CN112267134B - Alloy electroplating solution - Google Patents
Alloy electroplating solution Download PDFInfo
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- CN112267134B CN112267134B CN202011329985.4A CN202011329985A CN112267134B CN 112267134 B CN112267134 B CN 112267134B CN 202011329985 A CN202011329985 A CN 202011329985A CN 112267134 B CN112267134 B CN 112267134B
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Abstract
The invention provides an additive for a Co-Ni alloy electroplating solution for electroplating, which comprises chlorobenzaldehyde, 1, 3-propanedithiol, sodium butynol ether propane sulfonate and sodium diethylenetriamine pentaacetic acid.
Description
Technical Field
The invention belongs to an electroplating process, and relates to an additive composition of a porous copper plate Co-Ni alloy electroplating solution for a crystallizer.
Background
Continuous casting is used as the most main method for producing billets, and the crystallizer is compared with a heart of a continuous casting machine, wherein the quality of the casting billets, the production efficiency and the production cost of continuous casting are directly affected by the performance of a copper plate of the crystallizer, the copper plate of the crystallizer is used as an important heat conduction component for solidification molding of molten steel in continuous casting, and the primary function of the copper plate of the crystallizer is to release heat of the molten steel as soon as possible to form a solidified billet shell with enough thickness, so that the primary function requirement of the copper plate of the crystallizer is good in heat conduction performance, which is the reason for selecting copper as a material of the crystallizer, however, the working environment of the crystallizer is extremely bad, hot cracks are easily generated under the cold and hot fatigue effects of high-temperature molten steel and cooling water, and deformation can occur if the temperature difference is too large; is easy to cause chemical corrosion under the action of the protective slag; abrasion marks and abrasion are easy to cause under the conditions of dummy ingot, blank drawing and vibration, scratches and the like are easy to cause under the conditions of taper adjustment and section width adjustment, and most of the defects occur on the surface of a crystallizer copper plate, so that the basic performance requirements of the crystallizer copper plate are as follows: the copper plate of the continuous casting crystallizer is made of the materials with enough strength and rigidity, and the surface performance of the inner cavity of the continuous casting crystallizer is also provided with higher and higher requirements due to the improvement of the drawing speed of a continuous casting machine.
Among the surface treatment techniques of continuous casting crystallizer copper plates, electroplating techniques are the earliest developed, most applied and most mature. The electroplating technology has the advantages of good economy of surface treatment, less investment, low production cost and mature and simple process; and plating solutions are various, so that plating layers with different compositions can be obtained. Common single plating Cr layer, single plating Ni layer, ni-Cr double plating layer, ni-Fe alloy plating layer, ni-Co alloy plating layer, co-Ni alloy plating layer, etc.
Single Cr layer plating, the advantage: the hardness is high, and the chemical stability is good; disadvantages: no matter the thin and thick materials have cracks, the expansion coefficient and the thermal conductivity have larger difference with those of the copper matrix, and the copper matrix is easy to fall off, so that the copper matrix is abandoned.
Single plating Ni layer: the advantages are that: the thermal expansion coefficient and the thermal conductivity are similar to those of a copper matrix, the chemical stability is good, and the plating can be performed by 3-8mm; although the hardness of the nickel plating layer is 180-250 HV higher than that of copper, the chemical stability is better, the sealing capability is very strong, and the nickel plating layer can be plated to 3-8mm, but the hardness of the nickel plating layer is not worn by continuous casting billets, so the service life of the plating layer is not high.
Ni-Cr double plating: the surface of copper is plated with Ni coating and then plated with Cr coating. The advantages are that: ni plays an intermediate excessive role, so that the bonding strength is improved, the outer surface is a Cr layer, the wear resistance is good, and the net-shaped cracks on the surface of a casting blank can be eliminated; disadvantages: the plating process is complex, the thermal expansion coefficient and the thermal conductivity difference between Cr and Ni are large, the bonding strength between a Cr layer and a Ni layer is low, the electroplating process of a nickel-chromium plating layer is complex and mainly depends on the wear resistance of the nickel layer, so that the service life of the plating layer is limited, and the thin and porous chromium plating layer is extremely easy to generate potential corrosion (the current copper plates of most continuous casting crystallizers adopt double plating layers of inner-layer Ni plating and outer-layer Cr plating) except corrosion resistance under high-temperature and corrosion environments.
Ni-Fe alloy plating: the Ni-Fe alloy plating developed in China has strong high temperature resistance, good thermal shock resistance, higher hardness (about 500 HV) than that of a single Ni plating layer and better wear resistance. Disadvantages: the alloy plating solution is not easy to control, the yield is low, the content of iron in the ferronickel used as a plating layer of a slab crystallizer is generally controlled to be 3% -12%, the hardness of the ferronickel is 320-420 HV at normal temperature, and the wear resistance is enhanced; the brittleness is increased, the internal stress is high, and the bonding strength with the matrix metal is also affected, so that the nickel-iron coating has poor heat-alternating-resistance performance. In addition, the electrolyte used to deposit such alloys is also characterized by instability, which tends to result in reduced yields. These factors may be explained by how the application of nickel-iron alloys is limited over nickel-cobalt alloys.
Besides retaining the physical and chemical properties of the nickel coating, the Ni-Co alloy has two advantages: the hardness is obviously improved, and the hardness is also very high at high temperature; the chemical stability, especially the thermal stability is good. The alloy coating is an ideal coating of a slab crystallizer, but Co is too high in cost, so that the coating is high in cost, meanwhile, the hardness is high, the alloy coating is high in stress, the alternating resistance of the coating is poor, and the application of the Ni-Co alloy is limited.
