CN110158125B - Nickel-tungsten alloy coating curing liquid for copper foil surface curing treatment and preparation method thereof - Google Patents
Nickel-tungsten alloy coating curing liquid for copper foil surface curing treatment and preparation method thereof Download PDFInfo
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- CN110158125B CN110158125B CN201810256545.7A CN201810256545A CN110158125B CN 110158125 B CN110158125 B CN 110158125B CN 201810256545 A CN201810256545 A CN 201810256545A CN 110158125 B CN110158125 B CN 110158125B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C25D7/00—Electroplating characterised by the article coated
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Abstract
The invention discloses a nickel-tungsten alloy coating curing liquid for copper foil surface curing treatment and a preparation method thereof, wherein the nickel-tungsten alloy coating mainly comprises nickel sulfate, sodium tungstate and sodium citrate, wherein in each liter of the curing liquid, the addition amount of the nickel sulfate is 20-60g, the addition amount of the sodium tungstate is 30-80g, and the addition amount of the sodium citrate is 40-150 g. The method utilizes the induction codeposition of nickel and tungsten to induce the electrochemical deposition of tungsten ions while electroplating nickel, and leads the codeposition of nickel and tungsten alloy grains on the surface of the copper foil to be refined and have compact structural organization due to the oxidation resistance and corrosion resistance of nickel and the high-temperature stability, acid resistance and high hardness and wear resistance of tungsten, and the plating layer shows that the nickel can effectively improve the oxidation resistance and corrosion resistance of the copper foil, and simultaneously adds tungsten to further improve the high-temperature peeling strength, wear resistance and high-temperature resistance stability of the copper foil, thereby creating conditions for the continuous development of the copper foil industry.
Description
Technical Field
The invention belongs to the technical field of copper foil surface curing treatment, and particularly relates to a nickel-tungsten alloy plating layer curing liquid for copper foil surface curing treatment and a preparation method thereof.
Background
At present, the surface treatment process of copper foil adopted by various copper foil production enterprises at home and abroad can be generally summarized as follows: the method comprises the steps of raw foil pretreatment, coarsening treatment, curing (heat-resistant barrier layer) treatment, anti-oxidation treatment and surface treatment.
The solidification treatment is a process of plating a thin layer of single metal, binary or multi-element alloy on the surface of the copper foil, the types of main salt and additives of the plating solution can be adjusted according to the requirements of customers to obtain solidified layers with different colors (blackening nickel plating (grey black), ashing zinc alloy plating (grey white) and yellowing copper plating (light red)), and different process conditions (different plating solution components, pH values, temperatures, current densities and plating time) are adopted for solidification. A layer of fine single metal or alloy crystal is formed on the surface of nodular copper particles generated by coarsening the copper foil, so that the roughness of a coarsened layer is reduced, and the contact surface is enlarged, thereby enhancing the peeling strength of the copper foil on a base material. The solidification aims at generating a compact barrier layer, so that the copper foil is not in direct contact with the insulating matrix, external ions are prevented from diffusing into the copper foil matrix, and the oxidation resistance of the copper foil and the corrosion resistance of a plating layer are improved.
When domestic enterprises perform surface treatment on the electrolytic copper foil, the barrier layer mainly adopts a zinc coating. The common galvanizing process can only solve the heat-resistant problem, but does not completely solve the problems of high-temperature oxidation resistance, high-temperature stripping resistance and corrosion resistance of the copper foil; during the etching of the galvanized copper foil, the phenomenon of side etching is easy to occur, so that the binding force between the copper foil and the insulating matrix is reduced, particularly, the binding force is generally reduced in a high-temperature environment and is easy to peel, and the copper foil even falls off from the insulating matrix in serious conditions, which is one of the main differences between the performance of domestic electrolytic copper foil and the performance of foreign high-grade products. In addition, although the chromium plating solution passivation commonly used in industry has good heat resistance, wear resistance and chemical stability, hexavalent chromium is extremely toxic, the environment is seriously polluted, the recovery of plating solution and the treatment of waste water are difficult and the cost is high, and the electroplating gradually develops to the chromium-free state along with the enhancement of the environmental protection consciousness of people, so the research on the surface treatment process of the electrolytic copper foil has very important significance.
