CN115679395A - Iron plating solution, preparation method thereof, electroplating process and application - Google Patents
Iron plating solution, preparation method thereof, electroplating process and application Download PDFInfo
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- CN115679395A CN115679395A CN202211355454.1A CN202211355454A CN115679395A CN 115679395 A CN115679395 A CN 115679395A CN 202211355454 A CN202211355454 A CN 202211355454A CN 115679395 A CN115679395 A CN 115679395A
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Abstract
The present invention relates to an iron plating solution for manufacturing a polishing pad dresser, comprising: oxalic acid complex of ferric ions, pH buffering agent, chloride auxiliary reagent, stress remover and wetting agent; the pH of the iron plating solution is 3.0-3.8. The invention provides a preparation method of an iron plating solution for manufacturing a polishing pad dresser. The invention provides an electroplating process of an iron plating solution for manufacturing a polishing pad dresser. The invention also provides a polishing pad dresser obtained by the electroplating process of the iron plating solution for manufacturing the polishing pad dresser. The iron plating solution of the invention adopts ferric ions as main salt, and adopts ammonium oxalate to complex with the ferric ions to form stable soluble ferric salt, thereby eliminating the oxidation problem of the common main salt of the ferrous ions in the plating solution, preventing the generation and the precipitation of ferric hydroxide and solving the stability problem of the iron plating solution.
Description
Technical Field
The invention relates to the field of electroplating, in particular to an iron plating solution, a preparation method thereof, an electroplating process and application.
Background
The iron plating process has wide application in repairing crankshaft, camshaft, transmission shaft, wear, corrosion and machining parts. The iron plating layer obtained by the early chloride plating solution at room temperature is hard and brittle, has poor binding force with a substrate and has large internal stress. The method is widely applied to repairing worn devices by an improved high-temperature (85-105 ℃) chloride direct-current iron plating process. However, in the high-temperature iron plating process, the plating solution evaporation amount is large, the environmental pollution is serious, and the hardness and the wear resistance of the plating layer are poor.
The dresser is a consumable necessary for chemical mechanical planarization, and has the function of dressing the polishing pad, including appropriate cutting of the surface of the polishing pad to maintain the appropriate roughness of the surface of the polishing pad; meanwhile, abrasive dust in the polishing process is cleaned, and the surface of the polishing pad is prevented from glazing, so that the service life of the polishing pad is prolonged, and the polishing efficiency is improved. The fixation of diamond in the dresser includes plating, brazing, metal sintering, and the like. The process of fixing the diamond in the plating layer by the electroplating process involves manual operations such as sanding and unloading the diamond, and the high-temperature iron plating solution makes the operations extremely difficult, so that the high-temperature iron plating process is not suitable for manufacturing electroplated diamond trimmers.
Another significant problem with existing iron plating solution formulations and processes is that ferrous ions in the iron plating solution are easily oxidized to ferric ions. On one hand, the oxidation reaction reduces the concentration of ferrous ions in the iron plating solution, which causes the components of the iron plating solution to be unstable; on the other hand, in the iron plating solution having a pH value higher than 3, ferric ions are easily bonded with hydroxyl radicals to be precipitated in the form of precipitates, and the adsorption of ferric hydroxide on the cathode surface results in the surface roughness of the iron plating layer and the deterioration of mechanical properties. In order to solve the key problem that ferrous ions are oxidized into ferric ions and ferric hydroxide precipitates are formed, the current main technical approach is to adopt ferrous sulfate with slightly high oxidation resistance as a main salt and adopt ascorbic acid, glycolic acid, gluconic acid, ethylene diamine tetraacetic acid, monoethanolamine sulfamic acid, ammonium fluoroborate, ammonium bifluoride and the like as a reducing agent or a complexing agent of ferric ions. Among them, fluoride has a good effect, but a plating solution containing fluorine ions is harmful to workers greatly, and the treatment of electroplating wastewater is difficult. Further, as these reducing agents or complexing agents are consumed, the precipitation of iron hydroxide is inevitable even under continuous plating conditions. Therefore, none of the above methods fundamentally solves the stability problem of the iron plating solution.