Regarding cobalt nickel alloys: CN1500916 discloses a gradient composite coating for copper plate of continuous casting crystallizer, which contains Co 50-79.9% and Ni 20-49.9% of coating volume, 0.1-10% of dispersed Al203 particles with particle size less than 0.5 microns. The coating has a gradient structure, the content of Co and Al2O3 gradually increases in the direction from inside to outside, and the content of Ni gradually decreases. According to the plating method of the gradient composite plating layer, a sulfamate system added with 10-80 g/L of Al2O3 particles with the particle size smaller than 0.5 micron is used for depositing the Co-Ni-Al2O3 gradient composite plating layer on copper or copper alloy by utilizing specific Al2O3 particle activation pretreatment and electrodeposition technology. The activation pretreatment adopts FC-4 cationic surfactant as an ionic dispersing agent. The Co-Ni-Al2O3 composite coating can meet the use requirements of various high-temperature wear-resistant fields and has wide industrial application.
CN104759596A long-life composite coating continuous casting crystallizer copper plate and a preparation process thereof belong to the technical field of electroplating. The long-life composite coating continuous casting crystallizer copper plate comprises a copper plate substrate and a coating on the surface of the copper plate substrate, wherein the coating comprises an upper electroplated layer and a lower sprayed layer, the upper electroplated layer is a high-temperature-resistant corrosion-resistant pure nickel or low cobalt nickel alloy coating, the mass percentage of cobalt in the low cobalt nickel alloy coating is not more than 3%, and the lower sprayed layer is a wear-resistant coating or ceramic coating. The invention combines electroplating and supersonic thermal spraying processes to lead the upper part and the lower part of the crystallizer copper plate to be respectively different alloy plating layers, effectively solves the different requirements of continuous casting production on the upper part and the lower part of the crystallizer copper plate, leads the upper electroplated layer not to be easy to generate hot cracks and spalling at high temperature, leads the lower sprayed layer to have excellent wear resistance, and leads the service life, the product quality and the like of the crystallizer copper plate to be greatly improved.
As is apparent from the above results, the direction of improving the plating in the prior art is mainly focused on the adjustment and improvement of the plating components, parameters, or the effect of improving the plating by using composite plating through inorganic particles, but the prior art is rarely based on the copper plate and the plating solution at the same time, and the bonding force between the copper plate and the plating layer is improved by improving the state of the surface of the copper plate.
Disclosure of Invention
Based on the above, the invention provides an additive for Co-Ni alloy electroplating solution, which comprises chlorobenzaldehyde, 1, 3-propanedithiol, butynol ether propane sodium sulfonate and diethylenetriamine pentaacetic acid sodium salt, can effectively inhibit abnormal deposition of CoNi, has small crystal grains of a coating, smooth surface, low internal stress, strong deep plating capability and better electroplating effect than similar plating solution, and can obtain non-uniform rich pore channels on the surface of a copper material by a certain surface treatment method, wherein the pore channels provide high-quality attachment points for subsequent electroplating treatment, effectively improve the binding force of the coating and a base material and effectively prolong the service life of a crystallizer copper plate.
An electroplating Co-Ni alloy electroplating solution additive, wherein the electroplating solution comprises NiSO 4 . 6H 2 O，CoSO 4 . 7H 2 O, H3BO3, characterized in that the plating solution also comprises additives, wherein the contents of the chlorobenzaldehyde, 1, 3-propanedithiol, butynol ether propane sodium sulfonate and diethylenetriamine pentaacetic acid sodium are as follows:
NiSO 4 . 6H 2 O：260g/L-300g/L；
CoSO 4 . 7H 2 O：10-20g/L；
H 3 BO 3 ：20-30g/L；
chlorobenzaldehyde: 1-3g/L;
1, 3-propanedithiol 1-2g/L;
sodium butynol ether propane sulfonate: 0.5-1.5g/L;
1-3g/L of diethylenetriamine pentaacetic acid sodium salt
The balance of water.
Further, the electroplating parameters of the electroplating solution are as follows: the current density is 2-5A/dm 2 pH is 3-5, and temperature is 40-45 o C, magnetically stirring for 30-50min at 200-300rpm.
Further, the copper plate is a crystallizer copper plate subjected to surface treatment, and the copper plate is a porous chromium-zirconium-copper alloy plate.
Further, the surface treatment method comprises the following steps: (1) pretreatment; (2) alkaline electrochemical corrosion treatment; (3) And (3) high-temperature annealing reduction, wherein in the alkaline washing electrochemical corrosion treatment process, a crystallizer copper plate is used as a working electrode, an inert graphite carbon rod is used as a counter electrode, and a controllable positive and negative electrode reversing power supply is used.
Further, the pretreatment comprises mechanical polishing, degreasing, hot water washing, cold water washing, acid activation, alkali washing and water washing.
Further, the electrolyte used in the alkaline electrochemical corrosion treatment is 50-80g/L potassium hydroxide, 1-3g/LNa 2 SiO 3 The temperature is 30-40 ℃.
Further, the alkaline electrochemical corrosion treatment process comprises the following steps: starting a power supply, taking a copper plate as an anode, reacting for 2-5min, and controlling the current density to be 1.5-2.0A/dm 2 Turning off the power supply, ultrasonically stirring for 15s, turning on and switching the positive and negative directions of the power supply, taking the copper plate as a cathode, reacting for 5-8min, and controlling the current density to be 0.2-0.5A/dm 2 And stirring by ultrasonic for 30s.
Further, the alkaline electrochemical corrosion treatment comprises the steps of turning on the power supply, turning off the power supply, switching the power supply and turning off the power supply into one cycle, wherein the number of the cycles is 3-5, and the total alkaline electrochemical corrosion treatment time is not more than 40min.
Further, the high-temperature annealing reduction parameters are as follows: 5vol.% of a hydrogen/nitrogen mixture, 5 o The temperature rise rate of C/min is increased to 650 o C, preserving heat for 2-3h, removing heat source, continuously introducing mixed gas, and naturally cooling。
Further, the mechanical polishing is polishing by using 2000-mesh sand paper, and the degreasing and degreasing are as follows: 25g/LNa 2 CO 3 、10g/LNaOH、50g/LNa 3 PO 4 . 12H 2 O、7g/LNa 2 SiO 3 At a temperature of 70 to 80 o C, time 10min.
Further, the acid activates 10wt.% H 2 SO 4 For 50s, the alkaline wash was 10wt.% sodium carbonate for 60s.
