CN112626577B - Preparation method of quartz crystal electrode film - Google Patents

Preparation method of quartz crystal electrode film Download PDF

Info

Publication number
CN112626577B
CN112626577B CN202011392217.3A CN202011392217A CN112626577B CN 112626577 B CN112626577 B CN 112626577B CN 202011392217 A CN202011392217 A CN 202011392217A CN 112626577 B CN112626577 B CN 112626577B
Authority
CN
China
Prior art keywords
electroplating
plating
nickel
crystal oscillator
vacuum coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011392217.3A
Other languages
Chinese (zh)
Other versions
CN112626577A (en
Inventor
朱玉琴
罗来正
何建新
王成章
李佳蒙
张凯
封先河
黄朝志
吴帅
舒畅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
No 59 Research Institute of China Ordnance Industry
Original Assignee
No 59 Research Institute of China Ordnance Industry
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by No 59 Research Institute of China Ordnance Industry filed Critical No 59 Research Institute of China Ordnance Industry
Priority to CN202011392217.3A priority Critical patent/CN112626577B/en
Publication of CN112626577A publication Critical patent/CN112626577A/en
Application granted granted Critical
Publication of CN112626577B publication Critical patent/CN112626577B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated

Abstract

The invention provides a preparation method of a quartz crystal electrode film, which comprises the following steps: a) Purifying and activating the vacuum coating of the crystal oscillator; b) Pre-plating the vacuum coating after purification and activation in the step A) by adopting a nickel pre-plating electroplating solution to obtain a pre-nickel plating layer; c) Carrying out forward and reverse current electroplating on the surface of the nickel preplating layer by using a metal plating solution to obtain a crystal oscillator electroplating thickness layer; the ratio of the time of the forward electroplating to the time of the reverse electroplating is (5-10): 1, the ratio of the current density of the forward electroplating to the reverse electroplating is (3-10): 1, the current density of the forward electroplating is 1-5A/dm 2 . The method can fully purify and activate the surface of the vacuum coating, does not corrode the substrate, can obtain a coating with good bonding force and uniform surface on the surface of the crystal oscillator, and meets the subsequent test requirements.

