CN113913913A - Method for testing concentration of leveling agent in electroplating tin solution and electroplating blank solution - Google Patents
Method for testing concentration of leveling agent in electroplating tin solution and electroplating blank solution Download PDFInfo
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- CN113913913A CN113913913A CN202111280694.5A CN202111280694A CN113913913A CN 113913913 A CN113913913 A CN 113913913A CN 202111280694 A CN202111280694 A CN 202111280694A CN 113913913 A CN113913913 A CN 113913913A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
Abstract
The invention provides a method for testing the concentration of a leveling agent in an electroplating tin solution and the electroplating blank solution, wherein the prepared electroplating blank solution contains copper sulfate pentahydrate, sulfuric acid and chloride ions and does not contain lead, so that the concentration of the leveling agent in the electroplating tin solution can be accurately tested, namely, a CVS (chemical vapor deposition) measuring device can test and analyze the concentration result of the leveling agent, and an operator can not contact the lead solution in the testing process, so that the damage of heavy metal lead to a human body and the environment can be avoided, the operator can be protected, and the environment can be protected.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a method for testing the concentration of a leveling agent in an electrotinning solution and an electroplating blank solution for testing the concentration of the leveling agent in the electrotinning solution.
Background
The Cyclic Voltammetric Stripping (CVS) analysis method is an electrochemical technique for measuring the amount of organic additives (e.g., brighteners, levelers, carriers, etc.) in a plating bath and works on the principle that additives have a direct effect on plating rate.
In order to make the plating layer of the surface of a product uniform and flat in a high and low potential area, the concentration of a leveling agent in an electroplating tin solution (i.e., a working solution for performing the electroplating tin process) must be controlled, and the analysis of the concentration content needs to use a measuring device, namely a Cyclic Voltammetry Stripping (CVS) measuring device.
The main process of testing by adopting CVS measuring equipment is as follows: placing a known volume of electroplating blank Solution (VMS Solution for short, only containing inorganic chemical components in the electroplating tin Solution) on a test platform of CVS measurement equipment, automatically adding a standard sample Solution with known leveling agent concentration into the VMS Solution by an adding pipeline of the CVS measurement equipment according to a certain adding amount and adding times, drawing a calibration curve (namely a test curve of the standard sample Solution) by the CVS measurement equipment according to the change of electroplating rate after the standard sample Solution is added every time, and obtaining a calibration factor (equivalent to the slope of a straight line); and then, replacing the standard sample liquid with the known concentration of the leveling agent with the electroplating tin liquid, testing according to the same steps, drawing a test curve of the electroplating tin liquid by CVS (constant voltage system) measuring equipment, and fitting the two test curves by the CVS measuring equipment to obtain the concentration of the leveling agent in the electroplating tin liquid and automatically calculating according to the obtained calibration factor. Please refer to fig. 1, which is a simulation diagram of a test curve obtained by the CVS metrology apparatus. As shown in fig. 1, the CVS measurement apparatus obtains a test curve (i.e., calibration curve) 100 of the standard sample solution and a test curve 110 of the tin electroplating solution, and calculates a calibration factor according to the test curve, thereby obtaining the concentration of the leveling agent in the tin electroplating solution (i.e., the working solution to be tested).
The VMS solution used for leveling agent concentration analysis is usually only allowed to contain the same proportion of inorganic components as the tin electroplating solution, the existing leveling agent concentration analysis is an analysis method developed on the basis of the tin electroplating solution components including tin methanesulfonate, methanesulfonic acid, lead concentrated solution, RD concentrated solution and leveling agent, and the prepared VMS solution contains three components of tin methanesulfonate, methanesulfonic acid and lead concentrated solution.
