassium usually, by replacement(metathesis)reaction, realize, and potassium auric cyanide or citric acid gold potassium are for containing highly toxic substance, in use operator's health and life are caused to very large threat.
Along with the attention of country to environment protection, at present, research without cyanogen electroless plating or cyanideless electro-plating has also been become to focus, as disclosed a kind of chemical nickel-plating liquid that comprises single nickel salt, nickelous chloride, sodium hypophosphite, Trisodium Citrate, Tai-Ace S 150, brightening agent and ammoniacal liquor etc. in Chinese patent CN101709492A; Disclose for another example a kind of using in Chinese patent CN102747345A and soaked the method for nickel liquid to PCB copper circuit chemical nickel plating on surface by boric acid, organic acid or the preparations such as its sodium salt, sulfocompound and single nickel salt.
The aforesaid method agents useful for same is more, comprises the hazardous chemical such as strong acid, highly basic, and complex operation step, and the production time is long, has increased production difficulty and cost.
Summary of the invention
In order to overcome the above problems, the inventor is through research with keen determination, found that the metal finishing reagent without cyanogen electroless plating or cyanideless electro-plating, comprise the materials such as nickelous chloride, sodium hypophosphite, sodium wolframate and ammonium dihydrogen citrate, it is applicable to the metal finishing of electroless plating and plating, particularly, the object of the present invention is to provide following several respects:
First aspect, a kind of reagent of the metal finishing without the cyanogen electroless plating, is characterized in that, this reagent of metal finishing without the cyanogen electroless plating comprises following composition:
Surplus is water,
Wherein, described g/L is based on the weight of every liter of described composition of the reagent of the metal finishing without the cyanogen electroless plating.
Second aspect, the invention provides a kind of reagent of the metal finishing without the cyanogen electroless plating, it is characterized in that, this reagent of metal finishing without the cyanogen electroless plating comprises following composition:
Surplus is water,
Wherein, described g/L is based on the weight of every liter of described composition of the reagent of the metal finishing without the cyanogen electroless plating.
The third aspect, the invention provides a kind of metal surface treating method without the cyanogen electroless plating, it is characterized in that, comprises the following steps:
(1) pre-treatment, the processing before the unplated piece surface is plated;
(2) electroless plating, it comprises following sub-step:
(2-1) electroless plating process: in the electroless plating container, ratio dilute with water mother liquor according to water: mother liquor=3:1, obtain diluent, adjust diluent pH value to 6～6.5 with ammoniacal liquor, again the diluent after processing is warming up to 70～80 ℃, the unplated piece surface is immersed in to 30～60min in the diluent after intensification;
(2-2) washing: water rinses the unplated piece surface 60～120s after (2-1) processing;
Wherein, described mother liquor is the reagent of the metal finishing without the cyanogen electroless plating described in above-mentioned first aspect or second aspect.
Fourth aspect, the invention provides a kind of metal surface treating method without the cyanogen electroless plating, it is characterized in that, described pre-treatment comprises degreasing, washing for the first time, microetch, washing for the second time, pickling, washes for the third time, cleans, activates, washes and hot water wash for the 4th time.
The 5th aspect, the invention provides a kind of metal finishing reagent of cyanideless electro-plating, it is characterized in that, comprises following composition:
Surplus is water,
Wherein, described g/L is based on the weight of the described composition of metal finishing reagent of every liter of cyanideless electro-plating.
The 6th aspect, the invention provides a kind of metal finishing reagent of cyanideless electro-plating, it is characterized in that, comprises following composition:
Surplus is water,
Wherein, described g/L is based on the metal finishing reagent of every liter of cyanideless electro-plating, the weight of described composition.
The 7th aspect, the invention provides a kind of metal surface treating method of cyanideless electro-plating, it is characterized in that, comprises the following steps:
(1) pre-treatment, the processing before the unplated piece surface is plated;
(2) electroplate, it comprises following sub-step:
(2-1) electroplating process: in electroplating container, ratio dilute with water mother liquor according to water: mother liquor=3:1, obtain diluent, adjust diluent pH value to 6～6.5 with ammoniacal liquor, again the diluent after processing is warming up to 70～80 ℃, puts into insoluble anode in the diluent after heating up, and treat that part is placed on negative electrode, pass into direct current, make metal ion in cell reaction to negative electrode plating piece surface deposition;
(2-2) washing: water rinses the unplated piece surface 60～120s after (2-1) processing;
Wherein, the metal finishing reagent that described mother liquor is the cyanideless electro-plating described in the 5th aspect or the 6th aspect.
Eight aspect, the invention provides a kind of metal surface treating method of cyanideless electro-plating, it is characterized in that, described pre-treatment comprises degreasing, washing for the first time, microetch, washing for the second time, pickling, washing and hot water wash for the third time.
The 9th aspect, the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the invention, is characterized in that,
Microetch reagent used in the microetch process of described pre-treatment comprises following composition:
Wherein, described sulfuric acid is the sulfuric acid that weight fraction is 98%;
In the pickling of described pre-treatment, acid used is sulfuric acid, and wherein, sulfuric acid is the sulfuric acid that weight fraction is 3～8%;
Passing into galvanic current density in described electroplating process is 3.0ASD.
Described PCB, refer to printed circuit board (PCB) herein.
Described PCB-copper herein, refer to the copper on pcb board surface.