Disclosure of Invention
In order to overcome the defects and shortcomings of the existing iron plating technology and solve the problem that ferric ions in a divalent iron plating solution do harm to the stability and the plating performance of the iron plating solution, the invention mainly aims to provide the iron plating solution for manufacturing a polishing pad dresser, which is stable in components. The iron plating solution can be used for electrodepositing on a substrate of a trimmer to obtain a pure iron plating layer, the prepared pure iron plating layer is compact and uniform, has high hardness and good bonding strength with the substrate, and the diamond is easy to sand, thereby solving the problem of unstable plating solution caused by oxidation of ferrous ions.
It is an object of the present invention to address at least the above problems and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided an iron plating solution for manufacturing a pad dresser, comprising: oxalic acid complex of ferric ions, pH buffering agent, chloride auxiliary reagent, stress remover and wetting agent; the pH of the iron plating solution is 3.0-3.8.
Specifically, the concentration of iron in the iron plating solution is 0.3-0.5mol/L;
the concentration of the pH buffering agent is 0.4-0.7mol/L;
the concentration of the chloride auxiliary reagent is 0.2-0.7mol/L;
the concentration of the stress remover is 0.01-0.025mol/L;
the concentration of the wetting agent is 0.35-1.4mmol/L.
Specifically, the oxalic acid complex of ferric ions is one or more of a complex formed by ferric ammonium oxalate, a soluble ferric salt and a complex formed by ammonium oxalate.
Specifically, the soluble ferric salt is one or more of ferric chloride, ferric sulfate and ferric sulfamate.
Specifically, the molar ratio of the complexing agent to the soluble ferric salt is at least 3.1.
Specifically, the pH buffer is boric acid;
the chloride auxiliary reagent is one or more of ammonium chloride, manganese chloride and sodium chloride;
the stress remover is one or more of sodium o-benzoylsulfonyl imide, sodium p-toluenesulfonamide and sodium p-toluenesulfinate;
the wetting agent is one or more of sodium dodecyl sulfate and sodium methylene dinaphthalene sulfonate.
The invention also provides a preparation method of the iron plating solution for manufacturing the polishing pad dresser, which comprises the following steps:
s1, adding a pH buffering agent and a chloride auxiliary reagent into deionized water, heating to 60-80 ℃, stirring until the pH buffering agent and the chloride auxiliary reagent are completely dissolved, and adjusting the pH to 3 to obtain a first solution;
s2, adding an oxalic acid complex of ferric ions into the first solution, and stirring until the oxalic acid complex is completely dissolved to obtain a second solution;
s3, adding a stress remover and a wetting agent into the second solution, then supplementing deionized water to a preset volume, and adjusting the pH value range to 3.0-3.8 to obtain an iron plating solution;
the volume of the deionized water added in the step S1 is 2/3 of the preset volume.
The invention also provides an electroplating process of the iron plating solution, which comprises the following steps: using the base body of the trimmer as a cathode and a pure iron plate as an anode, the electroplating temperature is 30-40 ℃, the pH of the iron plating solution is 3.0-3.8, and the current density is 0.5-2.0A/dm 2 。
Specifically, the current waveform may be one of direct current, single pulse current or double pulse current;
when pulse electroplating is adopted, the duty ratio of pulse current is 5% -50%, and the peak current is 1.0-4.0A/dm 2 。
The invention also provides a trimmer for the polishing pad, wherein the roughness Ra of the plating layer of the trimmer is 0.3-0.5 mu m.
The invention at least comprises the following beneficial effects:
1. according to the iron plating solution, ferric ions are used as main salts, and ammonium oxalate is matched with the ferric ions to form stable soluble ferric salts, so that the problem of oxidation of common ferrous ion main salts in the plating solution is solved, generation and precipitation of ferric hydroxide are prevented, and the problem of stability of the iron plating solution is solved;
2. the surface appearance of the iron coating can be regulated and controlled by changing the electroplating temperature and current parameters, the roughness of the coating of the trimmer is controlled, and the obtained pure iron coating has strong binding force with the matrix and compact coating structure;
3. compared with the plating solution for preventing ferric hydroxide precipitation by adopting fluoride, fluoborate and the like, the iron plating solution provided by the invention is more environment-friendly in composition, low in cost and simple in preparation process.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a photomicrograph of the working surface of a dresser substrate after electroplating.
