CN114381792A - Method for stably controlling electroplating solution - Google Patents
Method for stably controlling electroplating solution Download PDFInfo
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- CN114381792A CN114381792A CN202111339377.6A CN202111339377A CN114381792A CN 114381792 A CN114381792 A CN 114381792A CN 202111339377 A CN202111339377 A CN 202111339377A CN 114381792 A CN114381792 A CN 114381792A
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Abstract
The invention discloses a method for stably controlling electroplating solution, which comprises the following steps: 1) calculating the amount of water, sulfuric acid and zinc needed by a tank of plating solution by taking the designed formula of the plating solution as a target value; 2) adding the calculated water amount and concentrated sulfuric acid in sequence, heating and melting zinc; preliminarily preparing needed electroplating solution; 3) titrating the plating solution, and adjusting components deviating from the target concentration in the plating solution; 4) determining key control parameters of an electroplating process in the electroplating process, and performing linkage adjustment on a corresponding control process in an electroplating solution control system in the electroplating process; realize the stable control of the electroplating solution. The method adopts a means of accurately controlling the parameters of the plating solution based on a core control factor linkage regulation and control technology and a high-efficiency processing means after abnormity occurs, can effectively improve the stability of the electrogalvanizing process, greatly reduces the quality improvement of field production, and simultaneously realizes the quick and high-efficiency deviation rectification adjustment of a plating solution system; the related process is simple, convenient to operate and suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of surface treatment, and particularly relates to a method for stably controlling electroplating solution.
Background
The gravity electroplating is one of vertical electroplating processes, during electroplating, a plating tank is not filled with plating solution, the plating solution only exists between an anode box and strip steel, and the flow of the plating solution is accelerated by the gravity of the plating solution. For high-speed electrogalvanizing production, the stable control of the electroplating solution is a core link of the production; mainly comprises three aspects of stability, namely plating solution components (acid content and zinc ion concentration), temperature and volume. The stable plating solution control is a necessary condition for producing high-quality electroplating plates and is a key factor of the uniformity of the thickness distribution of the zinc layer, the crystal thickness of the zinc layer and the surface smoothness of products. Such as zinc sulfate concentration, temperature, etc., have great influence on the surface quality of the electrogalvanized layer. The production shows that: the apparent brightness of the plating layer is reduced by increasing the current density, increasing the pH value, reducing the temperature and increasing the zinc ion concentration; this is because the above conditions make it difficult to diffuse zinc ions, and this leads to problems such as coarse crystals of the plating layer. How to well control the stability of the parameters of the plating solution is very important.
According to the traditional plating solution production process, the defects of whitening, floating ash, darkness, thick crystallization of a plating layer and the like of a steel plate are always found in the production process of electrogalvanizing, so that a great deal of judgment is caused. The production adjustment finds that the defect is caused to be closely related to the fluctuation of the parameters of the plating solution. When plating solution parameters are abnormal, because the number of the adjustable means of the machine set is often more than one, the adjustment means selected by different operators has great difference, and the adjustment time and the risks are also greatly different. Such problems once plague steelworks for a long time, how to thoroughly solve the problem of rapidly obtaining a stably controlled electroplating solution, reduce the occurrence of structural defects and partial surface quality defects of the plating layer, and reduce the need for improvement is urgent.
The plating solution control system generally comprises four circulating systems, namely an electroplating circulating system, a zinc dissolving system, an evaporation system and a sulfuric acid circulating system; the components and functions contained therein include: 1) electroplating circulating system: the device comprises a rectifier, a filter, a plating solution circulating tank and a plating solution storage tank, and mainly has the function of ensuring the thickness of a plating layer on the surface of a steel plate; 2) a zinc dissolving system: a zinc dissolving station; the main function is to improve the concentration of zinc ions in the plating solution; 3) an evaporation system: controlling the temperature and evaporating; the main function is to maintain the temperature of the plating solution and stabilize the concentration of the plating solution; 4) a sulfuric acid circulating system: an acid adding device and a sulfuric acid circulating tank; the main function is to maintain the concentration and pH value of free acid in the plating solution.