According to a kind of reagent of the metal finishing without cyanogen electroless plating or cyanideless electro-plating provided by the invention and method, there is following beneficial effect:
(1) metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the invention is owing to need not using potassium auric cyanide or citric acid gold potassium (that is, " Bing Erjin ") etc. containing the material of precious metal element, and cost can reduce approximately 30%; In addition, the technical process of the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the present invention is few, and discharging of waste liquid is few, and cost can reduce approximately 50%;
(2) with traditional technology, compare, the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the invention is simple to operate, and can reach identical, even better effect;
(3) reagent of the metal finishing without cyanogen electroless plating or cyanideless electro-plating provided by the invention does not contain the toxic substances such as potassium cyanide that traditional technology must be used, therefore in use need not control, and increase safety in utilization and also save flow process;
(4) hardness that adopts the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the invention to process the circuit card obtained reaches 500～600Hv, identical with the effect of traditional electrical plating nickel gold;
(5) erosion resistance of the circuit card that adopts the inventive method processing to obtain is strong, in volume fraction 10%HCl, soaks 20h, without the black pad of nickel dam, produces;
(6) reagent of the metal finishing without cyanogen electroless plating or cyanideless electro-plating long service life used in the present invention, use 10 months with interior without being changed;
(7) metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the present invention need not carry out frequently more groove operation, can reduce in maintenance and operational activity duration, saves human and material resources;
(8) according to the coating obtained without the metal surface treating method of cyanogen electroless plating or cyanideless electro-plating provided by the present invention, be to take the nickel-tungsten-phosphorus composite plating that nickel forms as principal element, have that intensity is large, wear resistance is strong, the performance such as high temperature resistant, acid and alkali-resistance, be widely used in need strengthening the metallic surface of hardness, wear resistance, the performance such as high temperature resistant, universality is strong, is applicable to widespread adoption.
The accompanying drawing explanation
Fig. 1 illustrates the thermal shock experimental result picture of gained coating in embodiment 3.
Fig. 2 illustrates the thermal shock experimental result picture of gained coating in embodiment 5.
Fig. 3 illustrates the thermal shock experimental result picture of gained coating in embodiment 7.
Embodiment
Below further explain and describe content of the present invention by embodiment, but embodiment is not to be construed as limiting the scope of the invention.
The invention provides a kind of reagent of the metal finishing without the cyanogen electroless plating, it obtains according to following concentration proportioning preparation:
Surplus is water,
Preferably, comprise
Surplus is water,
Wherein, described g/L is based on the weight of every liter of described composition of the reagent of the metal finishing without the cyanogen electroless plating.
Above each component prepares the metal finishing reagent without cyanogen electroless plating or cyanideless electro-plating by following steps:
(1) add nickelous chloride in the reactor that hot water more than 80 ℃ is housed, be stirred to nickelous chloride and dissolve, be mixed with the nickel chloride solution of above-mentioned concentration, stand-by after filtering;
(2) add sodium hypophosphite in the reactor that hot water more than 80 ℃ is housed, be stirred to sodium hypophosphite and dissolve, be mixed with the sodium hypophosphite solution of above-mentioned concentration, stand-by after filtering;
(3) add ammonium dihydrogen citrate in the reactor that hot water more than 80 ℃ is housed, be stirred to ammonium dihydrogen citrate and dissolve, be mixed with the dihydrogen citrate ammonium solution of above-mentioned concentration, stand-by after filtering;
(4) add sodium wolframate in the reactor that hot water more than 80 ℃ is housed, be stirred to sodium wolframate and dissolve, be mixed with the sodium tungstate solution of above-mentioned concentration, stand-by after filtering;
(5) the above-mentioned solution prepared is at room temperature mixed, every 16 hours circulating filtrations 8 hours, continue, after one week, standing 3～7 days, to complete the present invention.
In the metal conditioner without cyanogen electroless plating or plating, the source that nickelous chloride is nickel element in coating, when its concentration is greater than 100g/L, in gained coating, the content of nickel does not almost change, when its concentration is less than 30g/L, in gained coating, nickel content is too low, especially, concentration without nickelous chloride in the metal finishing reagent of cyanogen electroless plating is selected 30～100g/L, preferably 30～50g/L; In the metal finishing reagent of cyanideless electro-plating, nickelous chloride concentration is 30～100g/L, is preferably 30～60g/L.
In the metal finishing reagent without cyanogen electroless plating or cyanideless electro-plating, the reductive agent that sodium hypophosphite is electroless plating or electroplating reaction, in the metal finishing reagent without the cyanogen electroless plating, when its concentration is greater than 80g/L, due to its too high levels, can cause in the electroless plating process, excessive and the wayward reaction process of chemical reaction rate, when its concentration is less than 20g/L, can cause chemical reaction rate too small and expend a large amount of electroless plating time, thereby increase unnecessary time cost, and can cause gained coating hardness deficiency, therefore, concentration without sodium hypophosphite in the metal finishing reagent of cyanogen electroless plating is selected 20～80g/L, preferred 20～40g/L, in like manner, selecting sodium hypophosphite concentration in the metal finishing reagent of cyanideless electro-plating is 20～100g/L, is preferably 20～50g/L.