Detailed Description
The following discussion will focus on specific implementations and embodiments of the present disclosure. This detailed description is provided to aid in the description of certain embodiments and should not be construed in a limiting sense on the scope or applicability of the present disclosure. It is to be understood that other embodiments may be used based on the present disclosure.
The terminology used in the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Unless defined differently, all terms used herein including technical or scientific terms have the same meaning as commonly understood by one having ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The polishing pad is one of the main consumables in the chemical mechanical polishing system, and the structure and surface roughness of the polishing pad have a great influence on the removal rate of wafer material and surface roughness during the CMP process. The CMP pad dresser enables the surface of the polishing pad to be regenerated to an optimum state, and corrects the shape of the polishing pad and maintains the wafer polishing rate. The dresser primarily dresses the surface of the polishing pad with diamonds fixed to the substrate. The fixation of diamond in the dresser includes plating, brazing, metal sintering, and the like. The invention adopts an electroplating method to fix the diamond on the matrix of the trimmer.
Electroplating is a process of plating a thin layer of other metals or alloys on the surface of some metals by using the principle of electrolysis, and is a process of attaching a metal film on the surface of a metal or other material workpiece by using the action of electrolysis. During electroplating, plating metal or other insoluble materials are used as an anode, a workpiece to be plated is used as a cathode, and cations of the plating metal are reduced on the surface of the workpiece to be plated to form a plating layer. In order to eliminate the interference of other cations and make the coating uniform and firm, a solution containing the metal cations of the coating is used as an electroplating solution to keep the concentration of the metal cations of the coating constant.
In the iron plating process, ferric ions in the iron plating solution with the pH value of more than 3 are easily combined with hydroxide radicals to be separated out in a precipitation mode, and the adsorption of ferric hydroxide on the surface of a cathode can cause the surface roughness of an iron plating layer and the deterioration of mechanical properties. If the pH value of the iron plating solution is less than 3, the hydrogen evolution side reaction in the electroplating process is serious, and the precipitated hydrogen permeates into the plating layer and the substrate to generate hydrogen embrittlement, so that the performance of the plating layer is poor. If the evolved hydrogen stays on the surface of the part in the form of bubbles, voids and pockmarks of the plating layer are caused.
< iron plating solution >
The invention provides an iron plating solution for manufacturing a polishing pad dresser, which takes a pure iron or carbon steel substrate as a cathode in the electroplating process, precipitates elementary substance iron from the iron plating solution onto the substrate of the dresser, and holds diamonds distributed on the substrate. In the present embodiment, the specific components of the iron plating solution include: oxalic acid complex of ferric ions, pH buffering agent, chloride auxiliary reagent, stress remover and wetting agent; the pH of the iron plating solution is 3.0-3.8. The iron plating process is completed under an acidic condition, and the passivation of the iron anode can be avoided.
The iron plating solution in the embodiment of the invention adopts oxalic acid complex of ferric ion. The oxalic acid complex of ferric iron ions is one or more of a complex formed by ferric ammonium oxalate and a complex formed by soluble ferric iron salt and ammonium oxalate. The problem that the iron plating solution is oxidized is solved by adopting high-valence iron ions. Meanwhile, the electroplating solution is stable, and the problem of ferric hydroxide precipitation does not occur.
The effect of ammonium oxalate in plating is very important. The ammonium oxalate is matched with ferric ions to form an iron ammonium oxalate (III) complex, the iron ammonium oxalate (III) complex has very good stability, and can be used in an iron plating solution with the pH value of more than 3 to ensure that no ferric hydroxide precipitate is generated in the iron plating solution. The solubility of the ferrous oxalate is 0.03g/100g, and the ferrous oxalate is yellow precipitate in water and is insoluble in water. In practice, no yellow material was observed, indicating that no ammonium ferrous oxalate precipitate was formed during the iron plating process. By further illustration, after the ferric iron is reduced to the ferrous iron on the surface of the cathode, the ferric iron can be rapidly reduced to the elemental iron. Although citric acid can complex ferric iron, the stability constant of the formed complex is too large, the reduction potential of iron ions is more negative than that of oxalic acid complex, hydrogen evolution is promoted, and the internal stress of a plating layer is larger.