Description

Preparation method of quartz crystal electrode film
Technical Field
The invention belongs to the technical field of metal surface treatment, and particularly relates to a preparation method of a quartz crystal electrode film.
Background
The crystal oscillator is called a crystal oscillator (Crystal Oscillators) and is used for generating an original clock frequency, and the crystal oscillator becomes various bus frequencies in a computer after being amplified or reduced by a frequency generator. The crystal plate is also called a frequency plate, is a main body part of the crystal oscillator, and needs to be subjected to film coating treatment for adjusting the frequency of the crystal plate and simultaneously has a conductive function to form a magnetic field when the crystal oscillator is produced. At present, a layer of silver, gold and platinum films are mainly formed on the surface of a crystal face in a vacuum coating mode, and the crystal oscillator prepared by the film cannot meet the application requirements under severe conditions such as ocean, aviation, aerospace and the like due to the fact that the film is thinner. In order to improve the reliability and adapt to the severe service environment, a thick plating layer is required to be electroplated on the surface of the vacuum plating film.
The crystal oscillator matrix is usually lanthanum silicate crystal or silicon dioxide crystal, is physically combined with a vacuum plated silver, gold and platinum film, has a thin film layer, and can lead to the falling of a thinner vacuum plating film if pretreatment is carried out by strong acid and strong alkali before thick film plating or plating is directly carried out by high current; and the poor binding force between the vacuum plating film and the subsequent plating layer can be caused by the weak pretreatment.
Therefore, a reliable crystal oscillator vacuum coating thickening electroplating method is found, so that a layer of coating with good binding force and uniform thickness is obtained on the surface of the crystal oscillator, and the method is necessary.
Disclosure of Invention
The invention aims to provide a preparation method of a quartz crystal electrode film, which can prepare an electroplating thickness layer with good binding force and uniform thickness on the surface of a vacuum plating layer.
The invention provides a preparation method of a quartz crystal electrode film, which comprises the following steps:
a) Purifying and activating the vacuum coating of the crystal oscillator;
b) Pre-plating the vacuum coating after purification and activation in the step A) by adopting a nickel pre-plating electroplating solution to obtain a pre-nickel plating layer;
c) Carrying out forward and reverse current electroplating on the surface of the nickel preplating layer by using a metal plating solution to obtain a crystal oscillator electroplating thick plating layer;
the ratio of the time of the forward electroplating to the time of the reverse electroplating is (5-10): 1, the ratio of the current density of the forward electroplating to the reverse electroplating is (3-10): 1, wherein the current density of the forward electroplating is 1-5A/dm 2 。
Preferably, the nickel preplating electroplating solution comprises the following components:
nickel sulfamate: 400-500 ml/L, nickel chloride: 5-15 g/L, boric acid: 40-50 g/L, softening agent: 1-2 ml/L;
the pH value of the nickel preplating electroplating solution is 4.0-4.5; the preplating temperature is 50-60 ℃.
Preferably, the preplating current density is 1-5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pre-plating time is 1-10 min.
Preferably, the current is gradually changed from 0A to the specified current within 1-3 min, and the pre-plating potential is gradually changed from 0V to the specified potential within 1-3 min.
Preferably, the metal in the metal plating solution is one or more of nickel, copper, tin alloy, zinc alloy, silver, chromium and gold.
Preferably, the time of forward electroplating is 5-20 s; and C), electroplating for 10-50 min.
Preferably, the purifying and activating in the step A) is to sequentially remove oil, activate an activating agent and remove a film on the vacuum plating film of the crystal oscillator;
the activating agent comprises 10-20 g/L sulfamic acid, 5-10 g/L citric acid and 0.5-1 g/L corrosion inhibitor.
Preferably, the activation temperature is 30-40 ℃; the activation time is 0.5-5 min.
Preferably, after the step C), the plating layer is protected with an antioxidant protective agent.
Preferably, the vacuum plating film of the crystal oscillator is a silver, gold or platinum film with the thickness of 0.1-0.4 mu m.