In the metal finishing reagent without cyanogen electroless plating or cyanideless electro-plating, the catalyzer that sodium wolframate is electroless plating reaction, when concentration of sodium tungstate is greater than 90g/L, plating speed is without significantly promoting, and when concentration of sodium tungstate is less than 30g/L, plating speed can not meet the demand of metal finishing, for guaranteeing larger plating speed, concentration without sodium wolframate in the metal finishing reagent of cyanogen electroless plating is selected 30～90g/L, preferably 30～60g/L, more preferably 60g/L; In plating, because the content of W elements plays a decisive role to the plating piece solidity to corrosion, therefore the sodium wolframate as the W elements source becomes the corrosion proof important compound of enhancing plating piece, when its concentration is greater than 120g/L, in coating, the content of W no longer includes considerable change, the plating piece solidity to corrosion does not significantly strengthen, and continues to increase concentration of sodium tungstate and can make electroplating cost sharply raise, thereby cause the increase of the wasting of resources and cost; And, when its concentration is less than 30g/L, the solidity to corrosion of plating piece can not reach qualified requirement, therefore, it is 30～120g/L that the present invention selects concentration of sodium tungstate in the metal finishing reagent of cyanideless electro-plating, is preferably 30～60g/L.
In the metal finishing reagent without cyanogen electroless plating or cyanideless electro-plating, ammonium dihydrogen citrate is Ni
2+and WO
2 2+complexing ligand is provided, thereby strengthens the stability of nickel and tungsten and improve electroless plating or the speed of reaction of electroplating process, dihydrogen citrate and Ni
2+and WO
2 2+between all in the ratio complexing of 1:1, therefore, in the preparation of the metal finishing reagent without cyanogen electroless plating or cyanideless electro-plating, the concentration of ammonium dihydrogen citrate at least equals without Ni in the metal finishing reagent of cyanogen electroless plating or cyanideless electro-plating
2+and WO
2 2+the concentration sum, to guarantee abundant complexing, therefore, in the electroless plating process, its preferred concentration range is 30～120g/L, 40～60g/L more preferably, selecting the dihydrogen citrate ammonium concentration in the metal finishing reagent of cyanideless electro-plating is 30～100g/L, is preferably 30～60g/L.
The invention provides a kind of metal surface treating method without the cyanogen electroless plating, by using without the metal finishing reagent of cyanogen electroless plating, realize the surface treatment without the cyanogen electroless plating, particularly:
Comprise the following steps:
(1) pre-treatment, it comprises following sub-step:
(1-1) degreasing: under 45 ℃ of conditions, use and comprise that the reagent of following density component carries out skimming treatment:
Processing unplated piece surface, remove the unplated piece surface film oxide, makes the unplated piece surface exposure go out metal in order to carry out the carrying out of subsequent chemistry plating;
(1-2) washing for the first time: the unplated piece surface 20～30s after processing with water flushing (1-2), remove the degreasing reagent in the unplated piece surface attachment;
(1-3) microetch: under 45 ℃ of conditions, carry out the microetch alligatoring with microetch reagent on the unplated piece surface of processing through (1-1), stinging the erosion degree of depth is 0.5～1 μ m, and makes the unplated piece surface keep exposed uniform state, make the unplated piece surface coarsening, be beneficial to adhering to of follow-up metal plating;
(1-4) washing for the second time: the unplated piece surface 20～30s after processing with water flushing (1-2), remove the microetch reagent in the unplated piece surface attachment;
(1-5) pickling: the unplated piece surface of processing with 3～8% sulphuric acid soln washing (1-3), the material of removal unplated piece remained on surface, to increase the degree of cleaning on unplated piece surface, activation unplated piece surface;
(1-6) washing for the third time: the unplated piece surface 20～30s after processing with water flushing (1-4);
(1-7) clean: 30～60s is cleaned on the unplated piece surface after by ultrasonic wave, (1-5) being processed, and removes the residual material in above-mentioned treating processes existed on the unplated piece surface;
(1-8) activation: with comprising that the ionization preplating reagent of following density component carries out ionization preplating on clean unplated piece surface by replacement(metathesis)reaction, make copper surface preplating palladium metal, make the clean unplated piece surface can ionic adsorption, in order to make unplated piece and the better combination of metal finishing reagent without the cyanogen electroless plating; Wherein, ionization preplating reagent comprises:
Palladous sulfate 0.012g/L;
Sulfuric acid 9g/L;
Water 990cc/L;
Wherein, described sulfuric acid is the sulfuric acid that weight fraction is 98%;
(1-9) the 4th washing: water rinses the unplated piece surface 20～30s after (1-8) processing;
(1-10) hot water wash: be that 70～80 ℃ of water clean unplated piece surface 20～30s by temperature, remove the residual material in above-mentioned treating processes existed on the unplated piece surface, and make the unplated piece surface be warming up to 70～80 ℃, it can be reacted more fully in the metal finishing reagent without the cyanogen electroless plating, avoid the generation spot of product surface;
(2) electroless plating, it comprises following sub-step:
(2-1) electroless plating process: in the electroless plating container, ratio dilute with water mother liquor according to water: mother liquor=3:1, obtain diluent, adjust diluent pH value to 6～6.5 with ammoniacal liquor, again the diluent after processing is warming up to 70～80 ℃, the unplated piece surface is immersed in to 30～300min in the diluent after intensification;
(2-2) the 5th washing: the unplated piece surface 60～120s after processing with water flushing (2-1);
Wherein, the described reagent of the metal finishing without the cyanogen electroless plating comprises,
Surplus is water,
Preferably comprise,
Surplus is water,
Wherein, described g/L is based on the weight of the described composition of metal finishing reagent of every liter of cyanideless electro-plating.
Acid pickling step purpose of the present invention is to remove the metal oxide of unplated piece surface attachment, process and can realize with dilute sulphuric acid, and the use dilute sulphuric acid has also increased the security while using, in addition, the vitriol oil belongs to strong acid, chemical reaction can occur with unplated piece itself in it under hot conditions, therefore in the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the present invention, select dilute sulphuric acid to process the unplated piece surface, in step (1-4), the weight fraction of sulfuric acid used selects 3～8%, is preferably 4～6%.