Further, the following mass percentages are: 1-2wt.% of Cr, 0.2-0.4wt.% of Zr, 0.03-0.06wt.% of Fe, 0.003-0.007wt.% of P, 0.002-0.003wt.% of N, and the balance copper.
And further, after the high-temperature annealing reduction, carrying out vacuum sealing preservation on the obtained crystallizer copper plate.
As for chlorobenzaldehyde, chlorobenzaldehyde is mainly used as a stress remover, the chlorobenzaldehyde can effectively control the deposition speed during the whole electroplating process, and the deposition speed is higher under the condition of high current, for example, the current density is 5A/dm 2 On the premise that other conditions are completely consistent, when chlorobenzaldehyde is not added, the deposition speed is 153mg/H, the corresponding stress is 25Mpa, when chlorobenzaldehyde is added, the deposition speed is obviously reduced to 128mg/H, the corresponding stress is 13Mpa, the stress is generated due to unbalanced crystallization in the electrodeposition process, so that crystal lattice defects are generated, when H ions are diffused into the positions of the crystal lattice defects, if enrichment occurs, the pressure is generated on surrounding tissues, the problems of foaming, cracking and the like are generated, and the chlorobenzaldehyde can obviously reduce the stress in a coating, as shown in the following table:
regarding 1, 3-propanedithiol, which is a hydrogen evolution inhibitor, for thiol, mercapto is a main expression of its chemical properties, and because of a certain traction force between S and H, if in a pure thiol solution, a hydrogen evolution process is inevitably possible during cathode deposition, but under an acid-rich condition, such as pH 3-5 of the present invention, the hydrogen evolution inhibitor 1, 3-propanedithiol can effectively complex H ions and part of metal ions, thereby inhibiting the generation of hydrogen during electroplating treatment and reducing the amount of pores in a plating film, but if the content of 1, 3-propanedithiol in a plating solution is too high, it is difficult to form a plating layer.
Regarding butynol ether propane sodium sulfonate, regarding the plating solution, if the electroplating substrate is a copper plate, especially the surface is a porous copper plate, the plating solution is required to be provided with the plating solution, and the plating solution is required to be provided with the plating solution, so that the plating solution is known to a person skilled in the art, due to the existence of a plurality of holes, the cathode current density at a deep hole is small, the cathode polarization value is also small, the cathode negative potential is also less negative, the precipitation potential of metal is relatively not positive, and the deep plating capability is poor; the difference of the deep plating capability causes the difference of the plating growth and the change of the plating thickness, the addition of the plating displacement agent can improve the cathode polarization degree of the plating solution, improve the dispersion capability of the plating solution, lead the thickness distribution of the plating layer to be more uniform, improve the deep plating capability, fully cover the matrix, namely, the butynol ether propane sodium sulfonate expands the metal ion adsorption range in the plating solution, plays the role of dispersing the plating solution, improves the depositable current density range of the plating solution, and further reduces the depositable current density.
With respect to sodium diethylenetriamine pentaacetate, a complexing agent, those skilled in the art know that electrodeposited Co-Ni alloys exhibit abnormal Co-deposition, which is the more negative thermodynamic deposition potential of cobalt that is more readily deposited than the more positive deposition potential of nickel. The standard electrode potentials of Ni2+ and Co2+ are close, the standard electrode potentials of Ni/Ni2+ (more positive, the standard electrode potentials of Co/Co2+ are-0.250V and-0.277V respectively, but because Co-Ni alloy has abnormal Co-deposition phenomenon in the electro-deposition process, although the cobalt ion concentration in the plating solution is far smaller than that of nickel, alloy with higher cobalt content can be obtained, such as Co-Ni alloy plating layer with the Ni of which the mole fraction is 50 percent, nickel sulfate with the quantity being more than 20 times of that of cobalt sulfate needs to be added in the bath solution, and the potential of the metal ions can be positively moved or negatively moved by changing the concentration of the metal ions in the prior art to enable the Co-Ni alloy to meet the basic condition of Co-deposition, namely the precipitation potential to be close to or equal. According to Nernst's formula, it is theoretically possible, but in practice, when the concentration of divalent metal ions is increased by 10 times, the equilibrium potential is only shifted by 0.029V, and the solubility of metal ions is limited, so that it is difficult to adopt a method of changing the concentration of metal ions in the electrolyte to meet the requirement of co-deposition, especially cobalt-nickel alloy which is abnormally deposited, and therefore, the present invention changes the potential of metal ions by adding a complexing agent to realize co-deposition, which is a very effective method. The complexing agent is added to form metal complex ions in the electrolyte, so that the precipitation potential of the two metal ions is close to each other, and the co-deposition requirement is met.
According to the invention, through screening, the complexing of the diethylenetriamine pentaacetic acid sodium is best, the complexing agent can enable the overpotential of nickel and cobalt to be more approximate, so that the co-deposition is facilitated, and the diethylenetriamine pentaacetic acid sodium can be adsorbed on the surface of a cathode copper plate to form a compact adsorption layer so as to prevent the discharge process of metal coordination ions or the surface diffusion of metal adsorption atoms, so that the overvoltage of the cathode reaction is increased, and the 1, 3-propanedithiol can capture electrons at the cathode, thereby slowing down the reaction speed of the electrode and obtaining a casting layer with fine crystal grains and brightness smoothness.