When the plating solution is abnormal, the traditional method is to use a single adjustment method aiming at different problems, such as: when the concentration of zinc ions is lower or higher, adding zinc or adding water into the plating solution through a zinc dissolving system; adding acid or water into the plating solution through a sulfuric acid circulating system when the free acid is lower or higher; when the temperature is lower or higher, the heating or cooling is carried out through an evaporation system; if the liquid level and the pH value are lower or higher, water is added, acid is added or the water is discharged; the concentration of iron ions is higher, and the plating solution is discharged. Such a situation not only causes the plating solution parameters to fluctuate and be unstable for a long time, but also causes a large amount of waste of cost and brings a series of environmental protection treatment problems. Such problems once plague steelworks for a long time, how to thoroughly solve the problems of fast, precise and stable control of electroplating solution, reduce the occurrence of structural defects and partial surface quality defects of the plating layer, and reduce the possibility of improvement is urgent.
Disclosure of Invention
The invention mainly aims to solve the problems and the defects of the traditional original electrogalvanizing process, carry out process adjustment on the plating solution control of the traditional electrogalvanizing unit, and provide a means for accurately controlling plating solution parameters based on a core control factor linkage regulation and control technology and a high-efficiency treatment means after abnormity occurs; the method can effectively improve the stability of the electrogalvanizing process, greatly reduce the quality improvement of field production, and simultaneously realize the quick and efficient deviation rectification adjustment of the plating solution system; and the related process is simple, convenient to operate and suitable for popularization and application.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
a method for stably controlling a plating solution, comprising the steps of:
1) calculating the amount of water, sulfuric acid and zinc needed by a tank of plating solution by taking the designed formula of the plating solution as a target value;
2) adding the calculated water amount and concentrated sulfuric acid in sequence, heating and melting zinc; preliminarily preparing needed electroplating solution;
3) titrating the plating solution, and adjusting components deviating from the target concentration in the plating solution;
4) determining control parameters of an electroplating process in the electroplating process, and performing linkage adjustment on the control parameters corresponding to an electroplating circulating system, a zinc dissolving system, an evaporation system and a sulfuric acid circulating system of an electroplating solution control system in the electroplating process; realize the stable control of the electroplating solution.
In the scheme, the mass of the zinc is equal to the effective volume of the electroplating solution circulating tank multiplied by the concentration of zinc ions; weight of sulfuric acid is equal to weight of zinc particles multiplied by H2SO4Relative molecular weight of (1)/(relative molecular weight of Zn. times. sulfuric acid utilization coefficient).
In the above scheme, the process of preparing the electroplating solution comprises: adding water to 65-70% of the liquid level in the plating solution circulating tank, adding sulfuric acid, opening a heat exchanger at the evaporator part, and heating the plating solution to 45-50 ℃.
In the above scheme, the titration step comprises Zn2+Titration of concentration and free acid concentration.
In the above scheme, the Zn2+The titration of the concentration step comprises: accurately transferring 1mL of electroplating solution into a 250mL conical flask, and supplementing 30mL of deionized water; 10ml of an ammonia buffer solution was added (the specific preparation procedure included adding 54g of NH4Adding water to Cl for dissolving, adding 400mL of ammonia water with the concentration of 25 wt% for mixing, adding water for diluting to 1000mL), shaking up, adding 2-3 drops of chrome black T indicator, and slowly titrating the sample with 0.1mol/L of EDTA standard solution until the color of the solution changes from red to blue-green; recording the volume of EDTA solution consumed (mL); calculating Zn according to formula I2+The concentration of (a):
in the formula: c is the quantity concentration of EDTA standard solution, mol/L; v1In terms of volume, mL, of EDTA standard solution consumed; v0The number of the sampling volume of the sample is mL; 65.38 is the molar mass of zinc, g/mol; the specific calculation formula is as follows:
in the above embodiment, the titration of the free acid concentration step includes:
placing 10mL of electroplating solution sample in a 250mL conical flask, adding 30mL of deionized water, and adding 3-4 drops of methyl orange-Zhanlan carmine indicator (prepared by mixing 0.1 wt% methyl orange aqueous solution and 0.25 wt% indigo carmine aqueous solution according to a mass ratio of 3: 2); titrating with 0.1mol/L NaOH standard solution (when the content of free acid is more than 50g/L, titrating with 1mol/L NaOH standard solution instead of 0.1mol/L NaOH), wherein the solution is changed from purple to light green, stopping titrating, and recording the volume milliliter number of consumed standard solution; the concentration of free acid is calculated according to formula II:
in the formula: v1The volume of the NaOH standard solution consumed for titrating the test solution is mL; v0The amount is mL of the electroplating solution sample; c is the concentration of NaOH standard solution; 49.0 is
Molar mass of (a), g/mol; the specific calculation formula is as follows:
by adopting the titration steps, the problems of inaccurate titration color development and the like in the traditional titration process can be effectively avoided; because there are many acid solutions in electroplating, such as: acid washing, electroplating, conducting roller cleaning, double-sided post-plating cleaning, single-sided post-plating cleaning and the like, and the titration of these acid solutions generally uses a bromocresol green-methyl red indicator; however, in the electroplating, the concentration of free acid in the plating solution is low, and the color development of the bromocresol green-methyl red indicator is found to be uneven, so that methyl orange-panoxa carmine is particularly selected as the indicator for accurate control.