The invention provides a preparation method of a quartz crystal electrode film, which comprises the following steps: a) Purifying and activating the vacuum coating of the crystal oscillator; b) Pre-plating the vacuum coating after purification and activation in the step A) by adopting a nickel pre-plating electroplating solution to obtain a pre-nickel plating layer; c) Carrying out forward and reverse current electroplating on the surface of the nickel preplating layer by using a metal plating solution to obtain a crystal oscillator electroplating thickness layer; the ratio of the time of the forward electroplating to the time of the reverse electroplating is (5-10): 1, the ratio of the current density of the forward electroplating to the reverse electroplating is (3-10): 1, wherein the current density of the forward electroplating is 1-5A/dm 2 . The nickel plating layer is performed before electroplating, so that a good bottom layer can be provided for a subsequent electroplated layer, and the binding force of the whole deposited layer can be improved; the reverse current in the electroplating process can weaken the coarse crystallization condition, so that the crystallization is finer and the crystallization layer is more uniform. The method can fully purify and activate the surface of the vacuum coating, does not corrode the substrate, can obtain a coating with good bonding force and uniform surface on the surface of the crystal oscillator, and meets the subsequent test requirements.
Detailed Description
The invention provides a preparation method of a quartz crystal electrode film, which comprises the following steps:
a) Purifying and activating the vacuum coating of the crystal oscillator;
b) Pre-plating the vacuum coating after purification and activation in the step A) by adopting a nickel pre-plating electroplating solution to obtain a pre-nickel plating layer;
c) Carrying out forward and reverse current electroplating on the surface of the nickel preplating layer by using a metal plating solution to obtain a crystal oscillator electroplating thickness layer;
the ratio of the time of the forward electroplating to the time of the reverse electroplating is (5-10): 1, the ratio of the current density of the forward electroplating to the reverse electroplating is (3-10): 1, wherein the current density of the forward electroplating is 1-5A/dm 2 。
In the invention, a vacuum plating layer is arranged on the surface of the crystal oscillator, and the material of the vacuum plating layer can be silver plating film, gold plating film or platinum plating film, and the vacuum plating layer is thinner and has a thickness of 0.1-0.4 mu m of silver, gold or platinum film. The invention is to electroplate on the surface of the vacuum plating layer to form a protective thick plating layer.
The invention firstly purifies and activates the vacuum coating, preferably, the vacuum coating is sequentially deoiled, activated and de-molded;
the invention preferably immerses the crystal oscillator with the vacuum coating in the deoiling working solution to deoil so as to ensure that the dirt on the surface of the crystal oscillator vacuum coating is cleaned.
In the invention, the oil removing working fluid comprises a neutral oil removing agent, and the type of the neutral oil removing agent is not particularly limited, for example, a neutral oil removing agent of BEC-VI type can be adopted; the concentration of the neutral degreasing agent is preferably 40-60 g/L, more preferably 40-50 g/L, and the degreasing temperature is preferably 50-60 ℃; the oil removal time is preferably 5-10 min, more preferably 6-8 min.
After the oil removal is finished, the vacuum coating after the oil removal is activated, and the oxide on the surface of the vacuum coating is removed to provide an active surface.
In the present invention, the activation is used for the activation
The chemical agent is in a solution state and comprises the following components:
10-20 g/L sulfamic acid, preferably 13-18 g/L sulfamic acid, more preferably 15-16 g/L sulfamic acid; 5-10 g/L of citric acid, preferably 8-10 g/L; 0.5-1 g/L of corrosion inhibitor, preferably 0.5-0.8 g/L;
the activation temperature is preferably 30-40 ℃, more preferably 30-35 ℃; the activation time is preferably 1 to 10min, more preferably 2 to 8min, and most preferably 2 to 5min.
After the activation is completed, the activated vacuum coating is demoulded, and the demould is to remove the metal dust remained on the surface of the crystal oscillator vacuum film by adopting ultrasonic waves, so as to obtain the purified and activated vacuum coating.
The invention adopts the nickel preplating electroplating solution to preplate the nickel layer on the vacuum coating after purification and activation.
The nickel preplating electroplating solution is a low-stress nickel sulfamate system and comprises the following components:
nickel sulfamate: 400-500 ml/L, nickel chloride: 5-15 g/L, boric acid: 40-50 g/L, softening agent: 1-2 ml/L;
preferably, the composition comprises the following components:
nickel sulfamate: 400-450 ml/L, nickel chloride: 10-15 g/L, boric acid: 40-45 g/L, softening agent: 1 to 1.5ml/L;
the softener is preferably a softener model BN-2015 supplied by the martial arts materials protection institute.