Disclosure of Invention
The invention aims to provide a nickel-tungsten alloy coating curing liquid for copper foil surface curing treatment and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a nickel-tungsten alloy coating curing liquid for copper foil surface curing treatment, which takes deionized water as a solvent, and 20-60g of nickel sulfate, 30-80g of sodium tungstate and 40-150g of sodium citrate are added into per liter of curing liquid; the curing liquid also comprises additives: the curing agent comprises boric acid, ammonium chloride and ammonia water, wherein in each liter of curing liquid, the addition amount of the boric acid is 10-35g, the addition amount of the ammonium chloride is 15-50g, and the addition amount of the ammonia water with the concentration of 20% is 5-20 mL.
As the optimization of the invention to the scheme, 25g of nickel sulfate, 45g of sodium tungstate and 100g of sodium citrate are added into each liter of the curing liquid.
The invention is preferable to the scheme, the working temperature of the curing liquid is 15-65 ℃, and the working current density is 1-8A/dm2。
In the invention, the preferable scheme is that the working time of the curing solution is 5-60s, and the pH value of the plating solution is controlled to be 6-9.
The invention also provides a preparation method of the nickel-tungsten alloy coating curing liquid for copper foil surface curing treatment, which specifically comprises the following steps: firstly, adding a proper amount of deionized water into the electroplating bath, then sequentially adding weighed sodium citrate, nickel sulfate, sodium tungstate, boric acid, ammonium chloride and ammonia water according to the proportion, adjusting the pH value to 6-9, and finally using deionized water to fix the volume to prepare the required curing liquid.
The invention has the beneficial effects that: the nickel of iron group element induces the tungsten to codeposit on the surface of the copper foil in the form of alloy, thus improving the usability of the copper foil and the adaptation problem of external environment. The nickel has high corrosion resistance, the tungsten has high stability, and the sodium citrate is added into the plating solution to play the role of a complexing agent and is respectively mixed with Ni in the nickel sulfate and the sodium tungstate2+、WO4 2-Complexing to form a precursor, interacting at the cathode interface under the action of electroplating, and then forming Ni on the interface2+Promote WO4 2-The electrons obtained by discharging are reduced and precipitated on the surface of the copper foil in the form of Ni-W alloy, thereby changing the metalThe deposition potential of the ions and the structure of the deposited metal layer, the deposition potential ratio WO4 2-(deposited as tungsten blue oxide) and Ni2+The potential is corrected when the nickel is independently deposited, the microstructure of the formed Ni-W alloy plating layer is more compact and has no cracks compared with the microstructure of an independently nickel-plated layer, and meanwhile, because tungsten and the nickel-tungsten alloy thereof have excellent performances of high melting point, high density, strong heat resistance and corrosion resistance, good wear resistance, good conductivity and the like, the nickel-tungsten alloy barrier layer formed by electroplating on the surface of the copper foil can play a role in protecting the surface stability of the copper foil, improving the corrosion resistance, high-temperature peeling strength and high-temperature oxidation resistance, and effectively promoting the application of the copper foil. Wherein the precursor complex reacts: [ (Ni) (Cit)]-+
[(WO4)(Cit)(H)]-→[(Ni)(WO4)(Cit)(H)]2-+Cit3-. And (3) cathode reaction:
[(Ni)(HWO4)(Cit)]2-+8e+3H2O→Ni+W+7(OH)-+Cit3-。
the invention takes nickel sulfate, sodium tungstate and sodium citrate as main components under the condition of ensuring to meet the current environmental protection requirement (no toxicity, harmlessness and sustainable development), the solidifying solution utilizes the high-temperature stability and the nickel corrosion resistance of tungsten and the nickel-induced nickel-tungsten codeposition effect of nickel to prepare the Ni-W alloy layer with the nano structure by the electrodeposition method, the coating has low porosity and compact structure, and the amorphous Ni-W coating formed along with the increase of the W content shows good corrosion resistance and high-temperature resistance stability in an acid solution. The solidifying liquid coating has refined structure and bright surface, can effectively improve the high-temperature oxidation resistance and corrosion resistance of the copper foil, and can further improve the high-temperature peeling strength of the copper foil by forming abundant Cu-Ni-W ternary alloy phases through electrodeposition, thereby effectively ensuring the high-temperature use stability of the copper foil and creating conditions for the sustainable development of the industry.