In the above scheme, the (key) control parameters of the electroplating process include zinc ion concentration, sulfuric acid concentration, pH value, plating solution temperature, iron ion concentration and plating solution level, and the specific control conditions include: the temperature of the plating solution is 48-53 ℃; the concentration of zinc ions is 90-140 g/L; the concentration of sulfuric acid is 2-12 g/L; the pH value is 1.2-1.8; the concentration of iron ions is less than 3 g/L; the liquid level of the plating solution is 60-80%; preferred target values are: the temperature of the plating solution is 50 ℃; the concentration of zinc ions is 115 g/L; the concentration of sulfuric acid is 7 g/L; the pH value is 1.5; the concentration of iron ions is 0 g/L; the plating solution level is 70%. The traditional electroplating process mainly comprises the following control parameters: the temperature of the plating solution is 37-53 ℃; the concentration of zinc ions is 70-120 g/L; the concentration of sulfuric acid is 2-8 g/L; the pH value is 0.9-1.5.
In the scheme, in the plating solution temperature control process, the traditional plating solution temperature control means is mainly controlled by an evaporator system; when the temperature is higher than the set temperature, the heating device of the evaporation system is closed, and when the temperature is lower than the set temperature, the heating device of the evaporation system is opened, but the process is long in time consumption and high in energy consumption; in the temperature control process of the plating solution, the total current is adjusted according to the requirement of the galvanizing thickness, the temperature rise degree of the plating solution is different according to the total current amount, and then the temperature difference is compensated to 48-53 ℃ through an evaporator; in addition, the increase of the current density not only improves the temperature of the plating solution, but also improves the cathode polarization, which is beneficial to forming a fine-grain plating layer; wherein the zinc plating total current calculation formula is shown in formula III;
wherein G is the amount of zinc plating (G/m)2) (ii) a I is the total galvanizing current (A); b is the width (m) of the strip steel; v is the strip steel speed (m/min); η is the current efficiency (in 95%).
In the scheme, the plating solution concentration, the pH value and the plating solution liquid level are controlled by linkage adjustment steps, including more than two of electroplating rate control, evaporation control, zinc dissolution control, acid addition control and liquid guide control between the plating solution and a storage tank (the traditional regulation and control process only considers the control of a certain system);
the specific adjustment measures are as follows:
TABLE 1 plating bath Condition and corresponding adjustment measures
Note 1: the mode of accelerated plating + minimum zinc dissolution is the first choice, and the method requires a certain time to gradually improve the plating solution. If the unit is stopped, part of the plating solution in the circulating tank is directly pumped into the storage tank, and then the circulating tank is replenished with water to reduce the concentration of zinc ions.
Note 2: the plating solution is preferably drained, but if the storage tank has no liquid level, condensed water is added to replace the plating solution to increase the liquid level.
In the above adjustment measures, in the electroplating rate control, evaporation control, zinc dissolution control, acid addition control, and liquid guide control between the plating solution and the storage tank, the related parameter adjustment is regulated and controlled on the basis of the existing process parameter conditions corresponding to the specific plating solution working conditions.