In an embodiment of the present invention, the molar ratio of the ammonium oxalate to the soluble ferric salt is at least 3.1:1, capable of generating iron tris (oxalate) complex ion [ Fe (C) upon coordination reaction thereof 2 O 4 ) 3 ] 3- . Preferably, the molar ratio of the ammonium oxalate to the soluble ferric salt is 3.1-6:1; more preferably, the molar ratio of the ammonium oxalate to the soluble ferric salt is 3.1-5:1.
The soluble ferric salt in the embodiment of the invention is one or more of ferric chloride, ferric sulfate and ferric sulfamate, and can also be other soluble ferric salts.
The concentration of iron in the iron plating solution is closely related to the plating speed, the concentration is high, the current density is high, and the plating speed is high; the concentration is low and the plating speed is slow. However, too high a concentration may affect the dispersibility of the plating solution. Therefore, the present embodiment adopts an iron supply mode of the iron ammonium oxalate (iii) complex, and the iron-containing concentration in the iron plating solution is set to be 0.3 to 0.5mol/L; preferably, the concentration of ferric ammonium oxalate is 0.4mol/L.
In order to prevent the iron plating solution from raising the pH due to a gas (e.g., hydrogen) generated during the iron electroplating operation, which affects the plating performance. The pH buffering agent plays a great role in the stability of the pH value in the electroplating process, and the concentration of the pH buffering agent is 0.4-0.7mol/L in consideration of the stability and the economy of the iron plating solution; the pH buffer is boric acid, the mass concentration is converted, and the boric acid content is 24.73-43.28g/L. Preferably, the concentration of boric acid is 0.45 to 0.6mol/L. More preferably, the concentration of boric acid is 0.5mol/L. The pH buffering agent may also be a polybasic acid having a buffering action that does not form a precipitate or complex with ferric ions.
In the embodiment of the invention, the concentration of the chloride auxiliary reagent is 0.2-0.7mol/L. Preferably, the concentration of the chloride auxiliary reagent is 0.4-0.7mol/L. More preferably, the concentration of the chloride auxiliary reagent is 0.5-0.6mol/L. The chloride auxiliary reagent is one or more of manganese chloride, ammonium chloride and sodium chloride. The addition of manganese chloride, ammonium chloride and sodium chloride increases the conductivity of the solution and promotes the dissolution of the anode, and the brittleness of the plating layer increases with the increase of the content of the manganese chloride, the ammonium chloride and the sodium chloride, so that the addition of the manganese chloride, the ammonium chloride and the sodium chloride is not suitable for being excessive.
The internal stress of the plating layer is a balance force which is generated in the metal electro-crystallization process corresponding to the stress in the crystal growth process due to the influence of the operation conditions and the composition of the plating solution in the metal electro-deposition process. Since it is not stressed by external forces, it is called internal stress. From a microscopic view, the internal stress of the coating is also accumulated by abnormal electrodeposition when the metal is arranged in an order far away from the crystal lattice in the metal electrodeposition process. When the accumulated microscopic internal stress reaches a certain value, the coating can be seriously flaked or even cracked macroscopically in the releasing process. If the force is not sufficient to break the coating and release it, internal stress is exhibited, and when induced, release is exhibited, which may be manifested as brittleness of the coating and the like. The concentration of the stress relieving agent in the embodiment of the invention is 0.01-0.025mol/L; preferably, the concentration of the stress relieving agent is 0.01-0.02mol/L; more preferably, the concentration of the stress relieving agent is 0.015mol/L. Common stress relief agents used in electroplating processes are: naphthalenesulfonic acid, p-toluenesulfonamide, saccharin and the like. In the embodiment of the invention, the stress remover is one or more of sodium o-benzoylsulfonimide, sodium p-toluenesulfonamide and sodium p-toluenesulfinate.
The most basic requirement of the electroplating wetting agent is to better reduce the interfacial tension between the electrode and the plating solution interface, so that the plating solution is easy to spread on the electrode surface to achieve the purpose of uniform plating, has certain salt resistance, acid and alkali resistance and temperature resistance for the plating solution, and ensures that the plating layer is better attached to a substrate to reduce pores. The wetting agent of the present embodiment is one or more of sodium dodecyl sulfate and sodium methylene dinaphthalene sulfonate. The concentration of the wetting agent is 0.35-1.4mmol/L; preferably, the concentration of the wetting agent is 0.35-1.25mmol/L; preferably, the concentration of the wetting agent is 0.5-1.0mmol/L; more preferably, the concentration of the wetting agent is 0.5mmol/L. Most preferably, 1.0mmol/L sodium dodecyl sulfate may be used.