Specifically, the following table:
the table above shows that after the diethylenetriamine pentaacetic acid sodium is added, the electrodeposition of cobalt can be effectively inhibited, or nickel cobalt metal can be effectively complexed, the precipitation potential of the two can be balanced, and compared with the method without adding complexing agent, the abnormal precipitation of Co is obviously reduced. In addition, when the concentration of the diethylenetriamine pentaacetic acid sodium in the plating solution is 0.5g/L, the crystal grains in the plating layer are obviously smaller, but the influence is not obvious, and when the concentration is 1g/L, the crystal grains of the obtained plating layer are partially refined and are uneven in size. When the grain size of the obtained coating is 2g/L, the grain size of the obtained coating is partially refined, the grain size is not uniform and is completely fine, and the surface is flat. When the concentration is 5g/L, the surface is convex-concave, and the particle size is uneven. Obviously, the sodium diethylenetriamine pentaacetate can refine grains to make the surface of the coating flat, but too much sodium diethylenetriamine pentaacetate is disadvantageous to the grain refinement of the coating. Regarding the main salts and boric acid: nickel sulfate and cobalt sulfate are used as main salts, metal ions are mainly provided, the concentration of the main salts is increased or reduced in a proper range, certain influence is generated on the electrodeposition process and the performance of a casting layer, for example, the concentration of the main salts is increased, the deposition speed of casting liquid is increased, the current efficiency is increased, otherwise, the concentration is too low, a series of problems such as poor liquid conductivity, low current efficiency, slow deposition speed, poor dispersion capability and the like are caused, and boric acid stabilizes the pH value of electrolyte, the pH value of the solution is small in variation range, so that the quality of the casting layer is ensured.
Regarding the current density: one of the important parameters of electrodeposition is current density, which is convenient in terms of the texture and properties of the deposit
Important functions. The current density has an upper limit and a lower limit, and when the current density is lower than the lower limit, metal cannot be electroplated or the quality of an electroplated layer is poor; when the pH is higher than the upper limit, the pH is raised due to the hydrogen evolution reaction at the cathode, and the formed hydroxide is sandwiched in the plating layer. In order to prevent the generation of the phenomenon, the stirring speed can be increased or the mass transfer process can be improved, the cathode polarization effect can be increased within a certain current density value, the grain size can be effectively reduced, and the current density is 2-5A/dm 2 At 2-5A/dm 2 Within the range, the hardness of the coating is increased and then decreased when the current density is increased. The current density is lower than 2A/dm 2 The deposition rate at the cathode is slow, and the hardness is reduced; the current density is higher than 5A/dm 2 Pinholes appear on the surface of the plating layer, resulting in roughness of the plating layer.
Regarding the temperature: the temperature is increased, the diffusion speed of ions is increased, concentration polarization is reduced, crystallization is thicker, but the temperature can obviously increase the activity of metal ions, the temperature is 40-45 o C。
Regarding pH: the pH value is lower than 3, the current efficiency is reduced, the cast layer is dark, the pH value is higher than 5, hydroxide is easily formed by metal ions, the plating layer is rough and hydrogen embrittled, and the pH value is controlled within the range of 3-5.
Wherein, regarding the selection of the substrate: in the continuous casting and rolling process, the maximum temperature of the working surface of the copper plate contacted with molten steel can reach about 350 ℃, the maximum temperature of a high base material hot surface is low, and the working time of the crystallizer can be prolonged when the thermal deformation is small. The high-temperature strength is improved along with the increase of the strength of the base material, the heat deformation resistance and the high-temperature creep resistance are improved, the service life of the copper plate is prolonged, and the service life of the Cu-Cr-Zr is also prolonged because of high recrystallization temperature and high strength, so that the crystallizer copper plate plays a vital role in the service life of the crystallizer, and the crystallizer copper plate can be red copper, copper-silver alloy, copper-chromium alloy, chromium-zirconium-copper alloy and the like, wherein the preferable chromium-zirconium-copper alloy comprises the following components in percentage: 1-2wt.% of Cr, 0.2-0.4wt.% of Zr, 0.03-0.06wt.% of Fe, 0.003-0.007wt.% of P, 0.002-0.003wt.% of N, the remainder being copper, for the following reasons: (1) Compared with pure copper with the tensile strength of about 200Mpa, the yield strength of about 40Mpa and the hardness of 50Hv, the chromium-zirconium-copper has excellent tensile strength, yield strength and hardness, and generally has the tensile strength of about 350Mpa, the yield strength of about 280Mpa and the hardness of 115Hv, and has the most excellent performance in similar alloys; (2) The invention mainly obtains the surface state with rich pore channels through corrosion, namely, the more the metal alloy forms a second phase which is difficult to corrode in the smelting process, such as ZrCu 3 ，ZrCrCu 3 Or nitride, phosphide, the more pores it obtains on the surface, the more advantageous the subsequent electrodeposition treatment.
Wherein with respect to the pretreatment: the surface state and cleanliness of the copper plate substrate before electroplating are the preconditions for ensuring the quality of the plating layer. If the surface of the substrate is rough, rusted or oil stains exist, the binding force, corrosion resistance, abrasion resistance and other performances of the electroplated layer formed on the surface of the substrate are poor. Practice proves that when the substrate is not pretreated or is not pretreated properly, the obtained coating on the surface of the substrate is easy to generate phenomena of bubbling, falling off, poor corrosion resistance and the like. Therefore, to obtain a high quality coating, the copper plate substrate must be pretreated, and the pretreatment must be performed in accordance with strict requirements.
Before surface treatment, the copper plate of the continuous casting crystallizer needs to be subjected to pretreatment of mechanical polishing, degreasing, hot water washing, cold water washing, acid activation, alkali washing and water washing.
The mechanical polishing is 2000-mesh sand paper polishing, and 200# sand paper, 400# sand paper, 600# sand paper, 800# sand paper and 1200# sand paper can be sequentially used according to the surface condition of the copper material, so that the surface of the copper material is smooth, the roughness is reduced, macroscopic defects such as scratches, oxide layers, corrosion marks and rust spots on the surface are removed, the surface smoothness is improved, and the copper material reaches enough smoothness.
Wherein, regarding degreasing: 25g/LNa 2 CO 3 、10g/LNaOH、50g/LNa 3 PO 4 . 12H 2 O、7g/LNa 2 SiO 3 At a temperature of 70 to 80 o C, removing grease by saponification of the hot alkali solution in 10min, wherein the saponification reaction is as follows: (C17H 35 COO) 3 C 3 H 5 +3NaOH→3C 17 H 35 COONa+C 3 H 5 (OH) 3 The degreasing process includes one hot water washing, one cold water washing, washing the surface of the workpiece to be plated with deionized water heated to at least 45-50 deg.c, eliminating the residual alkali liquid, and washing with cold deionized water. After water washing, observing whether the surface of the workpiece to be plated is completely wetted or not, and taking the surface as a basis for judging whether grease is removed or not, if a water film on the surface of the workpiece to be plated is cracked or forms water drops and drops, the water film needs to be reprocessed, and after one procedure is finished, residual liquid on the surface of the workpiece to be plated is necessarily washed clean by deionized water, so that the influence on the next procedure is prevented.