In addition, the additive for the curing electroplating solution has the characteristics of low price, no corrosion and easy operation and implementation, is convenient and feasible for the reconstruction of the prior old process, does not need to add an additional process, and does not need to carry out any large process route reconstruction.
Drawings
FIG. 1 is a graph showing the effect of curing a copper foil by using a curing liquid according to an embodiment of the present invention.
FIG. 2 is a SEM image of the surface of the cured copper foil according to one embodiment of the present invention.
FIG. 3 is an EDS chart showing the surface energy spectrum analysis of the copper foil after the curing treatment according to the embodiment of the invention.
FIG. 4 is an XRD (X-ray diffraction analysis) pattern of the surface of the copper foil after the curing treatment according to the invention.
Fig. 5 is a tafel plot of electrochemical analysis under three curing liquids for copper foil curing in example one, example two and example three.
Fig. 6 is a graph showing the results of high temperature oxidation resistance experiments for green foils, conventional fully processed copper foils, and examples one, two, and three.
FIG. 7 is a graph showing the effect of curing the copper foil by the curing liquid in the second example.
FIG. 8 is a graph showing the effect of curing the copper foil by the curing liquid in the third example.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The general process flow of the surface treatment of the copper foil is as follows: the raw foil is subjected to oil removal, water washing, oxidation film removal, water washing, coarsening, water washing, solidification, water washing, passivation, water washing, silane coupling agent organic film and drying, the solidification solution in the embodiment of the invention is used for the solidification treatment process, the copper foil subjected to surface coarsening treatment in the copper foil surface treatment process is placed in a solidification tank with the solidification solution, a titanium plate is used as an anode, the copper foil is used as a cathode, and the current density is 1-8A/dm according to the working temperature of 15-65 ℃ and the current density of 1-8A/dm2And finishing the curing treatment of the copper foil within 5-60 s.
Example one
Preparing a curing liquid: adding 500mL of deionized water into a 1L electroplating bath, then sequentially adding 25g of accurately weighed nickel sulfate, 45g of sodium tungstate, 100g of sodium citrate, 20g of boric acid, 35g of ammonium chloride and 10mL of ammonia water (20%), adjusting the pH value to 6-9, and finally fixing the volume to 1L by using the deionized water to prepare the required curing solution.
The curing liquid is adopted to carry out curing treatment on the copper foil, the curing temperature is 30-60 ℃, and the current density is 3-6A/dm2The curing time is 5-60s, the photo of the effect after the curing is shown in figure 1, and as can be seen from figure 1, after the copper foil is cured by the curing liquid, the curing effect is obvious, and the surface is uniform and grey white. In the scanning image 2 of an electron microscope, it can be seen that a nickel-tungsten alloy coating is uniformly deposited on the surface of the nodular copper particles formed by the roughening treatment, most nickel-tungsten crystals are gathered at the pointed points of the roughened copper particles, the grains are fine and dense, and the dense coating is favorable for isolating the outside and improving the structure performance. In the EDS spectrum analysis of FIG. 3, the coating on the surface of the copper foil mainly contains 16.65 to 18.73 wt.% of Ni and 4.10 to 5.04 wt.% of W, except for 77.17 to 78.31 wt.% of Cu as a main component. The fine nickel-tungsten alloy layer crystals are regularly arranged on the surface of the nodular copper particles, so that the high-temperature oxidation resistance, high-temperature peeling resistance and corrosion resistance of the plating layer of the copper foil on the base material can be effectively enhanced. The XRD pattern of the X-ray diffraction analysis phase in figure 4 shows that the Ni-W alloy phase is formed on the surface of the coating after the copper foil is cured, and the surface of the copper foil is protected.
Example two
Preparing a curing liquid: adding 500mL of deionized water into a 1 liter electroplating bath, then sequentially adding 20g of accurately weighed nickel sulfate, 30g of sodium tungstate, 40g of sodium citrate, 10g of boric acid, 15g of ammonium chloride and 5mL of ammonia water (20%), adjusting the pH value to 6-9, and finally fixing the volume to 1L by using the deionized water to prepare the required curing solution.
The curing liquid is adopted to carry out curing treatment on the copper foil, the curing working temperature is 30-60 ℃, and the current density is 3-6A/dm2And curing for 5-60s, and the photograph of the effect of the copper foil after curing is shown in FIG. 7. The cured layer is pale gray under the same electrodeposition parameters, but can also beThe copper foil matrix is seen to be red, the surface uniformity is poor, the content of the components is obviously less than that of the copper foil matrix in the embodiment, the curing effect is relatively poor, the high-temperature oxidation resistance is poor, the high-temperature peeling strength is low, and the corrosion resistance is poor.