< method for producing iron plating solution >
The invention provides a preparation method of an iron plating solution for manufacturing a polishing pad dresser, which comprises the following steps:
s1, adding a pH buffering agent and a chloride auxiliary reagent into deionized water, heating to 60-80 ℃, stirring until the pH buffering agent and the chloride auxiliary reagent are completely dissolved, and adjusting the pH to 3 to obtain a first solution;
s2, adding ferric ammonium oxalate and/or soluble ferric iron salt and ammonium oxalate into the first solution, and stirring until the ferric ammonium oxalate and/or the soluble ferric iron salt and the ammonium oxalate are completely dissolved to obtain a second solution;
and S3, adding a stress remover and a wetting agent into the second solution, then supplementing deionized water to a preset volume, and adjusting the pH value to 3.0-3.8 to obtain the iron plating solution.
The pH adjustment is carried out using dilute sulfuric acid, and if the pH is lowered, the pH may be adjusted to a range of 3.0 to 3.8 using a 5% aqueous solution of sodium hydroxide.
The volume of deionized water added in step S1 of the present embodiment is 2/3 of the preset volume.
The embodiment of the invention adopts a method of adding step by step, which can prevent the iron plating solution from generating precipitation.
< electroplating Process of iron plating solution >
The invention provides an electroplating process of an iron plating solution for manufacturing a polishing pad dresser, which comprises the following steps:
s1, iron or carbon steel matrix plating pretreatment of a dresser;
in the invention, the pretreatment of the dresser substrate before plating comprises chemical degreasing, dilute hydrochloric acid soaking rust removal, electrochemical degreasing, electrochemical activation, distilled water leaching and the like, so as to achieve the purpose of enhancing the bonding strength of a plating layer and the substrate.
In the pre-plating treatment step of the substrate, chemical degreasing is firstly carried out. Soaking the substrate in a degreasing agent or a detergent solution, carefully scrubbing the substrate by using cotton yarn to stick sawdust, and then cleaning the substrate by using water. If only a partial area of the substrate is to be plated, the non-plated surface is to be insulated. The insulation treatment can be performed by using waterproof electrical tape for wrapping, coating insulating paint and the like. After insulation, the surface of the plating is to be derusted, and the substrate can be soaked in 10wt% dilute hydrochloric acid for 1-1.5min.
After the matrix is derusted, electrochemical oil removal is carried out: connecting the matrix subjected to rust removal treatment with a direct-current power supply cathode, and connecting a lead plate with an anode for electrifying for 2-3min; and then switching the substrate into an anode, namely connecting the substrate with the anode, connecting a lead plate with a cathode, electrifying for 1-2min, removing an oil film on an electroplating surface, and finally washing the substrate with clear water. Wherein the current density for removing oil is 3-8A/dm 2 The formula of the electrolyte is as follows: 16-40g/L of sodium hydroxide, 30-50g/L of sodium carbonate, 10-20g/L of sodium phosphate and 5-12g/L of sodium silicate.
Matrix electrochemicalAfter chemical degreasing, electrochemical activation should be performed to ensure the bonding strength between the iron-plated layer and the substrate. Electrochemical activation adopts 25-40% sulfuric acid solution as electrolyte, the matrix after electrochemical deoiling treatment is connected with DC power supply anode, lead plate is connected with cathode, and the concentration of lead plate is 10-20A/dm 2 The current density is electrified and activated for 1.5min, and finally the matrix is washed by clear water.
S2, putting the base body into the iron plating solution in an electrified manner after the pre-plating treatment. Using the substrate as cathode and pure iron plate as anode, electroplating temperature 30-40 deg.C, pH of iron plating solution 3.0-3.8, and current density 0.5-2.0A/dm 2 。
Preferably, the pH of the iron plating solution is in the range of 3.0 to 3.8.
Preferably, the plating temperature of the iron plating solution is maintained at 30 to 35 ℃.