The pre-plating in the invention adopts a soft start mode, and in the time of 1-3 min, the potential is gradually changed from 0V to the designated potential, and the current is gradually changed from 0A to the designated current; the electric potential in the pre-plating is preferably 0.5 to 2v, more preferably 1 to 1.5v, most preferably 1.2 to 1.3v, and the current in the pre-plating is preferably 0.01 to 0.3a, more preferably 0.05 to 0.25A, most preferably 0.1 to 0.2a, and specifically may be 0.15A.
In the present invention, the pH value of the nickel preplating plating solution is preferably 4.0 to 4.5, and the preplating temperature is preferably 50 to 60 ℃, more preferably 55 ℃.
The current density of the preplating is preferably 1-5A/dm 2 More preferably 2 to 4A/dm 2 Most preferably 2 to 3A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the Specifically, in an embodiment of the present invention, it may be 2A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pre-plating time is preferably 1-10 min, more preferably 3-8 min, and most preferably 5-6 min.
After the preplating is finished, the invention continues to electroplate on the nickel layer, wherein the electroplated metal is preferably one or more of nickel, copper, tin alloy, zinc alloy, silver, chromium and gold; the plating solution containing different metal ions can be selected according to actual requirements, and the plating solution can be prepared from plating solution components known in the art, such as nickel plating, and can be prepared from nickel preplating plating solution; the plating can also be carried out by adopting a nickel sulfate system, the nickel sulfate is 250g/L, the nickel chloride is 45g/L, the boric acid is 45g/L, the BN-2015 softener is 1.5ml/L, and the pH value is 4.2;
electroplating tin by adopting a weak acid tin plating system, wherein tin ions are 15g/L,500C complexing agent is 400g/L,500B conductive salt is 150g/L,500A additive is 30g/L, and the pH value is 4.4;
electroplating copper, namely adopting an acid copper plating system, 200g/L of copper sulfate, 60g/L of sulfuric acid, 80ppm of chloride ions, a small amount of acid copper additive and 25 ℃;
electrotinning, namely adopting an acid tinning process, wherein tin ions are 15g/L, methanesulfonic acid is 150g/L, BSn-1000 additive is 40ml/L, and the temperature is 20 ℃.
In order to improve the uniformity and compactness of the plating layer, the electroplating mode adopts forward and reverse current to carry out electroplating, wherein the time of forward electroplating is preferably 5-20 s, more preferably 10-15 s, and in particular, in the embodiment of the invention, the time ratio of forward electroplating to reverse electroplating is preferably (5-10): 1, more preferably (7 to 9): 1, in particular, may be 10:1 or 7:1 in embodiments of the invention.
The current density of the forward electroplating is preferably 1-5A/dm 2 More preferably 2 to 4A/dm 2 Specifically, in an embodiment of the present invention, it may be 1A/dm 2 、2A/dm 2 Or 3A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The ratio of the current density of the forward electroplating to the reverse electroplating is (3-10): 1, more preferably (4 to 9): 1, in particular, in an embodiment of the present invention, may be 4: 1. 5:1 or 6:1.
In the invention, the time of the electroplating can be regulated according to the specific required thickness of the plating layer, preferably, the total time of the electroplating is preferably 10-50 min, more preferably 20-40 min, and most preferably 20-30 min.
After the electroplated thick coating is obtained, the invention adopts the antioxidation protective agent to protect the electroplated thick coating so as to meet the requirements of crystal oscillator brazing, corrosion resistance and the like. Different types of antioxidant protective agents can be adopted for different plating types, and the specific types of the antioxidant protective agents can be the antioxidant protective agents commonly used by a person skilled in the art.
The invention provides a preparation method of a quartz crystal electrode film, which comprises the following steps: a) Purifying and activating the vacuum coating of the crystal oscillator;b) Pre-plating the vacuum coating after purification and activation in the step A) by adopting a nickel pre-plating electroplating solution to obtain a pre-nickel plating layer; c) Carrying out forward and reverse current electroplating on the surface of the nickel preplating layer by using a metal plating solution to obtain a crystal oscillator electroplating thickness layer; the ratio of the time of the forward electroplating to the time of the reverse electroplating is (5-10): 1, the ratio of the current density of the forward electroplating to the reverse electroplating is (3-10): 1, wherein the current density of the forward electroplating is 1-5A/dm 2 . The nickel plating layer is performed before electroplating, so that a good bottom layer can be provided for a subsequent electroplated layer, and the binding force of the whole deposited layer can be improved; the reverse current in the electroplating process can weaken the coarse crystallization condition, so that the crystallization is finer and the crystallization layer is more uniform. The method can fully purify and activate the surface of the vacuum coating, does not corrode the substrate, can obtain a coating with good bonding force and uniform surface on the surface of the crystal oscillator, and meets the subsequent test requirements.