Wherein with respect to acid activation: 10wt.% H 2 SO 4 The time is 50s, and the main purpose of the method is to remove the oxide on the surface of the metal which is not removed by the mechanical polishing in the preamble, so that the oxide film must be removed, otherwise, the oxide film on the surface of the metal wraps the crystalline structure of the metal, the crystalline structure of the metal cannot be displayed, the binding force between the base material and the coating can be obviously reduced, the acidification time cannot be too long, otherwise, the phenomenon of 'over corrosion' can occur, and thus, the overpotential of hydrogen on the surface of the plated part in the electroplating process can be greatly reduced, and a large amount of hydrogen is precipitated.
Regarding alkaline washing, the alkaline washing liquid is 10wt.% sodium carbonate, the time is 60s, the purpose of the alkaline washing is mainly to neutralize the acid washing of the acid washing activation liquid, the alkaline washing liquid can be sodium hydroxide, but the alkali property of the alkaline washing liquid is easy to cause corrosion or form particle precipitation, so that the alkaline washing liquid is sodium carbonate, alkaline use is performed, the reaction is carbon dioxide, precipitation of precipitation particles cannot exist, and meanwhile, the alkaline washing liquid also has a transition effect, and if the direct acid washing is completed, alkaline electrochemical corrosion is performed, the effect is poor, and the alkaline electrochemical corrosion effect is better by using the step of transition of sodium carbonate.
For alkaline electrochemical etching treatment, the electrochemical etching solution here is 50-80g/L potassium hydroxide and 1-3g/LNa 2 SiO 3 The electrochemical corrosion of the invention is alkali instead of acid, and the acid can also generate anodic oxidation reaction with copper at the anode in the corrosion process, however, for copper metal, the acid is used as corrosive liquid, obvious basic salt precipitate can be formed at the anode to influence the corrosion, and meanwhile, the possibility of copper passivation is also generated, so alkali liquid is used as corrosive liquid, and the alkali liquid contains Na2SiO 3 As a corrosion inhibitor, the excessive corrosion is obviously reduced, and the electrochemical cathode anode polishing is avoided without oxidation or reduction at the anode.
The temperature in the electrochemical corrosion process is 30-40 DEG C o C, in the electrochemical sample process, under the low-temperature condition, the formed oxide film is a loose film layer, which is more loose and is favorable for corrosion, if the temperature is raised to 70 DEG o And C, the corrosion does not occur, and a passivation film is directly formed to stop the corrosion.
For alkaline electrochemical corrosion treatment, a power supply is turned on, a copper plate is used as an anode, the reaction time is 2-5min, and the current density is 1.5-2.0A/dm 2 Turning off the power supply, ultrasonically stirring for 15s, turning on and switching the positive and negative directions of the power supply, taking the copper plate as a cathode, reacting for 5-8min, and controlling the current density to be 0.2-0.5A/dm 2 Ultrasonic stirring for 30s starts with anodic oxidation, and in the whole process, the copper plate is used as an anode to perform oxidation reaction, so that the time is short, the current density is high, local corrosion is facilitated, hole corrosion occurs, if the time is long, the whole corrosion is caused, a pore channel is not easy to form, and the method is more similar to electrolytic polishing, has high current density and is beneficial to occurrencePorous corrosion, the higher the density, the greater the pore density; the power supply is turned off, because partial oxide is formed in the pore canal, ultrasonic oscillation is needed to remove loose oxide in the pore canal, subsequent reduction treatment is facilitated, the ultrasonic frequency is 20-40KHz, the time is 30s, after anodic oxidation, a cathode reduction process is carried out, because the pore canal after anodic oxidation is shallower and flatter, and an oxide film in the pore canal needs to be removed, the direction of the power supply is switched, the copper plate becomes a cathode, reduction of copper of anodic oxidation products occurs at the cathode, copper ions are formed into electrolyte, the time is long in the cathode reduction process, the current density is small, the long time is favorable for sufficient oxide reduction, the low current density is favorable for small pore reduction, the ultrasonic stirring is turned off again for 30s, and the time is long, mainly, the copper ions hoped to be reduced near the pore canal of the cathode can fully enter the electrolyte instead of enriching near the pore canal.
Regarding the circulation, the repeated circulation is favorable for the deep corrosion of the pore canal, but excessive corrosion is not needed, the circulation times are 3-5 times, and the total alkaline electrochemical corrosion treatment time is not more than 40min.
Regarding the high-temperature annealing reduction parameters, mainly for reducing the thermal stress of the copper material and sufficiently removing oxide particles on the surface, if the high-temperature annealing reduction step is deleted in the whole process, the substrate and the coating are peeled off due to the thermal stress, and the binding force is not strong due to the existence of the oxide. The high-temperature annealing reduction parameters are as follows: 5vol.% of a hydrogen/nitrogen mixture, 5 o The temperature rise rate of C/min is increased to 650 o And C, preserving heat for 2-3h, removing a heat source, continuously introducing mixed gas, and naturally cooling.
In the sealing treatment, the subsequent plating process may be directly performed, and if the subsequent other steps are not performed temporarily, the vacuum sealing treatment is performed on the substrate.
The beneficial technical effects are as follows:
(1) The pore canal on the surface of the copper material is enriched through surface treatment, and a non-uniform pore structure is obtained;
(2) The thermal stress of the base material is reduced through surface treatment, the thermal fatigue resistance of the copper plate is improved, and the bonding force between the coating and the copper plate is improved;
(3) The plate has long service life and is a preferable copper plate base material.