In the above scheme, the control parameters included in the electroplating circulation system include: the current regulation range of each plating bath in 16 plating baths is 0-50 kA, and the total current density regulation range is 0-90A/dm2(ii) a The speed and flow rate regulation range of the plating solution circulating pump is 0-500 m3H; the control parameters included in the zinc dissolving system include: the regulation and control range of the speed and the flow of the zinc dissolving pump is 0-1000 kg/h; the control parameters included in the evaporation system include: the evaporation capacity regulating range is 0-800 m3H; the control parameters included in the sulfuric acid circulation system include: the flow rate control range of the acid adding pump is 0-100 m3/h。
In the scheme, in the iron ion control process, the traditional process is controlled by adding condensed water after discharging the plating solution, so that a large amount of cost waste and environmental protection treatment problems are caused; the regulation and control means of the invention lies in deplatingHigh concentration of Fe in zinc plating solution2+、Fe3+Only through oxidation-reduction reaction and flocculation precipitation, the acid can be easily removed, the consumption of acid is reduced, and meanwhile, the board surface quality and the corrosion resistance are improved; the method comprises the following specific steps:
1) fe in zinc plating solution is oxidized by strong oxidant (hydrogen peroxide)2+Is oxidized into Fe3+；
2) Adjusting pH of the zinc-plating solution to 3.6-3.9 by adjusting pH (pH regulator containing zinc oxide or zinc carbonate or alkali) to make Fe3+Form iron hydroxide precipitate and Zn2+No precipitate is formed, thereby realizing Fe2+And Fe3+Selective removal of (2);
3) a flocculant (PAM) was added to filter out the precipitate.
4) The pH value is adjusted back to 1.2-1.8 by using the sulfuric acid used for production.
The whole process flow can effectively and selectively remove metal impurity ions in the plating solution to reduce the waste of the plating solution and the production running cost, and does not introduce new impurity ions which have influence on the quality of the galvanized sheet
Compared with the prior art, the invention has the beneficial effects that:
1) the invention firstly provides a linkage adjustment mechanism based on four circulation systems, namely an electroplating circulation system, a zinc dissolving system, an evaporation system and a sulfuric acid circulation system, and finds out key control parameters of plating solution influencing the structure and the surface quality of an electroplating coating; the method is adjusted from the previous single four-system control electroplating to find the linkage key points among the four electroplating systems, so that the components of the plating solution can be more accurately controlled, and the severe parameter fluctuation is avoided; when the abnormal working condition is met, the deviation rectification adjustment of the plating solution system can be completed at the highest speed; greatly reducing the quality improvement of field production;
2) the process can improve the stability of the process, and effectively improve the defects of whitening, floating ash, darkness, coarse crystallization of a plating layer and the like which are easily found in the production process of the electrogalvanizing;
3) the invention improves the titration process and optimizes the indicator; the number of times of manual titration is reduced from the countless times of the prior general detection to the titration once per shift.
Drawings
FIG. 1 is a graph of (a) a micro-morphology and (b) a macro-morphology of a zinc-plated layer obtained in example 1;
fig. 2 is a (a) microscopic morphology and (b) macroscopic morphology graphs of the zinc-plated layer obtained in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In the following examples, the method for stably controlling the plating solution includes the following steps:
1) firstly, calculating the amount of water, sulfuric acid and zinc required by a tank of plating solution according to a target value;
2) adding the calculated water amount and concentrated sulfuric acid in sequence, heating and melting zinc; preliminarily preparing needed electroplating solution; in the specific preparation process, firstly adding water and then adding acid, adding the water to a position with a volume of 65-70% of the liquid level of the plating solution circulating tank, then adding required sulfuric acid, opening a heat exchanger of an evaporator part, and heating the plating solution to 45-50 ℃; filling the zinc granules in a zinc dissolving tank, and opening a zinc dissolving pump to dissolve the zinc granules until the pH value is 1.5; wherein the mass of zinc is effective volume of the plating solution circulation tank multiplied by zinc ion concentration (240 m)3X 90 g/L21600 kg); the mass of the sulfuric acid is multiplied by H of the weight of zinc particles2SO4Relative molecular weight/(Zn relative molecular weight × sulfuric acid utilization coefficient) (21600kg × 98/(65.4 × 0.96) ═ 33716 kg); after the solution preparation is finished, a circulating system is opened, and the temperature is increased to 45-50 ℃.