In order to further illustrate the present invention, the following examples are provided to describe in detail a method for preparing a quartz crystal electrode thin film according to the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Deoiling: the BEC-VI neutral degreasing agent is adopted for 50g/L, the temperature is 40 ℃, and the crystal oscillator is soaked in the degreasing agent working solution for 5min, so that the dirt on the vacuum coating surface of the crystal oscillator is ensured to be cleaned;
(2) Activating: activating with sulfamic acid 15g/L, citric acid 10g/L and corrosion inhibitor 0.5g/L solution at 30deg.C for 2min;
(3) Removing the film: ultrasonic water washing is adopted for 50S, so that the removal of metal dust remained on the surface of the crystal oscillator vacuum film is ensured;
(4) Pre-plating: adopts a low-stress nickel sulfamate system, and plating solution process parameters are as follows: 400ml/L of nickel sulfamate, 15g/L of nickel chloride, 45g/L of boric acid, 1.5ml/L of BN-2015 softener, pH value of 4.2, temperature of 55 ℃ and current density of 2A/dm2; the electroplating mode adopts a soft start mode, namely the time is 3min, the current is gradually changed from 0A to the specified current, and then the electroplating is continued for 5min for preplating.
(5) Electroplating nickel: adopts a low-stress nickel sulfamate system, and plating solution process parameters are as follows: 400ml/L of nickel sulfamate, 15g/L of nickel chloride, 45g/L of boric acid, 1.5ml/L of BN-2015 softener, pH value of 4.2, temperature of 55 ℃, forward current density of 2A/dm2, reverse current density of 0.5A/dm2, forward 10S and reverse 1S in one cycle, and accumulated electroplating for 20min;
(6) Nickel protection: adopting BN-96 nickel protective agent to protect, the concentration is 5ml/L, the temperature is 50 ℃, and the time is 1min.
Example 2
(1) Deoiling: adopting BEC-VI neutral degreasing agent 40g/L, soaking the crystal oscillator in the degreasing agent working solution for 5min at 50 ℃ to ensure that the dirt on the vacuum coating surface of the crystal oscillator is cleaned;
(2) Activating: activating with sulfamic acid 15g/L, citric acid 10g/L and corrosion inhibitor 0.5g/L solution at 30deg.C for 2min;
(3) Removing the film: ultrasonic water washing is adopted for 50S, so that the removal of metal dust remained on the surface of the crystal oscillator vacuum film is ensured;
(4) Pre-plating: adopts a low-stress nickel sulfamate system, and plating solution process parameters are as follows: 400ml/L nickel sulfamate, 15g/L nickel chloride, 45g/L boric acid, 1.5ml/L BN-2015 softener, pH value of 4.2, temperature of 55 ℃ and current density of 2A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The electroplating mode adopts a soft start mode, namely the time is 3min, the current is gradually changed from 0A to the specified current, and then the electroplating is continued for 5min for preplating.
(5) Electroplating tin: adopts a weak acid tinning system, and plating solution process parameters are as follows: 15g/L of tin ion, 400g/L of 500C complexing agent, 150g/L of 500B conductive salt, 30g/L of 500A additive, pH value of 4.4, temperature of 30 ℃ and forward current density of 1A/dm 2 Reverse current density 0.2. 0.2A/dm 2 One cycle is 7S forward and 1S backward, and electroplating is carried out for 20min in an accumulated mode;
(6) Tin protection: the BSn-2017 acidic tin protective agent is adopted for protection, the concentration is 10ml/L, the temperature is 30 ℃, and the time is 1min.
Example 3
Deoiling: adopting BEC-VI neutral degreasing agent to 30g/L, soaking the crystal oscillator in the degreasing agent working solution for 5min at the temperature of 60 ℃ to ensure that the dirt on the vacuum coating surface of the crystal oscillator is cleaned;
(2) Activating: activating with sulfamic acid 15g/L, citric acid 10g/L and corrosion inhibitor 0.5g/L solution at 30deg.C for 2min;
(3) Removing the film: ultrasonic water washing is adopted for 50S, so that the removal of metal dust remained on the surface of the crystal oscillator vacuum film is ensured;
(4) Pre-plating: adopts a low-stress nickel sulfamate system, and plating solution process parameters are as follows: 400ml/L nickel sulfamate, 15g/L nickel chloride, 45g/L boric acid, 1.5ml/L BN-2015 softener, pH value of 4.2, temperature of 55 ℃ and current density of 2A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The electroplating mode adopts a soft start mode, namely the time is 3min, the current is gradually changed from 0A to the specified current, and then the electroplating is continued for 5min for preplating.