Microetch reagent is the chemical reagent for the microetch alligatoring is carried out in unplated piece to be plated surface, its corrosive nature of utilizing strong oxidizer is carried out microetch (please be confirmed whether correct) to the unplated piece surface, and the reagent that the present invention selects following density component is as microetch reagent:
Wherein, described sulfuric acid is the sulfuric acid that weight fraction is 98%.
The present invention also provides a kind of metal surface treating method of cyanideless electro-plating, by the metal finishing reagent that uses cyanideless electro-plating, realizes the cyanideless electro-plating processing, particularly, comprises the following steps:
(1) pre-treatment, identical with the pre-treating process without the cyanogen electroless plating;
(2) electroplate, it comprises following sub-step:
(2-1) electroplating process: in electroplating container, ratio dilute with water mother liquor according to water: mother liquor=3:1, obtain diluent, adjust diluent pH value to 6～6.5 with ammoniacal liquor, again the diluent after processing is warming up to 70～80 ℃, the diluent after heating up is put into to anode, and unplated piece is positioned over negative electrode, form in ，Xiang loop line, loop line and pass into direct current;
(2-2) washing: the unplated piece surface 60～120s after processing with water flushing (2-1);
Wherein, the metal finishing reagent of described cyanideless electro-plating comprises,
Surplus is water;
Preferably comprise,
Surplus is water,
Wherein, described g/L is based on the weight of the described composition of metal finishing reagent of every liter of cyanideless electro-plating.
The coating obtained according to method provided by the invention, but it strengthens the metallic surface widespread use of hardness, wear resistance, the performance such as high temperature resistant at needs, can substitute the technique of traditional copper facing, other metal of plating such as zinc-plated.
According to the reagent of the metal finishing without cyanogen electroless plating or cyanideless electro-plating provided by the invention and the prepared coating of method, for nickel-phosphorus-tungsten composite deposite, the inventor infers that the principle of the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the present invention may be as follows:
(1) take the Ni-P codeposition theory that hypophosphite is reductive agent
1.H
2pO
2 -character
H
2pO
2 -be configured as tetrahedral, the quantum Chemical Study result shows, hydrogen atom is with 0.18984 negative charge, the overlapping population of P-H is 0.20602.And in the strong reductant sodium hypophosphite, the net charge of hydrogen atom is 0.00894 negative charge, be less than H
2pO
2 -middle hydrogen atom with net negative charge, the overlapping population of P-H is 0.34847, is greater than H
2pO
2 -the overlapping population of middle P-H.Because the Pauling electronegativity of P atom and H atom is all 2.1, above data declaration, in the P-H key, electron pair is distributed in the middle of two atoms basically, forms the covalent linkage that polarity is very little and stability is weak, but to there being equally the H of P-H key
2pO
2 -, owing to also there being two P-O keys in molecule simultaneously, the electronics population on atom obviously reduces, and is 14.05167, approximately reduce by 1 electronics, and the electronics population on the H atom increases to some extent, is 1.18984, approximately increases by 20%.These data declarations H
2pO
2 -middle P-H bond polarity obviously is better than PH
3, and share electron pair is partial to H atom one side slightly, so H
2pO
2 -p-H may be more easily and polar solvent have an effect, compare PH
3in the P-H key more easily rupture.Therefore have following phenomenon to produce:
(1) H
2pO
2 -can show extremely strong reductibility;
(2) H
2pO
2 -during middle P-H fracture, the hydrogen in dissociation product may be with the form appearance of H atom or H-ion,
H
2pO
2 -=H+HPO
2 -or H
2pO
2 -=H+HPO
2 -
2. atomic hydrogen theory
H
2pO
2 -+ H
2o=HPO
3 -+ 2H+H
+(on active surface) (1)
H+H=H
2↑ (2)
H
2PO
2 -+H
++H=P+2H
2O (3)
Ni
2++2H=Ni+2H
+ (4)
3. electrochemical theory
H
2PO
2 -+H
2O=H
2PO
3 -+2H+2e (5)
2H
++2e=H
2↑ (6)
2H
2PO
2 -+2H
++e=P+2H
2O (7)
Ni
2++2e=Ni (8)
H
2PO
2 -+H
2O=H
++HPO
3 2-+H
2↑ (9)
4. atomic hydrogen-electrochemistry associating is theoretical
H
2pO
2 -+ Ni (on active surface) → Ni...H-HPO
2 -(10)
Ni...H-HPO
2 -→Ni-H+·HPO
2 -
Or Ni...H-HPO
2 -→ [NiH]
-+ HPO
2(11)
Ni-H→Ni+H
++e (12)
[Ni-H]+e→Ni
2++H
++2e (13)
Ni
2++2e=Ni (14)
2H
++2e=H
2↑ (15)
5. hydride theory
HPO
2 -+ H
2o=HPO
3 2-+ 2H+H
-(on active surface) (16)
Ni
2++2H
-=Ni+2H (17)
H+H=H
2↑ (18)
H
++H
-=H
2↑ (19)
H now
-existence form and Ni bonding, form hydride [NiH]
-, the reaction that simultaneously generates P is:
HPO
3 2-=PO
2 -+OH
- (20)
6H
-+4H
2O+2PO
2 -=2P+8OH
-+3H
2 (21)
6. hydrate theory
Ni(OH)
2+H
2PO
2 -=NiOH+H
2PO
3 -+H (22)
NiOH+H
2PO
2 -=Ni+H
2PO
3 -+H (23)
NiOH+H
2O=Ni(OH)
2+H (24)
H+H=H
2↑ (25)
Ni+H
2PO
- 2=NiOH+P+OH
- (26)
This theoretical outstanding role is to have explained Ni
2+existence to H
2pO
2 -oxidation larger promoter action is arranged, but can not explain H
2source and the reason that descended with reaction of the pH value of solution, and the Direct precipitation of P does not meet experimental fact yet.