Specifically, the current waveform may be one of direct current, single pulse current or double pulse current;
when pulse electroplating is adopted, the duty ratio of pulse current is 5-50%, and the peak current is 1.0-4.0A/dm 2 。
Preferably, the current waveform adopts pulse current, the duty ratio is 20-30%, and the average current density is 0.8-1.2A/dm 2 。
And after the electroplating is finished, washing the diamond tool by using clear water to remove the residual plating solution on the surface of the diamond tool. If necessary, the diamond tool may be subjected to rust prevention treatment using mineral oil, grease, or the like after cleaning.
< pad dresser >
The invention provides a dresser for polishing pads, wherein the roughness Ra of a dressing coating of the dresser is 0.3-0.5 mu m. The polishing pad prepared by the electroplating process has a flat coating, can well control the edge height of the diamond, has small damage to the polishing pad in the cutting process, can prolong the service life of the polishing pad, and possibly also can prolong the service life of a polishing pad trimmer.
The advantages, features and methods of accomplishing the same will become more apparent with reference to the following detailed description of the embodiments.
< example 1>
An iron plating solution for use in manufacturing a polishing pad dresser, comprising: 0.4mol/L ferric ammonium oxalate, 0.5mol/L boric acid, 0.5mol/L ammonium chloride, 0.015mol/L sodium o-benzoylsulfonimide and 0.5mmol/L sodium dodecyl sulfate; the pH value of the iron plating solution is between 3.0 and 3.8.
< example 2>
An iron plating solution for use in manufacturing a polishing pad dresser, comprising: 0.3mol/L ferric chloride, 1.0mol/L ammonium oxalate, 0.45mol/L boric acid, 0.4mol/L sodium chloride, 0.01mol/L sodium p-toluenesulfonamide and 0.7mmol/L sodium methylenedinaphthalene sulfonate; the pH value of the iron plating solution is between 3.0 and 3.8.
< example 3>
An iron plating solution for use in manufacturing a polishing pad dresser, comprising: 0.5mol/L ferric sulfate, 1.6mol/L ammonium oxalate, 0.6mol/L boric acid, 0.6mol/L manganese chloride, 0.025mol/L sodium p-toluenesulfinate, and 1.4mmol/L sodium methylenedinaphthalene sulfonate; the pH value of the iron plating solution is between 3.0 and 3.8.
< example 4>
An iron plating solution for use in manufacturing a polishing pad dresser, comprising: 0.45mol/L ferric ammonium oxalate, 0.7mol/L boric acid, 0.7mol/L ammonium chloride, 0.02mol/L sodium o-benzoylsulfonimide and 1.0mmol/L sodium dodecyl sulfate; the pH value of the iron plating solution is between 3.0 and 3.8.
< example 5>
An iron plating solution for use in manufacturing a polishing pad dresser, comprising: 0.35mol/L ferric sulfamate, 1.1mol/L ammonium oxalate, 0.5mol/L boric acid, 0.6mol/L sodium chloride, 0.015mol/L sodium p-toluenesulfinate and 0.7mmol/L sodium methylenedinaphthalene sulfonate; the pH of the iron plating solution is between 3.0 and 3.8.
< example 6>
An iron plating solution for use in manufacturing a polishing pad dresser, comprising: 0.3mol/L ferric sulfate, 1.3mol/L ammonium oxalate, 0.4mol/L boric acid, 0.3mol/L manganese chloride, 0.01mol/L sodium p-toluenesulfonamide and 0.35mmol/L sodium dodecyl sulfate; the pH value of the iron plating solution is between 3.0 and 3.8.
< example 7>
This example provides a method of preparing an iron plating solution for use in the manufacture of a pad dresser, the iron plating solution prepared by the method having the composition levels shown in example 1. The preparation method comprises the following steps:
s1, adding boric acid and ammonium chloride into deionized water, heating to 60 ℃, stirring until the boric acid and the ammonium chloride are completely dissolved, and adjusting the pH value to 3 by using dilute sulfuric acid to obtain a first solution;
s2, adding ferric ammonium oxalate into the first solution, and stirring until the ferric ammonium oxalate is completely dissolved to obtain a second solution;
s3, dissolving the sodium o-benzoylsulfonyl imide and the sodium dodecyl sulfate, adding the dissolved sodium o-benzoylsulfonyl imide and the sodium dodecyl sulfate into a second solution, then supplementing deionized water to a preset volume, and adjusting the pH value range to 3.0-3.8 by adopting a 5wt% sodium hydroxide solution to obtain the iron plating solution.