With the requirement of environmental protection and the development of the tin electroplating solution, a lead-free tin electroplating solution appears, namely the tin electroplating solution only contains tin methanesulfonate, methanesulfonic acid, RD concentrated solution and leveling agent, so that the VMS solution theoretically only contains tin methanesulfonate and methanesulfonic acid, but actually a result cannot be measured when the VMS solution containing no lead concentrated solution is used for analysis through CVS measuring equipment, and a machine reports 'Error' information. When VMS solution containing tin methane sulfonate, methanesulfonic acid and lead concentrated solution is used according to the original method, the CVS measuring equipment operates normally, the measured concentration of the standard sample solution is within +/-10% of the theoretical configuration concentration (the allowable error of a machine is +/-10%), namely, a certain amount of lead concentrated solution is added into the VMS solution used for measuring the concentration of the leveling agent. In the process, operators can frequently contact with high-concentration lead concentrated solution (the lead content is 450g/L) and a large amount of lead-containing waste liquid generated by testing, and because lead belongs to heavy metals, the human body can be contacted for a long time and the waste liquid is not treated properly, so that great harm can be caused to the human body and the environment.
Therefore, how to perform the leveling agent concentration test by using the lead-free VMS solution to avoid the harm to human body and environment caused by the contact of personnel and the generation of heavy metal lead waste liquid becomes a difficult problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a method for testing the concentration of a leveling agent in an electroplating tin solution and an electroplating blank solution for testing the concentration of the leveling agent in the electroplating tin solution, so as to solve the problem that a certain amount of lead solution is added into a VMS solution used for testing the concentration of the leveling agent in the prior art, so that the human body and the environment are damaged.
In order to solve the technical problem, the invention provides a method for testing the concentration of a leveling agent in an electroplating tin solution, which comprises the following steps:
preparing an electroplating blank solution, wherein the electroplating blank solution contains copper sulfate pentahydrate, sulfuric acid and chloride ions and does not contain lead;
adding the prepared electroplating blank solution and a standard sample solution with known leveling agent concentration to cyclic voltammetry stripping measurement equipment to obtain a test curve of the standard sample solution and a calibration factor corresponding to the test curve of the standard sample solution;
adding the prepared electroplating blank solution and the prepared electroplating tin solution to the cyclic voltammetry stripping measurement equipment to obtain a test curve of the electroplating tin solution;
and obtaining the concentration of the leveling agent in the electroplating tin solution according to the test curve and the calibration factor of the standard sample solution and the test curve of the electroplating tin solution.
Optionally, in the test method of leveling agent concentration in the tin electroplating solution, the mass fraction of the sulfuric acid is more than 90%.
Optionally, in the test method of the leveling agent concentration in the tin electroplating solution, the mass fraction of the sulfuric acid is 96% to 98%.
Optionally, in the method for testing the leveling agent concentration in the tin electroplating solution, in the prepared electroplating blank solution, the content of copper sulfate pentahydrate is 70g/L to 170g/L, the content of sulfuric acid is 100ml/L to 260ml/L, and the content of chloride ions is 30ppm to 90 ppm.
Optionally, in the method for testing the leveling agent concentration in the tin plating solution, before adding the configured electroplating blank solution and the standard sample solution with a known leveling agent concentration to the cyclic voltammetry stripping measurement apparatus to obtain the test curve and the calibration factor of the standard sample solution, the method for testing the leveling agent concentration in the tin plating solution further includes: and preparing a standard sample solution with known leveling agent concentration according to the controlled median value of the leveling agent concentration in the electroplating tin solution.
Optionally, in the method for testing the leveling agent concentration in the tin electroplating solution, the leveling agent content of the prepared standard sample solution is 90ml/L to 110 ml/L.
Optionally, in the method for testing the leveling agent concentration in the tin electroplating solution, adding the configured electroplating blank solution and the standard sample solution with a known leveling agent concentration to a cyclic voltammetry stripping measurement device to obtain a test curve of the standard sample solution and a calibration factor corresponding to the test curve of the standard sample solution includes the following steps:
placing a certain volume of the electroplating blank solution on a test platform of the cyclic voltammetry stripping measurement equipment;
an adding pipeline of the cyclic voltammetry stripping measuring equipment automatically adds the standard sample solution into the electroplating blank solution according to a certain adding amount and adding times;
and the cyclic voltammetry stripping measurement equipment draws a test curve of the standard sample liquid according to the change of the electroplating rate after the standard sample liquid is added every time and obtains a calibration factor corresponding to the test curve of the standard sample liquid.