(2) unify mechanism
Isotropic substance tracking test phenomenon according to hydrogen, VandenMeeraker thinks no matter be with hypophosphite, or take sodium borohydride and dimethylin borine is reductive agent, the first step reaction of its reductive agent is dehydrogenation reaction, for take the dehydrogenation reaction that hypophosphite is reductive agent, following mechanism has been proposed:
Dehydrogenation H
2pO
2 -=HPO
2 -+ H (27)
Oxidation HPO
2 -+ OH-=H
2pO
3 -+ e (28)
Again in conjunction with H+H=H
2(29)
Oxidation OH
-+ H=H
2o+e (30)
Metal is separated out Ni
2++ 2e=Ni (31)
Liberation of hydrogen 2H
2o+2e=H
2+ 2OH
-(32)
P separates out mNiL
22 ++ H
2pO
2 -+ (2m+1)=Nim+P+2mL+2OH
-(33)
(3) autocatalysis theory
The surperficial autocatalysis theory proposed by the D Charlie Simpkins is thought, the deposition reaction of nickel is the catalytic activity that relies on the plating piece surface to have, make hypophosphite decompose the hydrogen atom that discharges status nascendi, then under the effect of active hydrogen, make the Hypophosporous Acid, 50 root in nickel ion and solution reduce, the nickel of separating out and phosphorus are deposited on the plating piece surface jointly simultaneously.And the alloy layer of this new formation has the autocatalysis performance, therefore reaction constantly continues, and coating is constantly thickeied.Concrete reaction can be expressed as follows:
H
2PO
3 -+H
2O=HPO
3 2-+2H+H
+ (34)
Ni
2++2[H]=Ni+2H
+ (35)
2[H]=H
2(36)
HPO
2 -+[H]=H
2O+P+OH
- (37)
H
2PO
2 -+Ni
2++3[H]=H
2PO
3 -+Ni+P+2H
++H
2↑ (38)
But, above-mentioned mechanism is only that the possibility of the principle of the invention is inferred, the present invention is not formed to any restriction, effect of the present invention is also not limited.
Metal finishing without cyanogen electroless plating or cyanideless electro-plating reagent provided by the invention and method have the following advantages:
The first, the metal surface treating method without cyanogen electroless plating and cyanideless electro-plating provided by the invention is owing to need not using potassium auric cyanide or citric acid gold potassium (that is, " Bing Erjin ") etc. containing the material of precious metal element, and cost can reduce approximately 30%; In addition, the technical process of the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the present invention is few, and discharging of waste liquid is few, and cost can reduce approximately 50%;
The second, with traditional technology, to compare, the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the invention is simple to operate, and can reach identical, even better effect;
The 3rd, the reagent of the metal finishing without cyanogen electroless plating or cyanideless electro-plating provided by the invention does not contain the toxic substances such as potassium cyanide that traditional technology must be used, therefore in use need not control, and increase safety in utilization and also save flow process;
The 4th, the hardness that adopts the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the invention to process the circuit card obtained reaches 500～600Hv, identical with the effect of traditional electrical plating nickel gold;
The 5th, the erosion resistance of the circuit card that adopts the inventive method processing to obtain is strong, in volume fraction 10%HCl, soaks 20h, without the black pad of nickel dam, produces;
The 6th, the reagent of the metal finishing without cyanogen electroless plating or cyanideless electro-plating long service life used in the present invention, use 10 months with interior without being changed;
The 7th, the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating provided by the present invention need not carry out frequently more groove operation, can reduce in maintenance and operational activity duration, saves human and material resources;
The 8th, according to the coating obtained without the metal surface treating method of cyanogen electroless plating or cyanideless electro-plating provided by the present invention, be to take the nickel-tungsten-phosphorus composite plating that nickel forms as principal element, have that intensity is large, wear resistance is strong, the performance such as high temperature resistant, acid and alkali-resistance, be widely used in need strengthening the metallic surface of hardness, wear resistance, the performance such as high temperature resistant, universality is strong, is applicable to widespread adoption.
Embodiment
Embodiment 1
Metal finishing reagent without the cyanogen electroless plating prepares and obtains by following steps:
(1) add nickelous chloride in the reactor that 85 ℃ of hot water are housed, be stirred to nickelous chloride and dissolve, be mixed with the nickel chloride solution of 41.9g/L, stand-by after filtering;
(2) add sodium hypophosphite in the reactor that hot water more than 85 ℃ is housed, be stirred to sodium hypophosphite and dissolve, be mixed with the sodium hypophosphite solution of 28.3g/L, stand-by after filtering;
(3) add ammonium dihydrogen citrate in the reactor that hot water more than 85 ℃ is housed, be stirred to ammonium dihydrogen citrate and dissolve, be mixed with the dihydrogen citrate ammonium solution of 43g/L, stand-by after filtering;
(4) add sodium wolframate in the reactor that hot water more than 85 ℃ is housed, be stirred to sodium wolframate and dissolve, be mixed with the sodium tungstate solution of 48.7g/L, stand-by after filtering;
(5) the above-mentioned solution prepared is at room temperature mixed, every 16 hours circulating filtrations 8 hours, continue, after one week, standing 5 days, to complete the present invention;
Wherein, described g/L is based on the weight of every liter of described composition of the reagent of the metal finishing without the cyanogen electroless plating.