(4) The additive can effectively inhibit the abnormal deposition of CoNi, and has small crystal grain, smooth surface, low internal stress, strong deep plating capability and better plating effect than similar plating solutions.
Drawings
Fig. 1 is an SEM image after pretreatment of the copper plate of the mold.
FIG. 2 is an SEM image after the alkaline electrochemical corrosion-reduction treatment of the present invention.
FIG. 3 is a SEM sectional view after an alkaline electrochemical corrosion-reduction treatment according to the invention.
FIG. 4 is a SEM sectional view of a copper plate of the crystallizer of the present invention after Co-Ni layer plating.
Fig. 5 is an SEM image of the surface treated copper plate of the crystallizer of comparative example 1.
FIG. 6 is an enlarged view of a portion of an SEM section of a copper plate of the crystallizer according to the present invention after Co-Ni layer plating.
Description of the embodiments
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
The surface treatment method of the crystallizer copper plate is characterized in that the copper plate is a chromium-zirconium-copper alloy, and the chromium-zirconium-copper alloy comprises the following steps: (1) pretreatment; (2) alkaline electrochemical corrosion treatment; (3) And (3) high-temperature annealing reduction, wherein in the alkaline washing electrochemical corrosion treatment process, a crystallizer copper plate is used as a working electrode, an inert graphite carbon rod is used as a counter electrode, and a controllable positive and negative electrode reversing power supply is used.
(1) The pretreatment comprises mechanical polishing, degreasing, hot water washing, cold water washing, acid activation, alkali washing and water washing, wherein the mechanical polishing comprises 2000-mesh sand paper polishing, and the degreasing comprises the following steps: 25g/LNa 2 CO 3 、10g/LNaOH、50g/LNa 3 PO 4 . 12H 2 O、7g/LNa 2 SiO 3 Temperature 70 o C, time 10min, the acid activates 10wt.% H 2 SO 4 For 50s, the alkaline wash was 10wt.% sodium carbonate for 60s.
(2) The electrolyte used in the alkaline electrochemical corrosion treatment is 50g/L potassium hydroxide and 1g/LNa 2 SiO 3 At a temperature of 30 o And C, the alkaline electrochemical corrosion treatment process is as follows: starting a power supply, taking a copper plate as an anode, reacting for 2min, and controlling the current density to be 1.5A/dm 2 Turning off the power supply, ultrasonically stirring for 15s, turning on and switching the positive and negative directions of the power supply, taking the copper plate as a cathode, reacting for 5min, and controlling the current density to be 0.2A/dm 2 And turning off the power supply, and performing ultrasonic stirring for 30s, wherein the alkaline electrochemical corrosion treatment is performed for 3 times by turning on the power supply, turning off the power supply, switching the power supply and turning off the power supply.
(3) The high-temperature annealing reduction parameters are as follows: 5vol.% of a hydrogen/nitrogen mixture, 5 o The temperature rise rate of C/min is increased to 650 o And C, preserving heat for 2-3h, removing a heat source, continuously introducing mixed gas, and naturally cooling.
(4) And (5) performing vacuum sealing preservation on the obtained crystallizer copper plate.
And (3) taking the obtained copper plate as a cathode, and performing electrodeposition treatment, wherein the electroplating solution comprises the following components:
NiSO 4 . 6H 2 O：260g/L；
CoSO 4 . 7H 2 O：10g/L；
H 3 BO 3 ：20g/L；
chlorobenzaldehyde: 1g/L;
1g/L of 1, 3-propanedithiol;
sodium butynol ether propane sulfonate: 0.5g/L;
1g/L of diethylenetriamine pentaacetic acid sodium salt
The balance of water.
Electroplating parameters are as follows current density 2A/dm 2 Temperature 40 o C, magnetic stirring for 30min at 200rpm.
Example 2
The surface treatment method of the crystallizer copper plate is characterized in that the copper plate is a chromium-zirconium-copper alloy, and the chromium-zirconium-copper alloy comprises the following steps: (1) pretreatment; (2) alkaline electrochemical corrosion treatment; (3) And (3) high-temperature annealing reduction, wherein in the alkaline washing electrochemical corrosion treatment process, a crystallizer copper plate is used as a working electrode, an inert graphite carbon rod is used as a counter electrode, and a controllable positive and negative electrode reversing power supply is used.
(1) The pretreatment comprises mechanical polishing, degreasing, hot water washing, cold water washing, acid activation, alkali washing and water washing, wherein the mechanical polishing comprises 2000-mesh sand paper polishing, and the degreasing comprises the following steps: 25g/LNa 2 CO 3 、10g/LNaOH、50g/LNa 3 PO 4 . 12H 2 O、7g/LNa 2 SiO 3 Temperature 75 o C, time 10min, the acid activates 10wt.% H 2 SO 4 For 50s, the alkaline wash was 10wt.% sodium carbonate for 60s.
(2) The electrolyte used in the alkaline electrochemical corrosion treatment is 65g/L potassium hydroxide and 2g/LNa 2 SiO 3 At a temperature of 35 o And C, the alkaline electrochemical corrosion treatment process is as follows: starting a power supply, taking a copper plate as an anode, reacting for 3.5min, and controlling the current density to be 1.75A/dm 2 Turning off the power supply, ultrasonically stirring for 15s, turning on and switching the positive and negative directions of the power supply, taking the copper plate as a cathode, reacting for 7.5min, and controlling the current density to be 0.3A/dm 2 And turning off the power supply, and performing ultrasonic stirring for 30s, wherein the alkaline electrochemical corrosion treatment is performed for 3 times by turning on the power supply, turning off the power supply, switching the power supply and turning off the power supply.
(3) The high-temperature annealing reduction parameters are as follows: 5vol.% of a hydrogen/nitrogen mixture, 5 o The temperature rise rate of C/min is increased to 650 o And C, preserving heat for 2-3h, removing a heat source, continuously introducing mixed gas, and naturally cooling.
(4) And (5) performing vacuum sealing preservation on the obtained crystallizer copper plate.