3) After the solution is prepared, titrating free acid and zinc ions, and verifying the concentration of the solution; the production process also needs 8 hours to carry out one-time examination titration; adjusting components deviating from the target concentration in the electroplating solution;
4) determining control parameters of an electroplating process in the electroplating process, and performing linkage adjustment on the control parameters corresponding to an electroplating circulating system, a zinc dissolving system, an evaporation system and a sulfuric acid circulating system of an electroplating solution control system in the electroplating process; the stable control of the electroplating solution is realized;
5) by controlling the zinc ion concentration, acid concentration, temperature, liquid level and other technological processes of the plating solution, various structural defects and partial surface defects of the plated layer can be thoroughly solved, and the production speed can reach 100-120 m/min.
6) Once an exception problem occurs, the exception handling may proceed as described in Table 1.
Note: in the following examples, the targeted plating solutions are all the existing solution preparations in the actual plating process in the plating solution control system; only when a series of plating solution problems that the production cannot be guaranteed, such as serious solution leakage, large amount of impurities entering the plating solution, and the like, occur, the solution is prepared again.
Example 1
A method for stably controlling electroplating solution aims at the working conditions that: the production speed is 110m/min, the temperature of the plating solution is 50 ℃, the concentration of zinc ions is 85g/L, the concentration of sulfuric acid is 2g/L, the pH value is 2.0, the concentration of iron ions is 2g/L, and the liquid level of the plating solution is 85 percent; the problems of coarse crystallization, uneven size, dark gray surface layer, uneven color, heavy dendritic crystal at the edge part and the like of the plating layer are caused;
the specific plating solution stability control process comprises the following steps:
1) carrying out titration detection on the electroplating solution, and determining the accurate value of each process parameter;
2) the production speed, the total current and the plating solution pump speed are kept unchanged, and the evaporation is accelerated to 150m3Accelerating a zinc dissolving pump by 50%, starting an acid adding pump to 2L/min, and introducing 10% of the plating solution in the electroplating circulating tank into a storage tank;
3) after half an hour, carrying out titration detection to determine each process parameter value; the detection result shows that the production speed after stable control can be increased to 120m/min, the temperature of the plating solution is 51 ℃, the concentration of zinc ions is 110g/L, the concentration of sulfuric acid is 6g/L, the pH value is 1.6, the concentration of iron ions is 2g/L, and the liquid level of the plating solution is 70%; the obtained plating layer has compact crystallization, uniform size, gray plate surface, uniform color and no dendritic crystal at the edge, as shown in figure 1;
4) after 8 hours, the titration test was carried out and all parameters were still within the normal range.
Example 2
A method for stably controlling electroplating solution aims at the working conditions that: the production speed is 120m/min, the temperature of the plating solution is 49 ℃, the concentration of zinc ions is 80g/L, the concentration of sulfuric acid is 10g/L, the pH value is 1.1, the concentration of iron ions is 1.5g/L, and the liquid level of the plating solution is 59%; the problems of thick and thick crystallization, uneven size, offwhite surface layer, uneven color, floating ash on the surface and the like of the plating layer are caused; the specific electroplating solution stable control process comprises the following steps:
1) carrying out titration detection on the electroplating solution, and determining the accurate value of each process parameter;
2) the production speed, the total current and the plating solution pump speed are unchanged, the evaporation system is closed, the zinc dissolving pump speed is increased by 50%, the acid adding pump speed is closed, and plating solution with 10% of the liquid level in the storage tank is led into the electroplating circulating tank;
3) after half an hour, carrying out titration detection to determine each process parameter value; the detection result shows that the production speed after stable control can be increased to 130m/min, the temperature of the plating solution is 49 ℃, the concentration of zinc ions is 100g/L, the concentration of sulfuric acid is 6g/L, the pH value is 1.5, the concentration of iron ions is 1.6g/L, and the liquid level of the plating solution is 70 percent; the obtained plating layer has compact crystallization, uniform size, gray plate surface, uniform color and no floating ash;
4) after 8 hours, the titration test was carried out and all parameters were still within the normal range.