Optionally, in the method for testing the leveling agent concentration in the tin electroplating solution, adding the configured electroplating blank solution and the configured tin electroplating solution to the cyclic voltammetry stripping measurement device to obtain a test curve of the tin electroplating solution includes the following steps:
placing a certain volume of the electroplating blank solution on a test platform of the cyclic voltammetry stripping measurement equipment;
an adding pipeline of the cyclic voltammetry stripping measuring equipment automatically adds the electroplating tin solution into the electroplating blank solution according to a certain adding amount and adding times;
and drawing a test curve of the electroplating tin solution by the cyclic voltammetry stripping measuring equipment according to the change of the electroplating rate after the electroplating tin solution is added every time.
Optionally, in the method for testing the concentration of the leveling agent in the tin electroplating solution, obtaining the concentration of the leveling agent in the tin electroplating solution according to the test curve and the calibration factor of the standard sample solution and the test curve of the tin electroplating solution includes: and the cyclic voltammetry stripping measurement equipment automatically calculates the concentration of the leveling agent in the electroplating tin solution according to the calibration factor through fitting of the test curve of the standard sample solution and the test curve of the electroplating tin solution.
The present invention also provides an electroplating blank solution for testing the concentration of a leveler in an electrolytic tin plating solution, the electroplating blank solution comprising copper sulfate pentahydrate, sulfuric acid, and chloride ions and being free of lead;
wherein the content of the blue vitriod is 70 g/L-170 g/L, the content of the sulphuric acid is 100 ml/L-260 ml/L, and the content of the chloride ion is 30 ppm-90 ppm.
Optionally, in the electroplating blank solution for testing the concentration of the leveling agent in the tin electroplating solution, the mass fraction of the sulfuric acid is 96-98%, the content of the copper sulfate pentahydrate is 70-120 g/L, the content of the sulfuric acid is 130-260 ml/L, and the content of the chloride ion is 50-70 ppm.
In the method for testing the concentration of the leveling agent in the tin electroplating solution and the corresponding electroplating blank solution, the prepared electroplating blank solution contains copper sulfate pentahydrate, sulfuric acid and chloride ions and does not contain lead, so that the concentration of the leveling agent in the tin electroplating solution can be accurately tested, namely, a CVS (chemical vapor deposition) measuring device can test and analyze the concentration result of the leveling agent, and an operator cannot contact with the lead solution in the testing process, so that the damage of heavy metal lead to a human body and the environment can be avoided, the operator can be protected, and the environment can be protected.
Drawings
FIG. 1 is a schematic diagram of a test curve of a standard sample solution and a test curve of an electrolytic tin plating solution obtained by a CVS measuring device in the prior art;
fig. 2 to 9 are schematic diagrams of test curves of a standard sample solution and a test curve of a tin plating solution obtained by a CVS metrology apparatus according to an embodiment of the present invention;
FIGS. 10 to 11 are graphs showing normalized effects of factor 3 in the example of the present invention;
FIG. 12 is a plot of the principal effect of fitted levelers in an embodiment of the present invention;
FIG. 13 is a flow chart illustrating a method for testing the leveler concentration in the tin electroplating solution according to an embodiment of the present invention.