The preparation of the metal finishing reagent of embodiment 2 cyanideless electro-platings
The step of the present embodiment is identical with embodiment 1, and difference only is that each concentration of component is:
Embodiment 3
Under 45 ℃ of conditions, process PCB-copper surface with the reagent 1 that comprises following concentration proportioning composition, remove PCB-copper surface film oxide; Carry out the microetch alligatoring with the reagent 2 that comprises following concentration proportioning composition, stinging the erosion degree of depth is 0.5 μ m, and make copper keep exposed uniform state, rinse the PCB-copper surface 30s after processing with counter-flow water, the copper surface that the sulphuric acid soln that the weight fraction of take is 3% is washed, the material of removal copper remained on surface; Rinse the PCB-copper surface 20s after processing with counter-flow water; By ultrasonic wave, 60s is cleaned in the PCB-copper surface after processing, removed the residual material in above-mentioned treating processes existed on PCB-copper surface; Carry out ionization preplating with the reagent 3 that comprises following concentration proportioning composition on clean PCB-copper surface, rinse the PCB-copper surface 20s after processing with counter-flow water, take temperature as 80 ℃ of water cleaning PCB-copper surface 20s, remove the residual material in above-mentioned treating processes existed on PCB-copper surface, and make PCB-copper surface be warming up to 75 ℃; In the electroless plating container, the reagent of the metal finishing without the cyanogen electroless plating according to preparation in the ratio dilute with water embodiment 1 of water: mother liquor=3:1, obtain diluent, regulate pH to 6.5 with ammoniacal liquor, temperature to 75 ℃ again raises, the PCB-copper of handling well is immersed in the diluent after intensification and rinses the PCB-copper surface 60s after processing by counter-flow water after 45min, and the gained thickness of coating is 60～90 μ in
Wherein,
Reagent 1 comprises,
Reagent 3 comprises,
Palladous sulfate 0.012g/L;
Sulfuric acid 9g/L;
Water 990cc/L;
Wherein, described in reagent 2 and reagent 3, sulfuric acid is the sulfuric acid that weight fraction is 98%.
Embodiment 4
Under 45 ℃ of conditions, process PCB-copper surface with agents useful for same in embodiment 31, remove the copper surface film oxide of PCB; Carry out the microetch alligatoring with agents useful for same in embodiment 32, stinging the erosion degree of depth is 1 μ m, and makes copper keep exposed uniform state, with counter-flow water, rinses the PCB-copper surface 30s after processing, the copper surface that the sulphuric acid soln that the weight fraction of take is 5% is washed, the material of removal copper remained on surface; Rinse the PCB-copper surface 30s after processing with counter-flow water; By ultrasonic wave, 30s is cleaned in the PCB-copper surface after processing, removed the residual material in above-mentioned treating processes existed on PCB-copper surface; Carry out ionization preplating with agents useful for same 3 in embodiment 3 on clean PCB-copper surface, rinse the PCB-copper surface 30s after processing with counter-flow water, take temperature as 80 ℃ of water cleaning PCB-copper surface 30s, remove the residual material in above-mentioned treating processes existed on PCB-copper surface, and make PCB-copper surface be warming up to 70 ℃; In the container of NPP plastic cement material, the reagent of the metal finishing without the cyanogen electroless plating according to preparation in the ratio dilute with water embodiment 1 of water: mother liquor=3:1, obtain diluent, regulate pH to 6.5 with ammoniacal liquor, temperature to 70 ℃ again raises, the PCB-copper of handling well is immersed in the diluent after intensification and rinses the PCB-copper surface 120s after processing with counter-flow water after 45min, and the gained thickness of coating is 60～90 μ in.
Embodiment 5
Under 45 ℃ of conditions, process PCB-copper surface with agents useful for same in embodiment 31, remove the copper surface film oxide of PCB; Carry out the microetch alligatoring with agents useful for same in embodiment 32, stinging the erosion degree of depth is 1 μ m, and makes copper keep exposed uniform state, with counter-flow water, rinses the PCB-copper surface 30s after processing, the copper surface that the sulphuric acid soln that the weight fraction of take is 5% is washed, the material of removal copper remained on surface; Rinse the PCB-copper surface 30s after processing with counter-flow water; By ultrasonic wave, 30s is cleaned in the PCB-copper surface after processing, removed the residual material in above-mentioned treating processes existed on PCB-copper surface; PCB-copper surface 30s after rinse processing with counter-flow water, the temperature of take is cleaned PCB-copper surface 30s as 80 ℃ of water, removes the residual material in above-mentioned treating processes existed on PCB-copper surface, and makes PCB-copper surface be warming up to 75 ℃; In electroplating container, metal finishing reagent according to the cyanideless electro-plating of preparation in the ratio dilute with water embodiment 2 of water: mother liquor=3:1, obtain diluent, with ammoniacal liquor, regulates pH to 6.5, temperature to 75 ℃ again raises, diluent after heating up is put into to anode, and PCB-copper is placed on negative electrode, when by direct current, nickel ion is deposited on cathodic copper in cell reaction, current density is 0.3A, energising 3min, and the gained thickness of coating is 90～120 μ in.