Comparative example 1
A method for stably controlling electroplating solution aims at the working conditions that: the production speed is 100m/min, the temperature of the plating solution is 50 ℃, the concentration of zinc ions is 70g/L, the concentration of sulfuric acid is 13g/L, the pH value is 1.0, the concentration of iron ions is 2.0g/L, and the liquid level of the plating solution is 82 percent;
the specific regulation and control steps comprise the following steps:
in order to reduce the consumption of zinc, the production speed is reduced to 60 m/min; the flow of a zinc dissolving pump of the zinc dissolving station is increased to 500kg/h, and a sulfuric acid pump is started to add acid-soluble zinc; after 1 hour, the liquid level rises to 83 percent, the temperature of the plating solution is 49 ℃, the concentration of sulfuric acid is 11g/L, the pH value is 1.1, the concentration of iron ions is 2.2g/L, and the concentration of zinc ions is 85 g/L; after 2 hours, the liquid level rises by 84 percent, the temperature of the plating solution is reduced to 48 ℃, the concentration of sulfuric acid is 10g/L, the pH value is 1.3, the concentration of iron ions is 2.3g/L, and the concentration of zinc ions is 90 g/L.
In the regulation and control process, the zinc particles in the zinc dissolving station are agglomerated due to the large amount of added zinc, and sediments are formed at the bottom of the plating solution circulating tank. Can only stir the zinc grain at dissolving zinc station top through the manual work, prevent that the zinc grain of caking from dropping into dissolving zinc station jar suddenly, the friction produces the spark, leads to the hydrogen explosion. The sediment at the bottom of the plating solution can be only solved by discharging the plating solution, which causes the problems of waste of a large amount of plating solution and environmental protection. And the plating layer on the plate surface still has large and loose crystals and gray scale, the plate surface is gray white, and uneven spots exist on the surface of the steel plate due to plating solution sediment (see figure 2).
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (8)
1. A method for stably controlling a plating solution, comprising the steps of:
1) calculating the amount of water, sulfuric acid and zinc needed by a tank of plating solution by taking the designed formula of the plating solution as a target value;
2) adding the calculated water amount and concentrated sulfuric acid in sequence, heating and melting zinc; preliminarily preparing needed electroplating solution;
3) titrating the plating solution, and adjusting components deviating from the target concentration in the plating solution;
4) determining key control parameters of an electroplating process in the electroplating process, and performing linkage adjustment on control processes corresponding to an electroplating circulating system, a zinc dissolving system, an evaporation system and a sulfuric acid circulating system in an electroplating solution control system in the electroplating process; realize the stable control of the electroplating solution.
2. The method for plating bath stability control as set forth in claim 1, wherein the titration step includes Zn2+Titration of concentration and free acid concentration.
3. The method for stable control of electroplating bath according to claim 1, wherein said electroplating process control parameters include zinc ion concentration, sulfuric acid concentration, pH, bath temperature, iron ion concentration and bath level.
4. The method of claim 3, wherein said plating process control parameters comprise: the temperature of the plating solution is 48-53 ℃; the concentration of zinc ions is 90-140 g/L; the concentration of sulfuric acid is 2-12 g/L; the pH value is 1.2-1.8; the concentration of iron ions is less than 3 g/L; the liquid level of the plating solution is 60-80%.
5. The method for stable control of plating solution according to claim 1, wherein the plating solution temperature controlling step comprises: firstly, adjusting the total current according to the requirement of the galvanizing thickness, heating the plating solution according to the temperature rise condition corresponding to the total current, and compensating the temperature difference to 48-53 ℃ through an evaporator.
6. The method for stably controlling the electroplating solution according to claim 1, wherein the control of the concentration, pH value and liquid level of the electroplating solution is performed by a linkage adjustment method, and the control process corresponding to the electroplating circulating system is electroplating rate control; the corresponding control step of the zinc dissolving system is zinc dissolving control; the control process corresponding to the evaporation system is evaporation control; the corresponding control process of the sulfuric acid circulating system is acid addition control; the linkage adjustment comprises more than two of electroplating rate control, zinc dissolving control, evaporation control, acid adding control and liquid guiding control between the electroplating liquid and an additional storage tank.