EXAMPLE III
Preparing a curing liquid: adding 500mL of deionized water into a 1 liter electroplating bath, then sequentially adding 60g of accurately weighed nickel sulfate, 80g of sodium tungstate, 150g of sodium citrate, 35g of boric acid, 50g of ammonium chloride and 20mL of ammonia water (20%), adjusting the pH value to 6-9, and finally fixing the volume to 1L by using the deionized water to prepare the required curing solution.
The curing liquid is adopted to carry out curing treatment on the copper foil, the curing working temperature is 30-60 ℃, and the current density is 3-6A/dm2And curing for 5-60s, and the photograph of the effect of the copper foil after curing is shown in FIG. 8. Under the same electrodeposition parameters, the solidified layer is dark gray, the surface uniformity is poor, compared with the first embodiment, the solidified layer is obviously caused by excessive plating solution components, the solidification effect is poor, and the environmental resistance performance of the copper foil is obviously inferior to that of the first embodiment.
Based on the above examples, it can be seen from fig. 5 that the copper foil has the best electrochemical corrosion test effect, the corrosion potential of the copper foil is shifted forward, and the corrosion current on the ordinate is the smallest in the first example, which indicates that the Ni-W plating layer of the first example effectively improves the corrosion resistance of the copper foil. Meanwhile, the Ni-W alloy plating layer has a self-passivation effect in the cathode polarization process, and the corrosion resistance of the copper foil is further enhanced.
Fig. 6 shows that the surface of the left-most green foil is oxidized and yellowed seriously by the experiment result of keeping the temperature of the box-type resistance furnace at 210 ℃ for 2 hours, the surface of the copper foil of the electrodeposited nickel-tungsten alloy coating layer through the embodiment still keeps the color of the original coating layer, and compared with the surface of the existing copper foil which is completely treated by a certain factory and is oxidized and yellowed and peeled, the electroplated nickel-tungsten alloy can effectively prevent the high-temperature oxidation of the copper foil, and is beneficial to the high-temperature stable use of the practical application environment of the copper foil.
Therefore, according to the invention, the content range of nickel sulfate in the curing liquid is 20-60g/L, the content range of sodium tungstate is 30-80g/L, and the content range of sodium citrate is 40-150g/L, as long as the addition amounts of boric acid, ammonium chloride and ammonia water, the curing working temperature, the current density and the curing treatment time are selected within the range defined by the process of the invention, the pH value is controlled, and the curing treatment effect of the copper foil is close to the treatment effect under the optimal process condition in the first embodiment, the treatment requirements can be met.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (3)
1. The surface curing treatment process of the copper foil is characterized by comprising the following steps: placing the copper foil subjected to surface roughening treatment in the copper foil surface treatment process into a curing tank containing curing liquid, using a titanium plate as an anode and a copper foil as a cathode, and controlling the working temperature at 15-65 ℃ and the current density at 1-8A/dm2And the curing treatment time is 5-60s to finish the curing treatment of the copper foil;
the curing liquid takes deionized water as a solvent, and 20-60g of nickel sulfate, 30-80g of sodium tungstate and 40-150g of sodium citrate are added into each liter of curing liquid; the curing liquid also comprises additives: boric acid, ammonium chloride and ammonia water, wherein in each liter of curing solution, the addition amount of the boric acid is 10-35g, the addition amount of the ammonium chloride is 15-50g, and the addition amount of the ammonia water with the concentration of 20% is 5-20mL, so that the pH value of the plating solution is controlled to be 6-9.
2. The process according to claim 1, wherein 25g of nickel sulfate, 45g of sodium tungstate and 100g of sodium citrate are added to each liter of the curing liquid.
3. The process of claim 1, wherein the curing fluid is prepared by: firstly, adding a proper amount of deionized water into the electroplating bath, then sequentially adding weighed nickel sulfate, sodium tungstate, sodium citrate, boric acid, ammonium chloride and ammonia water according to the proportion, adjusting the pH value to 6-9, and finally using deionized water to fix the volume to prepare the required curing liquid.
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