Detailed Description
The core idea of the invention is to provide a method for testing the concentration of a leveling agent in an electroplating tin solution and a corresponding electroplating blank solution, wherein the method for testing the concentration of the leveling agent in the electroplating tin solution comprises the following steps: preparing an electroplating blank solution, wherein the electroplating blank solution contains copper sulfate pentahydrate, sulfuric acid and chloride ions and does not contain lead; adding the prepared electroplating blank solution and a standard sample solution with known leveling agent concentration to cyclic voltammetry stripping measurement equipment to obtain a test curve of the standard sample solution and a calibration factor corresponding to the test curve of the standard sample solution; adding the prepared electroplating blank solution and the prepared electroplating tin solution to the cyclic voltammetry stripping measurement equipment to obtain a test curve of the electroplating tin solution; and obtaining the concentration of the leveling agent in the electroplating tin solution according to the test curve and the calibration factor of the standard sample solution and the test curve of the electroplating tin solution. Because the prepared electroplating blank solution contains blue vitriod, sulfuric acid and chloride ions and does not contain lead, the concentration of the leveling agent in the tin electroplating solution can be accurately tested, namely, the CVS measuring equipment can test and analyze the concentration result of the leveling agent, and an operator can not contact the lead solution in the test process, so that the damage of heavy metal lead to the human body and the environment can be avoided, the operator is protected, and the environment is protected.
In order to make the objects, advantages and features of the present invention more apparent, the following method for testing the concentration of leveling agent in an electroplating tin solution according to the present invention will be described in detail with reference to the accompanying drawings and specific examples. The advantages and features of the present invention will become more apparent from the following description. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention. Further, the structures illustrated in the drawings are often part of actual structures. In particular, the drawings may have different emphasis points and may sometimes be scaled differently.
Aiming at the problems that in the prior art, when a plating blank solution (VMS solution) without lead concentrated solution is used for carrying out leveling agent concentration analysis through cyclic voltammetry stripping measurement equipment (CVS measurement equipment), the result cannot be measured, and a machine reports 'Error' information, an inventor carries out deep research and experiments to find out the plating blank solution, which can realize that the leveling agent concentration is accurately tested by using the CVS measurement equipment without adding the lead concentrated solution. After numerous and intensive studies and experiments, the inventors have found that a plating blank solution prepared from a lead-free concentrate containing copper sulfate pentahydrate, sulfuric acid and chloride ions can satisfy this requirement.
For accurately testing the concentration of the leveling agent, the measured concentration of the leveling agent is usually required to be within +/-10% of the theoretical configuration concentration, namely +/-10% of the allowable error of a machine, and for the point, the inventor also performs research and comparison tests to find out the reasonable proportion of the blue vitriod, the sulfuric acid and the chloride ions, thereby not only realizing the accurate measurement of the concentration of the leveling agent, but also proving the feasibility of the concentration of the leveling agent.
To find the copper sulfate pentahydrate (CuSO) used in the VMS solution configuration4·5H2O), sulfuric acid (H)2SO4) And chloride ion (Cl-) and the optimum range of the concentrations of the chemical substances, the inventor analyzes the electrolytic tin plating solution with the known leveling agent concentration under the conditions of different concentration ratios by DOE test (Design of Experiment) and analyzes whether the measurement result meets the target range of 100 +/-10 percent, thereby obtaining the copper sulfate pentahydrate (CuSO)4·5H2O), sulfuric acid (H)2SO4) And the reasonable proportion of chloride ions (Cl-). The sulfuric acid is concentrated sulfuric acid with the mass fraction of more than 90%, preferably, the mass fraction of the sulfuric acid is 96-98%, and more preferably, the mass fraction of the sulfuric acid is 98%.
In the examples of this application, the experiments were conducted using a factor 3, 2 level, the factor 3 being copper sulfate pentahydrate (CuSO)4·5H2O), sulfuric acid (H)2SO4) And chloride ion (Cl-), wherein the 2 levels are two levels with different values, and the specific selection method refers to the following table 1:
TABLE 1
In the embodiment of the application, the mass fraction of the adopted sulfuric acid is 98%, the content of the leveling agent in the prepared electroplating tin solution is 100ml/L, that is, the electroplating tin solution with a known leveling agent concentration is prepared, and the test accuracy of the CVS measuring equipment is confirmed through a test, that is, the accuracy of the test result is judged by using whether the detection measurement result is 100ml/L or 100ml/L ± 10ml/L (within an error range allowed by a machine) as a standard.