7. The method for stably controlling a plating solution according to claim 6, wherein the plating solution concentration, pH and plating solution level linkage control means comprises:
when the liquid level of the circulating tank is more than 80 percent, the pH value is more than 1.8, and the concentration of zinc ions is more than 140 g/L; the control of the plating rate comprises increasing the total current by 20-30A/dm2And the plating solution pump speed is improved by 10-20%; the evaporation control comprises starting evaporation to 50m3H; control of zinc dissolutionThe preparation comprises the steps of closing a zinc dissolving pump; the acid addition control comprises reducing the acid addition pump speed by 10-30%; the liquid guiding control between the electroplating liquid and the external storage tank comprises that the electroplating liquid is unchanged or 5 to 20 percent of the electroplating liquid is guided into the external storage tank;
when the liquid level of the circulating tank is more than 80 percent, the pH value is more than 1.8, and the concentration of zinc ions is less than 90 g/L; the control of the electroplating rate is kept unchanged; the evaporation control comprises 100-200m of accelerated evaporation3H; controlling the zinc dissolving process including accelerating the zinc dissolving pump by 30-50%; the acid adding control comprises starting an acid adding pump to 2L/min; the liquid guiding control between the electroplating liquid and the external storage tank comprises that the electroplating liquid is unchanged or 5 to 20 percent of the electroplating liquid is guided into the external storage tank;
when the liquid level of the circulating tank is more than 80 percent, the pH value is less than 1.2, and the concentration of zinc ions is more than 140 g/L; the control of the plating rate comprises increasing the total current by 30-50A/dm2And the plating solution pump speed is improved by 10-20%; the evaporation control comprises starting evaporation to 50m3/h; the zinc dissolution control comprises minimum soluble zinc; the acid addition control comprises stopping acid addition; the liquid guiding control between the electroplating liquid and the external storage tank comprises that the electroplating liquid is unchanged or 5 to 20 percent of the electroplating liquid is guided into the external storage tank;
when the liquid level of the circulating tank is more than 80 percent, the pH value is less than 1.2, and the concentration of zinc ions is less than 90 g/L; the control of the electroplating rate is kept unchanged; the evaporation control comprises 100-200m of accelerated evaporation3/h; controlling the zinc dissolving process including accelerating the zinc dissolving pump by 30-50%; the acid addition control comprises stopping acid addition; the liquid guiding control between the electroplating liquid and the external storage tank comprises that the electroplating liquid is unchanged or 5 to 20 percent of the electroplating liquid is guided into the external storage tank;
when the liquid level of the circulating tank is less than 60 percent, the pH value is more than 1.8, and the concentration of zinc ions is more than 140 g/L; the control of the plating rate comprises increasing the total current by 20-30A/dm2And the plating solution pump speed is improved by 10-20%; the evaporation control includes turning off the evaporation function; the zinc dissolution control comprises minimum soluble zinc; the acid addition control comprises reducing the acid addition pump speed by 10-30%; the liquid guiding control between the electroplating liquid and the additional storage tank comprises that 10-20% of the electroplating liquid is guided out from the storage tank;
when the liquid level of the circulating tank is less than 60 percent, the pH value is more than 1.8, and the concentration of zinc ions is less than 90 g/L; the control of the electroplating rate is kept unchanged; the evaporation control comprises reducing evaporation by 10-50m3/h; controlling the zinc dissolving process including accelerating the zinc dissolving pump by 30-50%; the acid adding control comprises starting an acid adding pump to 2L/min; electroplating solution and external reservoirThe liquid guiding control between the storage tanks comprises that 10 to 20 percent of the plating solution is guided out from the storage tanks;
when the liquid level of the circulating tank is less than 60 percent, the pH value is less than 1.2, and the concentration of zinc ions is more than 140 g/L; the control of the plating rate comprises increasing the total current by 30-50A/dm2And the plating solution pump speed is improved by 10-20%; the evaporation control includes turning off the evaporation function; the zinc dissolution control comprises minimum soluble zinc; the acid addition control comprises stopping acid addition; the liquid guiding control between the electroplating liquid and the additional storage tank comprises that 10-20% of the electroplating liquid is guided out from the storage tank or 10-20% of condensed water is added;
when the liquid level of the circulating tank is less than 60 percent, the pH value is less than 1.2, and the concentration of zinc ions is less than 90 g/L; the control of the electroplating rate is kept unchanged; the evaporation control includes turning off the evaporation function; controlling the zinc dissolving process including accelerating the zinc dissolving pump by 30-50%; the acid addition control comprises stopping acid addition; the liquid guiding control between the electroplating liquid and the additional storage tank comprises the steps of guiding 10-20% of the electroplating liquid out of the storage tank or adding 10-20% of condensed water.