(5) Electroplating copper: adopting an acidic copper plating system, and plating solution process parameters: 200g/L copper sulfate, 60g/L sulfuric acid, 80ppm chloride ion, a small amount of acid copper additive, 25 ℃ temperature and 3A/dm forward current density 2 Reverse current density 0.5A/dm 2 One cycle is forward 10S, reverse 1S, and accumulated electroplating is carried out for 15min;
(6) Copper protection: adopting BCu-58 copper protective agent for protection, wherein the concentration is 10ml/L, the temperature is 50 ℃, and the time is 1min.
Example 4
Other contents are the same as in example 1, wherein the nickel sulfate system is adopted in the nickel plating process, and the technological parameters of the plating solution are as follows: 250g/L nickel sulfate, 45g/L nickel chloride, 45g/L boric acid, 1.5ml/L BN-2015 softener, pH value of 4.2, temperature of 55 ℃ and forward current density of 2A/dm 2 Reverse current density 0.5A/dm 2 One cycle is forward 10S and reverse 1S, and electroplating is accumulated for 20min.
Example 5
Otherwise, the method is the same as in the example 2, wherein the electrotinning adopts an acid tinning process, and the technological parameters of plating solution are as follows: 15g/L of tin ions, 150g/L of methylsulfonic acid, 40ml/L of BSn-1000 additive, 20 ℃ of temperature and 1A/dm of forward current density 2 Reverse current density 0.2. 0.2A/dm 2 One cycle is 7S forward and 1S backward, and electroplating is accumulated for 20min.
Example 6
Other matters are the same as in example 3, wherein the copper electroplating process adopts a cyanide-free alkaline copper plating process, and the technological parameters of plating solution are as follows: copper ion 10g/L, BCU-12 complexing agent 500ml/L, temperature 50 ℃, forward current density 1A/dm 2 Reverse current density 0.2. 0.2A/dm 2 One cycle is forward 10S and reverse 1S, and electroplating is accumulated for 30min.
Binding force and corrosion resistance experiments were performed on the coatings in the examples, and the results are shown in the following table:
TABLE 1 Performance test of the coatings in the examples of the invention
Figure SMS_1
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. The preparation method of the quartz crystal electrode film comprises the following steps:
a) Purifying and activating the vacuum coating of the crystal oscillator; the vacuum coating of the crystal oscillator is a silver, gold or platinum film with the thickness of 0.1-0.4 mu m;
b) Pre-plating the vacuum coating after purification and activation in the step A) by adopting a nickel pre-plating electroplating solution to obtain a pre-nickel plating layer;
c) Carrying out forward and reverse current electroplating on the surface of the nickel preplating layer by using a metal plating solution to obtain a crystal oscillator electroplating thick plating layer;
the metal in the metal plating solution is one or more of nickel, copper and tin; the ratio of the time of forward electroplating to the time of reverse electroplating is (5-10): 1, the ratio of the current density of the forward electroplating to the reverse electroplating is (3-10): 1, wherein the current density of the forward electroplating is 1-5A/dm 2 。
2. The method of claim 1, wherein the nickel preplating plating solution comprises the following components:
nickel sulfamate: 400-500 ml/L, nickel chloride: 5-15 g/L, boric acid: 40-50 g/L, softening agent: 1-2 ml/L;
the pH value of the nickel preplating electroplating solution is 4.0-4.5; the preplating temperature is 50-60 ℃.
3. The method according to claim 1, wherein the preplating current density is 1 to 5A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the The pre-plating time is 1-10 min.
4. The method according to claim 1, wherein the current is changed stepwise from 0A to a prescribed current within 1 to 3min, and the pre-plating potential is changed stepwise from 0V to a prescribed potential within 1 to 3 min.
5. The method of claim 1, wherein the forward plating time is 5-20 s; and C), electroplating for 10-50 min.
6. The method according to claim 1, wherein the purifying and activating in the step a) is sequentially performing degreasing, activating with an activating agent and stripping on the vacuum coating of the crystal oscillator;
the activating agent comprises 10-20 g/L sulfamic acid, 5-10 g/L citric acid and 0.5-1 g/L corrosion inhibitor.
7. The method according to claim 1, wherein the activation temperature is 30 to 40 ℃; the activation time is 0.5-5 min.
8. The method according to claim 1, wherein the plating layer is protected with an antioxidant protective agent after the step C).
CN202011392217.3A 2020-12-01 2020-12-01 Preparation method of quartz crystal electrode film Active CN112626577B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011392217.3A CN112626577B (en) 2020-12-01 2020-12-01 Preparation method of quartz crystal electrode film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011392217.3A CN112626577B (en) 2020-12-01 2020-12-01 Preparation method of quartz crystal electrode film