Specifically, please refer to table 2 below and please refer to fig. 2 to fig. 9 in combination:
TABLE 2
Wherein, table 2 shows the concentration results (i.e. measured results) of the leveling agent in the obtained tin electroplating solution under different combinations of the factor 3, and the target value of each of the leveling agent is 100ml/L (of course, the range of ± 10% is included, i.e. between 90ml/L and 110 ml/L). Fig. 2 to 9 show test curves given by the CVS measuring apparatus after the tin electroplating solution (here, the tin electroplating solution of a known leveler concentration configured to have a leveler concentration of 100ml/L) and the standard sample solution (here, the standard sample solution used to have a leveler concentration of 100ml/L) were tested on the CVS measuring apparatus using the plating blank solution containing copper sulfate pentahydrate, sulfuric acid, and chloride ions and containing no lead (particularly, a lead-free concentrated solution). Specifically, fig. 2 corresponds to sequence 1 in table 2, fig. 3 corresponds to sequence 2 in table 2, fig. 4 corresponds to sequence 3 in table 2, fig. 5 corresponds to sequence 4 in table 2, fig. 6 corresponds to sequence 5 in table 2, fig. 7 corresponds to sequence 6 in table 2, fig. 8 corresponds to sequence 7 in table 2, and fig. 9 corresponds to sequence 8 in table 2, wherein 200 represents a calibration curve (i.e., a test curve of a standard sample solution), and 210 represents a test curve of an electrolytic tin plating solution. According to the calibration curve 200 and the test curve 210, the CVS measurement apparatus can obtain the calibration factor and the concentration of the leveling agent in the tin electroplating solution, i.e., a list of measurement results in table 2. Further, the concentration of the leveling agent in the electroplating tin liquid obtained by CVS measuring equipment is compared with a target value, and the corresponding copper sulfate pentahydrate (CuSO) can be judged within the range of 90 ml/L-110 ml/L4·5H2O), sulfuric acid (H)2SO4) And whether the electroplating blank solution prepared under the proportion of the chloride ions (Cl-) is usable or not, namely whether an accurate measurement result of the concentration of the leveling agent can be obtained or not.
Referring next to fig. 10-12, wherein fig. 10 and 11 are 3-factor normalized effect plots, fig. 12 is a fitted leveler master effect plot, designated by the factor A, B in fig. 10-12, respectivelyC denotes the factor CuSO4·5H2O (Cu, main component) and H2SO4(main component H), Cl- (main component Cl). As shown in fig. 10, of the A, B, C three factors and the AB, AC, and BC three interaction factors, the factor A, B exceeds the reference line 12.71, i.e., the factor A, B can be considered as a significant effector; meanwhile, referring to fig. 11, only the P value of the factor A, B is less than 0.05, and the critical P value with a significant difference in general industrial judgment is 0.05. From this, it follows from the above experiments: in CuSO4·5H2O(Cu)、H2SO4(H) Among the Cl- (Cl)3 factors, CuSO4·5H2O(Cu)、H2SO4(H) As a main influence factor, the influence of Cl ions is relatively weak; this conclusion can also be drawn with further reference to fig. 12. Further analysis by DOE experiments revealed that the composition CuSO when the leveling agent content was analyzed using a plating blank solution containing copper sulfate pentahydrate, sulfuric acid and chloride ions and containing no lead concentrate4·5H2O、H2SO4Is a main factor influencing the result, and the concentration is preferably set in the range of 70 g/L-170 g/L, 100 ml/L-260 ml/L; the content of Cl ions is relatively weak, and the concentration of the Cl ions can be configured between 30ppm and 90 ppm.