The SEM characterization of the copper plate after the surface treatment of the above example 2 is shown in fig. 1, the surface of the metal is smooth and flat after the surface pretreatment, as shown in fig. 2, a large number of corrosion channels are obtained after alkaline electrochemical corrosion, and fig. 3 is a partial enlarged view, in addition, the copper plate with the crystallizer is used as a substrate, and the surface of the copper plate is electroplated with a metal alloy, as shown in fig. 4, so that the plating layer and the metal are tightly combined.
And (3) taking the obtained copper plate as a cathode, and performing electrodeposition treatment, wherein the electroplating solution comprises the following components:
NiSO 4 . 6H 2 O：280g/L；
CoSO 4 . 7H 2 O：15g/L；
H 3 BO 3 ：25g/L；
chlorobenzaldehyde: 2g/L;
1.5g/L of 1, 3-propanedithiol;
sodium butynol ether propane sulfonate: 1g/L;
2g/L of diethylenetriamine pentaacetic acid sodium salt
The balance of water.
Electroplating parameters are as follows current density 3A/dm 2 Temperature 43 o C, time 40min, magnetic stirring 250rpm.
The sample obtained was S-2.
Examples
The surface treatment method of the crystallizer copper plate is characterized in that the copper plate is a chromium-zirconium-copper alloy, and the chromium-zirconium-copper alloy comprises the following steps: (1) pretreatment; (2) alkaline electrochemical corrosion treatment; (3) And (3) high-temperature annealing reduction, wherein in the alkaline washing electrochemical corrosion treatment process, a crystallizer copper plate is used as a working electrode, an inert graphite carbon rod is used as a counter electrode, and a controllable positive and negative electrode reversing power supply is used.
(1) The pretreatment comprises mechanical polishing, degreasing, hot water washing, cold water washing, acid activation, alkali washing and water washing, wherein the mechanical polishing comprises 2000-mesh sand paper polishing, and the degreasing comprises the following steps: 25g/LNa 2 CO 3 、10g/LNaOH、50g/LNa 3 PO 4 . 12H 2 O、7g/LNa 2 SiO 3 Temperature 80 o C, time 10min, the acid activates 10wt.% H 2 SO 4 For 50s, the alkaline wash was 10wt.% sodium carbonate for 60s.
(2) The alkaline electrochemical corrosion siteThe electrolyte used was 80g/L potassium hydroxide, 3g/LNa 2 SiO 3 At a temperature of 40 o And C, the alkaline electrochemical corrosion treatment process is as follows: starting a power supply, taking a copper plate as an anode, reacting for 3min, and controlling the current density to be 2.0A/dm 2 Turning off the power supply, ultrasonically stirring for 15s, turning on and switching the positive and negative directions of the power supply, taking the copper plate as a cathode, reacting for 5min, and controlling the current density to be 0.5A/dm 2 And turning off the power supply, and carrying out ultrasonic stirring for 30s, wherein the alkaline electrochemical corrosion treatment is carried out for one cycle, namely turning on the power supply, turning off the power supply, switching the power supply and turning off the power supply, and the cycle times are 4 times.
(3) The high-temperature annealing reduction parameters are as follows: 5vol.% of a hydrogen/nitrogen mixture, 5 o The temperature rise rate of C/min is increased to 650 o And C, preserving heat for 2-3h, removing a heat source, continuously introducing mixed gas, and naturally cooling.
(4) And (5) performing vacuum sealing preservation on the obtained crystallizer copper plate.
And (3) taking the obtained copper plate as a cathode, and performing electrodeposition treatment, wherein the electroplating solution comprises the following components:
NiSO 4 . 6H 2 O：300g/L；
CoSO 4 . 7H 2 O：20g/L；
H 3 BO 3 ：30g/L；
chlorobenzaldehyde: 3g/L;
2g/L of 1, 3-propanedithiol;
sodium butynol ether propane sulfonate: 1.5g/L;
3g/L of diethylenetriamine pentaacetic acid sodium salt
The balance of water.
Electroplating parameters are as follows current density 5A/dm 2 Temperature of 45 o C, magnetic stirring at 300rpm for 50 min.
Comparative example 1
The surface treatment method of the crystallizer copper plate is characterized in that the copper plate is a chromium-zirconium-copper alloy, and the chromium-zirconium-copper alloy comprises the following steps: (1) pretreatment; (2) acid anodic corrosion; (3) high-temperature annealing reduction.
(1) The pre-treatmentThe treatment comprises mechanical polishing, degreasing, hot water washing, cold water washing, acid activation, alkali washing and water washing, wherein the mechanical polishing is performed by using 2000-mesh sand paper, and the degreasing is performed by: 25g/LNa 2 CO 3 、10g/LNaOH、50g/LNa 3 PO 4 . 12H 2 O、7g/LNa 2 SiO 3 Temperature 75 o C, time 10min, the acid activates 10wt.% H 2 SO 4 For 50s, the alkaline wash was 10wt.% sodium carbonate for 60s.
(2) The electrolyte used in the alkaline electrochemical corrosion treatment is 10wt.% sulfuric acid, 2g/LNa 2 SiO 3 At a temperature of 35 o C, a reaction time of 35min and a current density of 1.75A/dm 2 。
(3) The high-temperature annealing parameters are as follows: nitrogen gas, at 5 o The temperature rise rate of C/min is increased to 650 o And C, preserving heat for 2-3h, removing a heat source, continuously introducing mixed gas, and naturally cooling.
(4) And (5) performing vacuum sealing preservation on the obtained crystallizer copper plate.
As shown in figure 5, after surface treatment, the surface is of a passivation layer structure, and a sheet structure exists after high temperature, so that corrosion holes are avoided.
And (3) taking the obtained copper plate as a cathode, and performing electrodeposition treatment, wherein the electroplating solution comprises the following components:
NiSO 4 . 6H 2 O：280g/L；
CoSO 4 . 7H 2 O：15g/L；
H 3 BO 3 ：25g/L；
chlorobenzaldehyde: 2g/L;
1.5g/L of 1, 3-propanedithiol;
sodium butynol ether propane sulfonate: 1g/L;
2g/L of diethylenetriamine pentaacetic acid sodium salt
The balance of water.