The volume of the deionized water added in the step S1 is 2/3 of the preset volume.
< example 8>
This example provides a method of preparing an iron plating solution for use in the manufacture of a pad dresser, the iron plating solution prepared by the method having the composition levels shown in example 2. The preparation method comprises the following steps:
s1, adding boric acid and sodium chloride into deionized water, heating to 70 ℃, stirring until the boric acid and the sodium chloride are completely dissolved, and adjusting the pH value to 3 by using dilute sulfuric acid to obtain a first solution;
s2, adding ferric chloride and ammonium oxalate into the first solution, and stirring until the ferric chloride and the ammonium oxalate are completely dissolved to obtain a second solution;
s3, dissolving the p-toluenesulfonamide sodium and the methylene dinaphthalene sodium sulfonate, adding the dissolved p-toluenesulfonamide sodium and the dissolved methylene dinaphthalene sodium sulfonate into the second solution, then supplementing deionized water to a preset volume, and adjusting the pH value range to 3.0-3.8 by adopting a 5wt% sodium hydroxide solution to obtain the iron plating solution.
The volume of the deionized water added in the step S1 is 2/3 of the preset volume.
< example 9>
In this example, the plating process of the dresser substrate using the iron plating solution of example 1 includes the steps of:
s1, pre-treating a dresser substrate, namely carrying out chemical oil removal, dilute hydrochloric acid soaking rust removal, electrochemical oil removal, electrochemical activation and distilled water leaching by using a detergent.
S2, putting the trimmer matrix into the iron plating solution in an electrified manner after the pre-plating treatment. The substrate is used as a cathode, and the pure iron plate is used as an anode. The used electroplating process parameters are as follows: the temperature of the plating solution is 35 ℃; pulse current parameter, duty ratio 30%, average current density 1.2A/dm 2 . Electroplating the dresser substrate for 20 minutes, and then sanding by adopting a sand burying method; burying sand for 1hr, removing sand, and coating until the diamond is embedded by iron coating to 70% of the diamond particle size. And taking the diamond out of the groove and cleaning the diamond to obtain the trimmer of the electroplated diamond with the pure iron coating. The microphotograph of the diamond-encased dresser substrate after iron plating is shown in fig. 1, and the dresser substrate has fine crystals and smooth surface.
< example 10>
The plating process of this example was the same as example 8, except that the dresser substrate was charged after the above-described pre-plating treatment and placed in the iron plating solution of example 2. The used electroplating process parameters are as follows: the temperature of the plating solution is 30 ℃; pulse current parameter, duty ratio of 35%, average current density of 1.5A/dm 2 。
< example 11>
The plating process of this example was the same as example 8, except that the dresser substrate was charged after the above-described pre-plating treatment and placed in the iron plating solution of example 3. The used electroplating process parameters are as follows: the temperature of the plating solution is 40 ℃; pulse current parameter, duty ratio 25%, average current density 1.0A/dm 2 。
< comparative example 1>
This comparative example provides an iron plating solution for use in the manufacture of a pad dresser, the contents of the components in the iron plating solution being as shown in example 1. Except that the pH of the iron plating solution was about 4.5.
< comparative example 2>
This comparative example provides an iron plating solution for use in the manufacture of a pad dresser, the contents of the components in the iron plating solution being as shown in example 1. Wherein the difference is that the pH of the iron plating solution is about 6.
< comparative example 3>
The plating process of this comparative example was the same as in example 9, except that the plating process parameters: the temperature of the plating solution is normal temperature; pulse current parameter, duty cycle 30%, average current density 3A/dm 2 。
< comparative example 4>
The plating process of this comparative example was the same as example 9, except that the plating process parameters used were: the temperature of the plating solution is 50 ℃; pulse current parameter, duty cycle 30%, average current density 3A/dm 2 。
< test example 1>
The iron plating solutions of examples 1 to 6 and comparative examples 1 to 2 were allowed to stand at normal temperature, and the color and turbidity of the iron plating solutions were observed; the observation results are shown in table 1.
TABLE 1 stability of iron plating solutions
As is clear from Table 1, the iron plating solutions of examples 1 to 6 were stable and no iron hydroxide precipitates were formed. As is clear from comparison between example 1 and comparative examples 1 to 2, the pH of the iron plating solution affects the formation of precipitates.