Further, after the proportion of the electroplating blank solution is obtained, the inventor further verifies the proportion. The specific verification process is as follows:
then CuSO is obtained4·5H2O、H2SO4After the optimum range of (c), while fixing the Cl ion content at 60ppm, an experiment was performed using a factor 2, level 3, to set the leveler content in the tin electroplating bath at 100ml/L (which may also be referred to herein as a standard sample), the following tables 3 and 4 were obtained:
TABLE 3
TABLE 4
As can be confirmed again from the above tables 3 and 4, CuSO4·5H2O、H2SO4The concentration of the leveling agent can be measured particularly accurately in the ranges of 70g/L to 170g/L and 100ml/L to 260ml/L, respectively. More preferably, in the configured electroplating blank solution, the mass fraction of the sulfuric acid is 96-98%, the content of the copper sulfate pentahydrate is 70-120 g/L, the content of the sulfuric acid is 130-260 ml/L, and the content of the chloride ion is 50-70 ppm, so that the concentration of the leveling agent in the tin electroplating solution can be measured more accurately, and the accuracy can be basically controlled within a range of +/-8%.
Through a series of research and development, the inventor finally finds an electroplating blank solution which can accurately test the concentration of the leveling agent in the electroplating tin solution and can prevent operators from contacting a high-concentration lead concentrated solution in the test process, so that the concentration of the leveling agent in the electroplating tin solution can be conveniently and safely tested, namely the concentration of the leveling agent in the working solution (the electroplating tin solution used in the actual electroplating process) used in the ordinary electroplating process can be tested.
Specifically, please refer to fig. 13, which is a flowchart illustrating a method for testing the concentration of the leveling agent in the tin electroplating solution according to an embodiment of the present invention. As shown in fig. 13, in the embodiment of the present application, the method for testing the concentration of the leveling agent in the tin electroplating solution mainly includes the following steps:
step S10: preparing an electroplating blank solution which contains copper sulfate pentahydrate, sulfuric acid and chloride ions and is free of lead, in particular, a lead-free concentrated solution;
step S20: adding the prepared electroplating blank solution and a standard sample solution with known leveling agent concentration to cyclic voltammetry stripping measurement equipment to obtain a test curve of the standard sample solution and a calibration factor corresponding to the test curve of the standard sample solution;
step S30: adding the prepared electroplating blank solution and the prepared electroplating tin solution to the cyclic voltammetry stripping measurement equipment to obtain a test curve of the electroplating tin solution;
step S40: and obtaining the concentration of the leveling agent in the electroplating tin solution according to the test curve and the calibration factor of the standard sample solution and the test curve of the electroplating tin solution.
Preferably, in the prepared electroplating blank solution, the mass fraction of the sulfuric acid is more than 90%, and more preferably, the mass fraction of the sulfuric acid is 96-98%. Wherein, in the prepared electroplating blank solution, the content of the blue copperas is 70-170 g/L, the content of the sulfuric acid is 100-260 ml/L, and the content of the chloride ions is 30-90 ppm. More preferably, the content of the copper sulfate pentahydrate is 70-120 g/L, the content of the sulfuric acid is 130-260 ml/L, and the content of the chloride ion is 50-70 ppm, so that the concentration of the leveling agent in the tin plating solution can be measured more accurately, and the accuracy can be basically controlled within the range of +/-8%.
Through using this electroplating blank solution, CVS measuring equipment can test and analyze out the concentration result of evener in the tin plating liquid, can not make operating personnel contact the lead concentrate of high concentration again in the test procedure to can avoid heavy metal lead to the injury of human body and environment, protect operating personnel and realize the environmental protection.
In this embodiment, before adding the configured electroplating blank solution and the standard sample solution with a known leveler concentration to the cyclic voltammetry stripping measurement apparatus to obtain the test curve and the calibration factor of the standard sample solution, the method for testing the leveler concentration in the tin electroplating solution further includes: and preparing a standard sample solution with known leveling agent concentration according to the controlled median value of the leveling agent concentration in the electroplating tin solution. Therefore, the prepared standard sample liquid is more matched with the electrolytic tinning liquid to be tested, the obtained calibration factor is more accurate, and the concentration of the leveling agent in the obtained electrolytic tinning liquid is more accurate. Specifically, the leveling agent content of the prepared standard sample solution can be 90 ml/L-110 ml/L.