Electroplating parameters are as follows current density 3A/dm 2 Temperature 43 o C, time 40min, magnetic stirring 250rpm.
The sample obtained was D-1.
Comparative example 2
The surface treatment method of the crystallizer copper plate is characterized in that the copper plate is a chromium-zirconium-copper alloy, and the chromium-zirconium-copper alloy comprises the following steps: (1) pretreatment; (2) alkaline electrochemical corrosion treatment; (3) And (3) high-temperature annealing reduction, wherein in the alkaline washing electrochemical corrosion treatment process, a crystallizer copper plate is used as a working electrode, an inert graphite carbon rod is used as a counter electrode, and a controllable positive and negative electrode reversing power supply is used.
(1) The pretreatment comprises mechanical polishing, degreasing, hot water washing, cold water washing, acid activation, alkali washing and water washing, wherein the mechanical polishing comprises 2000-mesh sand paper polishing, and the degreasing comprises the following steps: 25g/LNa 2 CO 3 、10g/LNaOH、50g/LNa 3 PO 4 . 12H 2 O、7g/LNa 2 SiO 3 Temperature 75 o C, time 10min, the acid activates 10wt.% H 2 SO 4 For 50s, the alkaline wash was 10wt.% sodium carbonate for 60s.
(2) The electrolyte used in the alkaline electrochemical corrosion treatment is 65g/L potassium hydroxide and 2g/LNa 2 SiO 3 At a temperature of 35 o And C, the alkaline electrochemical corrosion treatment process is as follows: starting a power supply, taking a copper plate as an anode, reacting for 3.5min, and controlling the current density to be 1.75A/dm 2 Turning off the power supply, ultrasonically stirring for 15s, turning on and switching the positive and negative directions of the power supply, taking the copper plate as a cathode, reacting for 7.5min, and controlling the current density to be 0.3A/dm 2 And turning off the power supply, and performing ultrasonic stirring for 30s, wherein the alkaline electrochemical corrosion treatment is performed for 3 times by turning on the power supply, turning off the power supply, switching the power supply and turning off the power supply.
(3) The high-temperature annealing reduction parameters are as follows: 5vol.% of a hydrogen/nitrogen mixture, 5 o The temperature rise rate of C/min is increased to 650 o And C, preserving heat for 2-3h, removing a heat source, continuously introducing mixed gas, and naturally cooling.
(4) And (5) performing vacuum sealing preservation on the obtained crystallizer copper plate.
And (3) taking the obtained copper plate as a cathode, and performing electrodeposition treatment, wherein the electroplating solution comprises the following components:
NiSO 4 . 6H 2 O：280g/L；
CoSO 4 . 7H 2 O：15g/L；
H 3 BO 3 ：25g/L；
and (2) a surfactant:
the balance of water.
Electroplating parameters are as follows current density 3A/dm 2 Temperature 43 o C, time 40min, magnetic stirring 250rpm.
The sample obtained was D-2.
The binding force of the S-2, D-1, D-2 plating layer is characterized:
from the above table, it can be seen that the plating obtained by the porous copper surface and the four additive plating solutions of the present invention is excellent in both binding force and hardness.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (2)
1. An alloy plating solution is characterized by comprising the following components:
NiSO 4 . 6H 2 O：260g/L-300g/L；
CoSO 4 . 7H 2 O：10-20g/L；
H 3 BO 3 ：20-30g/L；
chlorobenzaldehyde: 1-3g/L;
1, 3-propanedithiol 1-2g/L;
sodium butynol ether propane sulfonate: 0.5-1.5g/L;
1-3g/L of diethylenetriamine pentaacetic acid sodium;
the balance deionized water;
the electroplating parameters of the electroplating solution are as follows: current density 2-5A/dm 2 The pH is 3-5, the temperature is 40-45 ℃, the time is 30-50min, and the magnetic stirring is 200-300rpm;
the electroplating solution is used for electroplating the copper plate;
the copper plate is a crystallizer copper plate subjected to surface treatment, and the crystallizer copper plate is subjected to the following treatment processes:
(1) Pretreatment: the pretreatment comprises mechanical polishing, degreasing, hot water washing, cold water washing, acid activation, alkali washing and water washing, wherein the mechanical polishing comprises 2000-mesh sand paper polishing, and the degreasing comprises the following steps: 25g/LNa 2 CO 3 、10g/LNaOH、50g/LNa 3 PO 4 . 12H 2 O、7g/LNa 2 SiO 3 The temperature is 70-80 ℃ and the time is 10min, and the acid is activated to 10wt.% H 2 SO 4 Time 50s, alkali wash 10wt.% sodium carbonate, time 60s;
(2) Alkaline electrochemical corrosion treatment: the electrolyte used in the alkaline electrochemical corrosion treatment is 50-80g/L potassium hydroxide, 1-3g/LNa 2 SiO 3 The temperature is 30-40 ℃, and the alkaline electrochemical corrosion treatment process comprises the following steps: starting a power supply, taking a copper plate as an anode, reacting for 2-5min, and controlling the current density to be 1.5-2.0A/dm 2 Turning off the power supply, ultrasonically stirring for 15s, turning on and switching the positive and negative directions of the power supply, taking the copper plate as a cathode, reacting for 5-8min, and controlling the current density to be 0.2-0.5A/dm 2 The ultrasonic stirring is turned off for 30s;
(3) High-temperature annealing reduction: the high-temperature annealing reduction parameters are as follows: and (3) raising the temperature to 650 ℃ at a temperature raising rate of 5 ℃ per minute by 5vol.% of hydrogen/nitrogen mixed gas, preserving heat for 2-3h, removing a heat source, continuously introducing the mixed gas, and naturally cooling.
2. An alloy plating solution according to claim 1, wherein the alkaline electrochemical etching treatment is performed for a cycle of 3 to 5 times with a total alkaline electrochemical etching treatment time of not more than 40 minutes.
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