< test example 2>
The roughness Ra, rz of the coatings of the working surfaces of the dressers of examples 9 to 11 and of comparative examples 3 to 4 were measured using a model name VK-X3000 from KEYENCE (Keyence) under a 20 Xcondition of the objective lens, and the results of the measurements are shown in Table 2.
TABLE 2 roughness of dresser working surface
| Numbering | Ra/μm | Rz/μm |
| Example 9 | 0.423 | 4.267 |
| Example 10 | 0.468 | 4.984 |
| Example 11 | 0.325 | 3.725 |
| Comparative example 3 | 0.712 | 6.799 |
| Comparative example 4 | 0.557 | 5.632 |
In Table 2, the roughness of examples 9-11 indicates that the conditioners prepared using the electroplating process of the present invention are flat.
Example 9 compares with comparative examples 3-4 and shows that the higher or lower plating solution temperature has an effect on the roughness of the dresser surface.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (10)
1. An iron plating solution for use in manufacturing a polishing pad dresser, comprising: oxalic acid complex of ferric ions, pH buffering agent, chloride auxiliary reagent, stress remover and wetting agent; the pH of the iron plating solution is 3.0-3.8.
2. The iron plating solution for manufacturing a pad dresser of claim 1, wherein the iron concentration in the iron plating solution is 0.3 to 0.5mol/L;
the concentration of the pH buffering agent is 0.4-0.7mol/L;
the concentration of the chloride auxiliary reagent is 0.2-0.7mol/L;
the concentration of the stress remover is 0.01-0.025mol/L;
the concentration of the wetting agent is 0.35-1.4mmol/L.
3. The iron plating solution for manufacturing a polishing pad conditioner according to claim 1, wherein the oxalic acid complex of ferric ion is one or more of a complex formed by ferric ammonium oxalate, a soluble ferric salt and a complex formed by ammonium oxalate.
4. The iron plating solution for manufacturing a polishing pad conditioner of claim 3 wherein the soluble ferric salt is one or more of ferric chloride, ferric sulfate, ferric sulfamate.
5. The iron plating solution for manufacturing a pad conditioner of claim 3 or 4, wherein the molar ratio of the ammonium oxalate to the soluble ferric salt is at least 3.1.
6. The iron plating solution for manufacturing a polishing pad dresser of claim 1, wherein said pH buffering agent is boric acid;
the chloride auxiliary reagent is one or more of ammonium chloride, manganese chloride and sodium chloride;
the stress remover is one or more of sodium o-benzoylsulfonyl imide, sodium p-toluenesulfonamide and sodium p-toluenesulfinate;
the wetting agent is one or more of sodium dodecyl sulfate and sodium methylene dinaphthalene sulfonate.
7. The method of preparing an iron plating solution for use in manufacturing a polishing pad dresser as claimed in any one of claims 1 to 6, comprising the steps of:
s1, adding a pH buffering agent and a chloride auxiliary reagent into deionized water, heating to 60-80 ℃, stirring until the pH buffering agent and the chloride auxiliary reagent are completely dissolved, and adjusting the pH to 3 to obtain a first solution;
s2, adding an oxalic acid complex of ferric ions into the first solution, and stirring until the oxalic acid complex is completely dissolved to obtain a second solution;
s3, adding a stress remover and a wetting agent into the second solution, then supplementing deionized water to a preset volume, and adjusting the pH value range to 3.0-3.8 to obtain an iron plating solution;
the volume of the deionized water added in the step S1 is 2/3 of the preset volume.
8. The electroplating process of the iron plating solution according to any one of claims 1 to 6 or the iron plating solution prepared by the preparation method according to claim 7, comprising the steps of: using the base body of the trimmer as a cathode and a pure iron plate as an anode, the electroplating temperature is 30-40 ℃, the pH of the iron plating solution is 3.0-3.8, and the current density is 0.5-2.0A/dm 2 。
9. The electroplating process of claim 8, wherein the current waveform is one of direct current, single pulse current, or double pulse current;
when pulse electroplating is adopted, the duty ratio of pulse current is 5% -50%, and the peak current is 1.0-4.0A/dm 2 。
10. A pad dresser prepared by the electroplating process of claim 8, wherein the dresser coating has a roughness Ra of 0.3 to 0.5 μm.
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