In this embodiment of the present application, adding the configured electroplating blank solution and the standard sample solution with a known leveler concentration to a cyclic voltammetry stripping measurement apparatus to obtain the test curve of the standard sample solution and the calibration factor corresponding to the test curve of the standard sample solution specifically includes the following steps:
step S21: and placing a certain volume of the electroplating blank solution on a test platform of the cyclic voltammetry stripping measurement equipment, namely placing a certain amount of electroplating blank solution which can be obtained.
Step S22: and an adding pipeline of the cyclic voltammetry stripping measurement equipment automatically adds the standard sample liquid into the electroplating blank solution according to a certain adding amount and adding times, namely, the CVS measurement equipment automatically adds the acquired standard sample liquid in quantity and adds the standard sample liquid for multiple times.
Step S23: and the cyclic voltammetry stripping measurement equipment draws a test curve of the standard sample liquid according to the change of the electroplating rate after the standard sample liquid is added every time and obtains a calibration factor corresponding to the test curve of the standard sample liquid, namely the CVS measurement equipment automatically draws a corresponding test curve according to the change of the electroplating rate after the standard sample liquid is added every time and obtains a corresponding calibration factor.
Namely, the test curve of the standard sample liquid and the corresponding calibration factor can be obtained according to the steps.
Then, the CVS measuring apparatus performs the same operation on the electrolytic tin plating solution, specifically including:
step S31: placing a certain volume of the electroplating blank solution on a test platform of the cyclic voltammetry stripping measurement equipment;
step S32: an adding pipeline of the cyclic voltammetry stripping measuring equipment automatically adds the electroplating tin solution into the electroplating blank solution according to a certain adding amount and adding times;
step S33: and drawing a test curve of the electroplating tin solution by the cyclic voltammetry stripping measuring equipment according to the change of the electroplating rate after the electroplating tin solution is added every time.
Therefore, the CVS measuring equipment can obtain the test curve of the tin plating solution.
And then, the cyclic voltammetry stripping measurement equipment can automatically calculate the concentration of the leveling agent in the electroplating tin solution according to the calibration factor through fitting of the test curve of the standard sample solution and the test curve of the electroplating tin solution. Namely, the CVS measuring device can automatically give the concentration of the leveling agent in the electroplating tin liquid.
In summary, in the method for testing the concentration of the leveling agent in the tin electroplating solution provided by the invention, the prepared electroplating blank solution contains copper sulfate pentahydrate, sulfuric acid and chloride ions and does not contain a lead concentrated solution, so that the concentration of the leveling agent in the tin electroplating solution can be accurately tested, namely, a CVS (chemical vapor deposition) measuring device can test and analyze the concentration result of the leveling agent, and an operator cannot be in contact with the high-concentration lead concentrated solution in the testing process, so that the damage of heavy metal lead to a human body and the environment can be avoided, the operator can be protected, and the environment can be protected.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.
Claims (11)
1. A method for testing the concentration of a leveling agent in an electrolytic tinning liquid is characterized by comprising the following steps:
preparing an electroplating blank solution, wherein the electroplating blank solution contains copper sulfate pentahydrate, sulfuric acid and chloride ions and does not contain lead;
adding the prepared electroplating blank solution and a standard sample solution with known leveling agent concentration to cyclic voltammetry stripping measurement equipment to obtain a test curve of the standard sample solution and a calibration factor corresponding to the test curve of the standard sample solution;
adding the prepared electroplating blank solution and the prepared electroplating tin solution to the cyclic voltammetry stripping measurement equipment to obtain a test curve of the electroplating tin solution;
and obtaining the concentration of the leveling agent in the electroplating tin solution according to the test curve and the calibration factor of the standard sample solution and the test curve of the electroplating tin solution.
2. The method for measuring the leveler concentration in the tin electroplating bath according to claim 1, wherein the mass fraction of the sulfuric acid is 90% or more.