Embodiment 6
Under 45 ℃ of conditions, process PCB-copper surface with agents useful for same in embodiment 31, remove the copper surface film oxide of PCB; Carry out the microetch alligatoring with agents useful for same in embodiment 32, stinging the erosion degree of depth is 1 μ m, and makes copper keep exposed uniform state, with counter-flow water, rinses the PCB-copper surface 30s after processing, the copper surface that the sulphuric acid soln that the weight fraction of take is 5% is washed, the material of removal copper remained on surface; Rinse the PCB-copper surface 30s after processing with counter-flow water; By ultrasonic wave, 30s is cleaned in the PCB-copper surface after processing, removed the residual material in above-mentioned treating processes existed on PCB-copper surface; PCB-copper surface 30s after rinse processing with counter-flow water, the temperature of take is cleaned PCB-copper surface 30s as 80 ℃ of water, removes the residual material in above-mentioned treating processes existed on PCB-copper surface, and makes PCB-copper surface be warming up to 75 ℃; In electroplating container, metal finishing reagent according to the cyanideless electro-plating of preparation in the ratio dilute with water embodiment 2 of water: mother liquor=3:1, obtain diluent, with ammoniacal liquor, regulates pH to 6.5, temperature to 75 ℃ again raises, diluent after heating up is put into to anode, and PCB-copper is placed on negative electrode, when by direct current, nickel ion is deposited on cathodic copper in cell reaction, current density is 0.3A, energising 3min, and the gained thickness of coating is 85～110 μ in.
Embodiment 7
Under 45 ℃ of conditions, process PCB-copper surface with agents useful for same in embodiment 31, remove the copper surface film oxide of PCB; Carry out the microetch alligatoring with agents useful for same in embodiment 32, stinging the erosion degree of depth is 1 μ m, and makes copper keep exposed uniform state, with counter-flow water, rinses the PCB-copper surface 30s after processing, the copper surface that the sulphuric acid soln that the weight fraction of take is 5% is washed, the material of removal copper remained on surface; Rinse the PCB-copper surface 30s after processing with counter-flow water; By ultrasonic wave, 30s is cleaned in the PCB-copper surface after processing, removed the residual material in above-mentioned treating processes existed on PCB-copper surface; PCB-copper surface 30s after rinse processing with counter-flow water, the temperature of take is cleaned PCB-copper surface 30s as 80 ℃ of water, removes the residual material in above-mentioned treating processes existed on PCB-copper surface, and makes PCB-copper surface be warming up to 75 ℃; In electroplating container, metal finishing reagent according to the cyanideless electro-plating of preparation in the ratio dilute with water embodiment 2 of water: mother liquor=3:1, obtain diluent, with ammoniacal liquor, regulates pH to 7, temperature to 75 ℃ again raises, diluent after heating up is put into to anode, and PCB-copper is placed on negative electrode, when by direct current, nickel ion is deposited on cathodic copper in cell reaction, current density is 0.3A, energising 3min, and the gained thickness of coating is 85～110 μ in.
Embodiment 8
Measure the weight percentage of element in the coating that according to the present invention prepared by reagent and method by energy dispersion x-ray spectrometer (EDX), data are in Table 1.
The present embodiment used test sample is by embodiment 3～7 preparations
Each element wt percentage composition in table 1 coating
Experimental example
Experimental example 1 corrosion resistance of coating test
This experiment used test sample is by embodiment 3～6 preparations
Coating soaks corrosion data after 24h in Table 2 and table 3 in sulfuric acid and hydrochloric acid:
The solidity to corrosion of table 2 coating in sulfuric acid
(soak 24h, summer room temperature)
The solidity to corrosion of table 3 coating in hydrochloric acid
(soak 24h, summer room temperature)
The wearability test of experimental example 2 coating
This experiment used test sample is by embodiment 3～7 preparations
Testing standard or method: JIS H8503-1989
The wearability test of table 4 coating
| Sample | Wear resistance (inferior/mg) |
| Embodiment 3 | 195 |
| Embodiment 4 | 155 |
| Embodiment 5 | 133 |
| Embodiment 6 | 124 |
| Embodiment 7 | 119 |
Experimental example 3 coating acid resistance tests
This experiment used test sample is by embodiment 4 preparations
Test procedure:
To be immersed in volume fraction 31% hydrochloric acid by the sample of embodiment 4 preparations, after 5min, take out and observe, continue to soak hydrochloric acid, take out sample after 60min and observe.
Test result:
Sample surfaces does not have the situation of variable color, thus draw according to method provided by the invention to PCB-copper surface treatment can antiacidly corrode.
Experimental example 4 coating electroconductibility tests
Testing standard: IPC TM-6502.6.7
By embodiment 3-7, prepared by specimen
The test of table 5 coating electroconductibility
Experimental example 5 coating thermal shock tests
Specimen is by embodiment 3,5,7 preparations
Testing standard: IPC TM-6502.6.7.2
Condition: D-55+0/-5 ℃ (30min)
Cycle index: 100 switching time<5min
The test of table 6 coating thermal shock
Experimental example 6 bonding force tests
By embodiment 3-7, prepared by specimen
Adopt the bonding force of the crooked method test coating that fractures: nickel-tungsten-phosphorus coating is come and gone to crooked 180 degree, until fracture, observe under 50 power microscopes, coating is all without obscission, and hence one can see that, and coating provided by the invention has good bonding force.
Experimental example 7 oxidation-resistance tests
By embodiment 3-7, prepared by specimen
Coating in 400 ℃, 500 ℃, 600 ℃, 700 ℃ and 800 ℃ of High Temperature Furnaces Heating Apparatuss respectively after continuous calcination 1h, coating all without decortication, take off slag and the phenomenon that increases weight, hence one can see that, and coating provided by the invention has stronger high thermal resistance.