8. The method of claim 7, wherein the control parameters included in the plating circulation system include: the current regulation and control range of the plating bath is 0-50 kA, and the total current density regulation and control range is 0-90A/dm2(ii) a The speed and flow rate regulation range of the plating solution circulating pump is 0-500 m3H; the control parameters included in the zinc dissolving system include: the regulation and control range of the speed and the flow of the zinc dissolving pump is 0-1000 kg/h; the control parameters included in the evaporation system include: the evaporation capacity regulating range is 0-800 m3H; the control parameters included in the sulfuric acid circulation system include: the flow rate control range of the acid adding pump is 0-100 m3/h。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166539A (en) * | 1996-01-31 | 1997-12-03 | 川崎制铁株式会社 | Method for controlling concentration of electroplating bath components in continuous electroplating |
| CN202482481U (en) * | 2012-03-29 | 2012-10-10 | 天津泽强金属表面处理有限公司 | Automatic control system for continuous electroplating |
| CN104677969A (en) * | 2013-11-27 | 2015-06-03 | 上海宝钢工业技术服务有限公司 | Online electroplate liquid detecting system and online electroplate liquid detecting method |
| US20150315720A1 (en) * | 2009-10-12 | 2015-11-05 | Novellus Systems, Inc. | Electrolyte concentration control system for high rate electroplating |
| CN106498483A (en) * | 2016-11-29 | 2017-03-15 | 延康汽车零部件如皋有限公司 | A kind of electroplating technological parameter inter-linked controlling method |
| CN107287650A (en) * | 2017-08-14 | 2017-10-24 | 江东电子材料有限公司 | A kind of electrolyte automatic regulating system and adjusting method |
| CN109097689A (en) * | 2018-09-10 | 2018-12-28 | 武汉钢铁有限公司 | A kind of automobile exterior panel with high-grade surface topography electrogalvanizing spy's ultra-deep punching and its production method |
| CN109537003A (en) * | 2018-12-26 | 2019-03-29 | 河北超亚精密冲制电子有限公司 | It is a kind of to facilitate the system and method for controlling molten zinc slot molten zinc speed and galvanizing bath Zn content |
-
2021
- 2021-11-12 CN CN202111339377.6A patent/CN114381792B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1166539A (en) * | 1996-01-31 | 1997-12-03 | 川崎制铁株式会社 | Method for controlling concentration of electroplating bath components in continuous electroplating |
| US5858196A (en) * | 1996-01-31 | 1999-01-12 | Kawasaki Steel Corporation | Method of controlling component concentration of plating solution in continuous electroplating |
| US20150315720A1 (en) * | 2009-10-12 | 2015-11-05 | Novellus Systems, Inc. | Electrolyte concentration control system for high rate electroplating |
| CN202482481U (en) * | 2012-03-29 | 2012-10-10 | 天津泽强金属表面处理有限公司 | Automatic control system for continuous electroplating |
| CN104677969A (en) * | 2013-11-27 | 2015-06-03 | 上海宝钢工业技术服务有限公司 | Online electroplate liquid detecting system and online electroplate liquid detecting method |
| CN106498483A (en) * | 2016-11-29 | 2017-03-15 | 延康汽车零部件如皋有限公司 | A kind of electroplating technological parameter inter-linked controlling method |
| CN107287650A (en) * | 2017-08-14 | 2017-10-24 | 江东电子材料有限公司 | A kind of electrolyte automatic regulating system and adjusting method |
| CN109097689A (en) * | 2018-09-10 | 2018-12-28 | 武汉钢铁有限公司 | A kind of automobile exterior panel with high-grade surface topography electrogalvanizing spy's ultra-deep punching and its production method |
| CN109537003A (en) * | 2018-12-26 | 2019-03-29 | 河北超亚精密冲制电子有限公司 | It is a kind of to facilitate the system and method for controlling molten zinc slot molten zinc speed and galvanizing bath Zn content |
Non-Patent Citations (2)
| Title |
|---|
| 左正勋等: "薄钢板锌酸盐连续镀锌工艺研究", 《材料保护》 * |
| 蔡玲等: "武钢连续电镀锌机组电镀段技术特点", 《轧钢》 * |
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