3. The method for measuring the leveler concentration in an electrolytic tin plating bath according to claim 2, wherein the mass fraction of the sulfuric acid is 96% to 98%.
4. The method for testing leveler concentration in electrolytic tin plating bath according to claim 2, wherein the plating blank solution is prepared such that the copper sulfate pentahydrate is contained in an amount of 70g/L to 170g/L, the sulfuric acid is contained in an amount of 100ml/L to 260ml/L, and the chloride ion is contained in an amount of 30ppm to 90 ppm.
5. The method for testing the concentration of the leveling agent in the electroplating tin solution according to any one of claims 1 to 4, wherein before adding the configured electroplating blank solution and the standard sample solution with known leveling agent concentration to the cyclic voltammetry stripping measurement equipment to obtain the test curve and the calibration factor of the standard sample solution, the method for testing the concentration of the leveling agent in the electroplating tin solution further comprises: and preparing a standard sample solution with known leveling agent concentration according to the controlled median value of the leveling agent concentration in the electroplating tin solution.
6. The method for measuring the leveler concentration in the tin electroplating solution according to claim 5, wherein the leveler content of the prepared standard sample solution is 90ml/L to 110 ml/L.
7. The method for testing the concentration of the leveling agent in the tin electroplating solution according to any one of claims 1 to 4, wherein the step of adding the configured electroplating blank solution and the standard sample solution with the known concentration of the leveling agent to the cyclic voltammetry stripping measurement equipment to obtain the test curve of the standard sample solution and the calibration factor corresponding to the test curve of the standard sample solution comprises the following steps:
placing a certain volume of the electroplating blank solution on a test platform of the cyclic voltammetry stripping measurement equipment;
an adding pipeline of the cyclic voltammetry stripping measuring equipment automatically adds the standard sample solution into the electroplating blank solution according to a certain adding amount and adding times;
and the cyclic voltammetry stripping measurement equipment draws a test curve of the standard sample liquid according to the change of the electroplating rate after the standard sample liquid is added every time and obtains a calibration factor corresponding to the test curve of the standard sample liquid.
8. The method for testing the leveling agent concentration in the tin electroplating solution according to any one of claims 1 to 4, wherein the step of adding the configured electroplating blank solution and the tin electroplating solution to the cyclic voltammetry stripping measurement equipment to obtain the test curve of the tin electroplating solution comprises the following steps:
placing a certain volume of the electroplating blank solution on a test platform of the cyclic voltammetry stripping measurement equipment;
an adding pipeline of the cyclic voltammetry stripping measuring equipment automatically adds the electroplating tin solution into the electroplating blank solution according to a certain adding amount and adding times;
and drawing a test curve of the electroplating tin solution by the cyclic voltammetry stripping measuring equipment according to the change of the electroplating rate after the electroplating tin solution is added every time.
9. The method for testing the concentration of the leveling agent in the tin electroplating solution according to any one of claims 1 to 4, wherein obtaining the concentration of the leveling agent in the tin electroplating solution according to the test curve and the calibration factor of the standard sample solution and the test curve of the tin electroplating solution comprises: and the cyclic voltammetry stripping measurement equipment automatically calculates the concentration of the leveling agent in the electroplating tin solution according to the calibration factor through fitting of the test curve of the standard sample solution and the test curve of the electroplating tin solution.
10. An electroplating blank solution for testing leveler concentration in a tin electroplating solution, the electroplating blank solution comprising copper sulfate pentahydrate, sulfuric acid, and chloride ions and being free of lead;
wherein the content of the blue vitriod is 70 g/L-170 g/L, the content of the sulphuric acid is 100 ml/L-260 ml/L, and the content of the chloride ion is 30 ppm-90 ppm.
11. The electroplating blank solution for testing the concentration of the leveling agent in the tin electroplating solution according to claim 10, wherein the mass fraction of the sulfuric acid is 96-98%, the content of the copper sulfate pentahydrate is 70-120 g/L, the content of the sulfuric acid is 130-260 ml/L, and the content of the chloride ion is 50-70 ppm.
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