Experimental example 8 hardness tests
Specimen is by embodiment 4 preparations
During without thermal treatment, its hardness is 594Hv, and after 800 ℃ of thermal treatment, hardness is 830Hv, and hence one can see that, and the coating hardness intensity made according to method provided by the invention is large.
Experimental example 9 heat-resistant anti-fatigue drag tests
Specimen is by embodiment 3,5,7 preparations
Be heated to 800 ℃ from room temperature in 10s, insulation l0s, water-cooled 5s is reduced to below 100 ℃ its temperature, and insulation 10s, reheat 800 ℃, and so cold cycling is 250 times, and three samples are not all found any crackle, and hence one can see that, and the thermal fatigue resistance of this coating is strong.
Experimental example 10 chemical stabilities
Specimen is by embodiment 3,5,7 preparations
Coating is soaked to 3.5h in 1:1 sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid, corroded, soak 2h unchanged in the mixed solution of nitric acid and hydrochloric acid, hence one can see that, according to coating provided by the invention, has good chemical stability.
Known by above experimental example, the coating obtained according to reagent provided by the invention and method has good solidity to corrosion, wearability, acid resistance, electroconductibility, cold-and-heat resistent impact, bonding force, oxidation-resistance, hardness, heat-resistant anti-fatigue drag and chemical stability.
Abovely in conjunction with embodiment and exemplary example, the present invention is had been described in detail, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that in the situation that do not depart from spirit and scope of the invention, can carry out multiplely of equal valuely replacing, modifying or improve to technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (9)
1. the reagent of the metal finishing without the cyanogen electroless plating, is characterized in that, this reagent of metal finishing without the cyanogen electroless plating comprises following composition:
Surplus is water,
Wherein, described g/L is based on the weight of every liter of described composition of the reagent of the metal finishing without the cyanogen electroless plating.
2. a kind of reagent of the metal finishing without the cyanogen electroless plating according to claim 1, is characterized in that, this reagent of metal finishing without the cyanogen electroless plating comprises following composition:
Surplus is water,
Wherein, described g/L is based on the weight of every liter of described composition of the reagent of the metal finishing without the cyanogen electroless plating.
3. the metal surface treating method without the cyanogen electroless plating, is characterized in that, comprises the following steps:
(1) pre-treatment, the processing before the unplated piece surface is plated;
(2) electroless plating, it comprises following sub-step:
(2-1) electroless plating process: in the electroless plating container, the ratio dilute with water mother liquor according to water: mother liquor=3:1, obtain diluent, with ammoniacal liquor, adjusts diluent pH value to 6～6.5, then the diluent after processing is warming up to
70～80 ℃, the unplated piece surface is immersed in to 30～60min in the diluent after intensification;
(2-2) washing: water rinses the unplated piece surface 60～120s after (2-1) processing;
Wherein, described mother liquor is the reagent of the metal finishing without the cyanogen electroless plating described in claim 1 or 2.
4. a kind of metal surface treating method without the cyanogen electroless plating according to claim 3, it is characterized in that, described pre-treatment comprises degreasing, washing for the first time, microetch, washing for the second time, pickling, washes for the third time, cleans, activates, washes and hot water wash for the 4th time.
5. the metal finishing reagent of a cyanideless electro-plating, is characterized in that, the metal finishing reagent of this cyanideless electro-plating comprises following composition:
Surplus is water,
Wherein, described g/L is based on the weight of the described composition of metal finishing reagent of every liter of cyanideless electro-plating.
6. the metal finishing reagent of a kind of cyanideless electro-plating according to claim 5, is characterized in that, the metal finishing reagent of this cyanideless electro-plating comprises following composition:
Surplus is water,
Wherein, described g/L is based on the weight of the described composition of metal finishing reagent of every liter of cyanideless electro-plating.
7. the metal surface treating method of a cyanideless electro-plating, is characterized in that, comprises the following steps:
(1) pre-treatment, plated pre-treatment by the unplated piece surface;
(2) electroplate, it comprises following sub-step:
(2-1) electroplating process: in electroplating container, ratio dilute with water mother liquor according to water: mother liquor=3:1, obtain diluent, adjust diluent pH value to 6～6.5 with ammoniacal liquor, again the diluent after processing is warming up to 70～80 ℃, put into insoluble anode in the diluent after heating up, and unplated piece is placed on negative electrode, pass into direct current, make metal ion in cell reaction to negative electrode plating piece surface deposition;
(2-2) washing: water rinses the unplated piece surface 60～120s after (2-1) processing;
Wherein, the metal finishing reagent that described mother liquor is the cyanideless electro-plating described in claim 5 or 6.
8. the metal surface treating method of a kind of cyanideless electro-plating according to claim 7, is characterized in that, described pre-treatment comprises degreasing, washing for the first time, microetch, washing for the second time, pickling, washing and hot water wash for the third time.
9. according to claim 3, claim 4, claim 7 or the metal surface treating method without cyanogen electroless plating or cyanideless electro-plating claimed in claim 8, it is characterized in that,
Microetch reagent used in the microetch process of described pre-treatment comprises following composition:
Wherein, described sulfuric acid is the sulfuric acid that weight fraction is 98%;
In the acid cleaning process of described pre-treatment, acid used is sulfuric acid, and wherein, sulfuric acid is the sulfuric acid that weight fraction is 3～8%;
Passing into galvanic current density in described electroplating process is 3.0ASD.
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| Publication number | Priority date | Publication date | Assignee | Title |
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