Publications (2)

Publication Number Publication Date
CN112626577A CN112626577A (en) 2021-04-09
CN112626577B true CN112626577B (en) 2023-05-19

Family

ID=75307809

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011392217.3A Active CN112626577B (en) 2020-12-01 2020-12-01 Preparation method of quartz crystal electrode film

Country Status (1)

Country Link
CN (1) CN112626577B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115216735B (en) * 2022-06-09 2023-07-25 广西自贸区睿显科技有限公司 Quartz crystal oscillator piece deposition monitoring device and method in OLED production process

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103806064A (en) * 2012-11-08 2014-05-21 无锡新三洲特钢有限公司 Aluminum alloy surface imitation gold plating technology
CN105220194A (en) * 2015-10-16 2016-01-06 宁波韵升磁体元件技术有限公司 A kind of method for electroplating nickel of neodymium iron boron thin slice magnet steel product
CN105586615A (en) * 2016-01-21 2016-05-18 华南理工大学 Method for pulse pre-nickeling of surface of magnesium alloy
CN109338432A (en) * 2018-11-27 2019-02-15 东莞市慧泽凌化工科技有限公司 A kind of electroplating technology of stainless steel and aluminium alloy compound part

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000046811A (en) * 1998-07-30 2000-02-18 Hitachi Constr Mach Co Ltd Ultrasonic probe
EP2803756A1 (en) * 2013-05-13 2014-11-19 Atotech Deutschland GmbH Method for depositing thick copper layers onto sintered materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103806064A (en) * 2012-11-08 2014-05-21 无锡新三洲特钢有限公司 Aluminum alloy surface imitation gold plating technology
CN105220194A (en) * 2015-10-16 2016-01-06 宁波韵升磁体元件技术有限公司 A kind of method for electroplating nickel of neodymium iron boron thin slice magnet steel product
CN105586615A (en) * 2016-01-21 2016-05-18 华南理工大学 Method for pulse pre-nickeling of surface of magnesium alloy
CN109338432A (en) * 2018-11-27 2019-02-15 东莞市慧泽凌化工科技有限公司 A kind of electroplating technology of stainless steel and aluminium alloy compound part

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"镁合金涂镀预处理及膜层结构与性能研究";李亚丽;《中国优秀硕士学位论文全文数据库 工程科技I辑》;第B022-458页 *

Also Published As

Publication number Publication date
CN112626577A (en) 2021-04-09

Similar Documents

Publication Publication Date Title
US4232060A (en) Method of preparing substrate surface for electroless plating and products produced thereby
CA1127994A (en) Electroplating aluminium
CN101618616B (en) Zinc alloy product and preparation method thereof
US3726771A (en) Process for chemical nickel plating of aluminum and its alloys
JP2671612B2 (en) Zinc-based direct electroplating method for aluminum strip
CN112626577B (en) Preparation method of quartz crystal electrode film
CN104562112A (en) Lead brass silver plating process
US4670312A (en) Method for preparing aluminum for plating
JP5247142B2 (en) Silver plating method
CN110552030B (en) Copper-aluminum electric contact and preparation method thereof
US4474838A (en) Electroless direct deposition of gold on metallized ceramics
CN111636077A (en) Process for preventing ceramic chip from being plated with nickel or gold by creeping plating
CN116065208A (en) Preparation method of variable-frequency power ultrasonic electro-deposition nano nickel-based composite layer on magnesium alloy surface
CN113774366B (en) Aluminum alloy surface plating process
CN112680757B (en) Electroplating nickel plating process of electrode
US2662054A (en) Method of electrodepositing chromium directly on aluminum
US3505181A (en) Treatment of titanium surfaces
JPH1018055A (en) Method for metallizing surface of plastic by plating
US2966448A (en) Methods of electroplating aluminum and alloys thereof
JP2006219724A (en) Electroless plating process
CN111826695A (en) Electroplating process for LED lead frame
JPS61166986A (en) Metal plated amorphous alloy
CN1250772C (en) Electroplating pretreatment solution and electroplating pretreatment method
US4363705A (en) Passivating and silver removal method
KR100528638B1 (en) Plating Process of Nickel on Magnesium Alloy

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant