CN104818512A - Device and method for preparing magnetically soft alloy continuous films through electric deposition of soluble separated anodes - Google Patents

Abstract

The invention provides a device and a method for preparing magnetically soft alloy continuous films through electric deposition of soluble separated anodes. Annular thin strips plated with titanium nitride on the surfaces of a stainless steel strip and a titanium strip serve as cathodes; soluble monometal anodes are separately arranged in parallel; branch anodes are dissolved to a scale through adjusting the current and the voltage of the branch anodes to achieve the balance between the cathode deposition quantity and the anode dissolution amount; and the content of metal ions in plating liquid is kept stable. The device and the method prevent the addition of a plating liquid supplementation metal ion device, effectively solve the problems of metal ion stability and regenerability of the plating liquid in continuous production, keep the stability of the metal content in continuous alloy plating layers, and are suitable for continuous production of magnetically soft alloy films.

Description

Apparatus and method for preparing continuous film of soft magnetic alloy by electrodeposition of soluble separated anode

technical field

The invention belongs to the field of electrochemical deposition, and in particular relates to a device and a method for preparing a soft magnetic alloy continuous thin film by electrodeposition of a soluble separated anode.

Background technique

Soft magnetic alloy thin film is a magnetic material with low coercive force and high magnetic permeability under weak magnetic field. Soft magnetic materials are easy to magnetize and demagnetize, and are widely used in electrical equipment and electronic equipment, as well as in the field of magnetic field shielding.

The preparation methods of soft magnetic alloy include rolling, magnetron sputtering and electrodeposition, among which the preparation of iron-nickel alloy by electrodeposition is simple, low in cost and easy to operate. However, in the process of continuous electrodeposition of iron-nickel alloy film, the metal ion concentration in the plating solution is reduced due to the continuous deposition of the cathode and the consumption of metal ions in the plating solution, which in turn causes the imbalance of the metal content of the coating, making the continuous strip produced. unstable. The current continuous electrodeposition equipment supplements the reduced metal ions in the plating solution by adding metal ions. U.S. Patents US5360525 and US4076597 have introduced a method of replenishing metal ions, which are obtained by dissolving metals in acid and replenishing metal ions to the plating solution. This method requires a large amount of strong acid to dissolve metals, which is harmful to the environment, products and personal safety. Negative Effects. At the same time, according to the introduction of the Chinese patent CN100564606C metal film continuous electrodeposition device and its method, when the plating solution is circulated and electroplated for a period of time, the metal ions in the plating solution will drop, and the electroplating solution in the electroplating tank will be supplemented with metal by means of different types of metal ion replenishment devices. Ion plating solution, to achieve metal ion concentration balance. However, this method of supplementing metal ions needs to continuously dissolve various metal salts in the liquid replenishing device, the process is complicated and lengthy, and the equipment requirements are high.

Contents of the invention

In order to overcome the technical problems existing in the existing continuous electrodeposition devices, the present invention provides a device and method for preparing soft magnetic alloy continuous films by electrodeposition of soluble separated anodes. The technical scheme adopted is: select the appropriate cathode material, use soluble anodes, separate and arrange the anodes in parallel, adjust the current and voltage of the branch anodes, and then control the dissolution amount of the branch anodes to be equal to the deposition amount of cathode metal ions to achieve cathode deposition. The purpose of maintaining the balance between the amount and the dissolved amount of the anode, keeping the metal ion content of the plating solution stable, and producing a continuous soft magnetic film with excellent performance and stable component content.

A device for preparing a continuous film of soft magnetic alloy by electrodeposition of a soluble separated anode, including an electroplating tank containing an electroplating solution; a circular metal cathode that can be rotated circularly; a soluble anode; a power supply device; a motor transmission device; a circulation device, a filter device; temperature control Device; peeling device; cleaning device; passivation device; drying device; An annular thin strip formed of stainless steel strips and titanium strips combined to form an insulating layer.

Further, in the electrodeposition process, the anode material is any two of pure iron, pure nickel, and pure cobalt. Different metal anodes form separate anodes and are arranged alternately. Each anode forms an independent anode, and different metal anodes are connected in parallel to form a comprehensive anode. ; Separated anodes are controlled by a single power supply or multiple power supplies, and the current and voltage of different branch anodes are adjustable.

Further, it is characterized in that an ion-permeable isolation membrane is arranged between the cathode and the anode, and the membrane is arranged in parallel with the cathode belt; the plating solution is horizontally flowed between the cathode and the ion-permeable isolation membrane by a circulation pump.

The method for preparing a soft magnetic alloy continuous thin film using the device is characterized in that the lower end of the circularly moving titanium nitride cathode is immersed in the plating solution, the parallel branch soluble anode current and voltage are adjusted, and the branch anode is controlled according to the metal ratio of the coating layer. Dissolving, the metal ions are evenly mixed under the action of the ion-permeable isolation membrane and the circulation pump, and a layer of alloy film is deposited on the cathode. The film is stripped, cleaned, passivated, and dried, and then rolled into a material.

According to above-mentioned purpose, the present invention adopts following technical measures:

1. In order to produce a continuous soft magnetic film, it is necessary to be able to easily peel off the electrodeposited layer from the cathode strip, which requires a smooth and clean surface of the cathode strip, good corrosion resistance, and good peelability of the coating. The invention uses an annular stainless steel strip and an annular titanium thin strip with a thickness of 0.05-0.5mm, coats a layer of titanium nitride film with a thickness of 0.0005-0.05mm on the surface, and forms an insulating layer by laminating the back side with an electrically insulating polymer film. The ring-shaped stainless steel and titanium strips are welded end-to-end. There are defects in the welds, and the coating is not easy to peel off. The purpose of titanium nitride plating is to mask the defects of the weld seam of the annular belt, and the second is that the coating on titanium nitride is easier to peel off than the coating on stainless steel and titanium.

2. The soluble anode materials used in the present invention are pure iron, pure nickel, and pure cobalt, and different metal anodes are alternately arranged in the anode tank, and insulating materials are separated between the two anode tanks. At the same time, different metal anodes are connected in parallel, and the dissolution rate of different branch anodes can be controlled by adjusting the current and voltage of the iron anode and nickel anode in the parallel circuit. In order to control the current and voltage of the anode of the parallel branch, two power supply methods are used, one uses a separate power supply, and a current and voltage regulating device is installed on the anode of the parallel branch, including a sliding rheostat and an ammeter; the other directly uses two power supplies Adjust the current and voltage of parallel branch anodes respectively, so that the dissolved amount of the first soluble anode is equal to the amount of metal deposited on the cathode, and the dissolved amount of the second soluble anode is equal to the amount of deposited metal on the cathode.

3. The composition content in the alloy coating is mainly determined by the composition of the plating solution and the process parameters. In order to obtain an iron-nickel alloy coating with an iron content of 5% to 95%, it can be obtained by changing the composition and process parameters of the plating solution. The composition and parameters of the electroplating solution include: nickel sulfate 20-300g/L, ferrous sulfate 5g-120g/L L, 20-60g/L boric acid, sodium citrate 5-50g/L, ascorbic acid 1g-15/L, sodium lauryl sulfate 0.1-0.5g/L, saccharin 1-5g/L, benzenesulfinic acid Sodium 0.1-0.6g/L, butynediol 0.1-0.8g/L, pH 1.5-4.5, temperature 20-65°C, current density 1-100A/dm ² . In order to obtain an alloy film with a stable iron-nickel content ratio in the coating, it is necessary to keep the concentration of each component in the above plating solution constant, which requires that the amount of dissolved iron in the anode is equal to the amount of iron deposited on the cathode, and the amount of dissolved nickel in the anode is equal to the amount of nickel on the cathode. amount of deposition. The current ratio of the parallel branch iron anode to nickel anode ranges from 1:17 to 20:1.

The calculation method of the ratio of the anode current of the parallel branch is as follows:

W _{first soluble anode} - the mass fraction of the first soluble anode metal in the coating

W _{second soluble anode} - the mass fraction of the second soluble anode metal in the coating

R _{the first soluble anode} —the electrochemical equivalent of the first soluble anode

_{RSecond soluble anode} —The electrochemical equivalent of the second soluble anode

4. In order to eliminate the difference in local metal ion concentration of the plating solution caused by the dissolution of alternately arranged different metal anodes, the present invention places an ion-permeable isolation membrane parallel to the cathode band between the cathode and the anode, and the membrane can pass through soluble The metal ions dissolved in the anode and different metal ions are mixed evenly when passing through the ion isolation membrane, and the membrane also has the function of filtering impurities. At the same time, a circulating water pump is used to make the plating solution flow horizontally between the cathode belt and the ion-permeable isolation membrane, so as to eliminate the difference in metal ion concentration and take away the gas generated on the cathode.

Description of drawings

Fig. 1 is the device schematic diagram that is used for the continuous electrodeposition of soft magnetic alloy film provided by the present invention

Figure 2 is a schematic diagram of the electroplating tank

Figure 3 is a schematic diagram of a single power supply separated parallel anode circuit

Figure 4 is a schematic diagram of a dual power supply separated parallel anode circuit

Detailed ways

The present invention is described in detail in conjunction with accompanying drawing and specific embodiment now:

A soft magnetic alloy thin film continuous electrodeposition device, as shown in Figure 1, Figure 2, Figure 3, and Figure 4, wherein 1 is the first supporting conveying roller, 4 is the second supporting conveying roller, and 5 is the third supporting conveying roller Roller, 6 is the fourth support transfer roller, 2 is the graphite cathode conductive roller, 3 is the annular titanium nitride cathode belt, 7 is the electroplating tank, 8 is the electroplating solution, 9 is the water inlet of the plating solution, 10 is the water outlet of the plating solution, 11 is an anode filter, 12 is an ion-permeable isolation membrane, 13 is an anode tank, 14 is a circulating water pump, 15 is a temperature control device, 16 is a filter, 17 is a coating stripping roller, 21 is a coating cleaning and passivation device, Including cleaning solution 18, liquid storage tank 19, passivation solution 20 and supporting rotating roller, 22 is a drying device, 23 is a first pressure guide roller, 24 is a second pressure guide roller, 25 is a third pressure guide roller, 26 is a tension sensor, 27 is a tension controller, 28 is a magnetic powder coupler, 29 is a winding roller, 30 is a graphite conductive plate, 31 is a graphite conductive rod, 32 is the first soluble anode, 33 is the second soluble anode, 34 is the power supply Wire, 35 is an electroplating power supply, and 36 is a current and voltage regulating device.

Referring to Fig. 1, Fig. 2, Fig. 3 and Fig. 4, the electroplating solution is injected into the electroplating tank, the annular cathode is set on the supporting conveying roller as the electrodeposition cathode, and the lower end of the cathode strip is immersed in the electroplating solution to ensure that the lower end of the cathode strip remains horizontal. Put the anode conductive device graphite plate and graphite rod in the anode tank, put the first soluble anode and the second soluble anode, add a filter screen and an ion-permeable isolation membrane on the upper end of the anode, and the graphite conductive roller is close to the ring cathode belt. The upper surface is connected to the negative pole of the power supply, the anode conductive device is connected to the positive pole of the power supply, and the current and voltage regulating device is connected between the positive pole of the power supply and the anode. Turn on the circulating water pump, temperature control device and filter, and the electroplating solution reaches the set temperature after a period of time. Turn on the stepper motor, set parameters, and control the rotation speed of the cathode cycle. Turn on the power supply, adjust the current and voltage of the iron anode and nickel anode with the current and voltage regulating device, and deposit a layer of alloy coating on the cathode. The drying device obtains a dry and clean coating, and finally controls the tension of the film to be constant through the tension control system, including pressure guide rollers, tension sensors and tension controllers, and winds the film on the winding device composed of magnetic powder coupler and winding roller. The ring-shaped cathode belt circulates, the soluble anode continuously dissolves and replenishes metal ions, and the coating layer is continuously peeled off and curled into a material, thus forming a continuous soft magnetic alloy thin film strip.

The present invention uses an annular stainless steel thin strip and an annular titanium thin strip with a thickness of 0.05-0.5mm, and coats a layer of titanium nitride film with a thickness of 0.0005-0.05mm on the surface, and the back side is bonded with an electrically insulating polymer film to form an insulating layer. The purpose of titanium nitride is to cover the welding seam of the endless belt and make it easier to peel off the coating. Part of the supporting guide roller will be immersed in the plating solution, which requires that the guide roller does not undergo chemical corrosion and electrochemical reaction with the plating solution, and under the condition of power on, Endless metal belt can generate heat, and this just requires guide roller to have certain heat resistance, the polytetrafluoroethylene that the material of making guide roller among the present invention uses. The stepper motor is connected to a supporting rotating roller supporting the annular cathode.

Use a graphite roller with good conductivity as the cathode conductive medium. The position of the graphite roller can be adjusted up and down to ensure that the surface of the graphite roller is closely attached to the upper surface of the cathode belt. The surface of the graphite roller is polished so that the cathode belt will not be scratched when relative movement occurs. , A carbon brush is added at one end of the graphite roller, and the negative electrode of the power supply is connected to the carbon brush to energize the cathode.

The anode conductive device is composed of a graphite plate and a graphite rod. The graphite rod is connected to the graphite plate at one end to ensure good electrical conductivity. The other end extends out of the plating tank to connect with the positive electrode of the power supply. The soluble first anode and the second anode are alternately arranged on the graphite plate. Immerse in the plating solution.

In order to prevent the impurities produced by the dissolution of the anode from entering the coating, a polyester filter is added between the anode and cathode, and a filter is added to the circulation system to filter the plating solution, and the filter device is cleaned regularly. Add a temperature control device in the circulation system to keep the temperature of the plating solution constant, add a heater and a thermocouple in a liquid storage tank, connect the heater and thermocouple to the temperature controller, set and adjust the temperature value on the temperature controller .

The distance between the cathode and anode can be adjusted between 5mm and 100mm. Due to the dissolution of the soluble anode, there are local differences in the concentration of metal ions in the plating solution. An ion-permeable isolation membrane is added between the cathode and the anode, and different metal ions pass through the ion-permeable separator. Mix well while isolating the membrane.

The circulating water pump makes the plating solution flow horizontally between the cathode and the anode, and the liquid flow direction is opposite to the movement direction of the annular cathode, increasing the relative movement speed of the plating solution and the cathode. Eliminate the concentration difference of the plating solution and take away the gas generated on the cathode at the same time. A protective film is formed on the surface, and the drying device is used to dry the liquid remaining on the surface of the coating.

The winding speed of the coil is controlled by adjusting the parameters of the stepping motor. As the thickness of the coil increases, the pulling tension of the coil increases. If the tension is too high, the film will be torn. This invention uses a set of tension control system, including a tension sensing device. , tension controller, magnetic powder coupler, the alloy film passes through the tension sensing device, the tension change is reflected on the tension controller, the tension controller changes the current and acts on the magnetic powder coupler connected to the winding roller, the current changes, the magnetic powder coupler The torque changes, thereby changing the winding speed, and the winding roller curls into a material.

Example:

Electroplating solution composition: 78g/L nickel sulfate. 9g/L ferrous sulfate, 40g/L boric acid, 20g/L sodium citrate, 5g/L ascorbic acid, 0.2g/L sodium lauryl sulfate, 3g/L saccharin, 0.3g/L sodium benzenesulfinate L, butynediol 0.5g/L

(1) Preparation of electroplating iron-nickel alloy solution

① Add about 70% volume of deionized water into a clean plating tank with a capacity of 8L, and heat it to 55°C.

② Add the calculated amount of nickel sulfate and sodium chloride and stir to dissolve.

③In a separate container, dissolve the calculated amount of boric acid with deionized water above 90°C, and dissolve every kilogram of boric acid with 4-6kg of deionized water.

④ Add the calculated amount of sodium citrate and stir to dissolve.

⑤ Add the calculated amount of ferrous sulfate and stir to dissolve.

⑥Add the calculated amount of saccharin, ascorbic acid, sodium benzenesulfinate, butynediol, stir to dissolve, and add deionized water to the required volume.

⑦ Adjust the pH value to 2.5 with 5% dilute sulfuric acid.

(2) Put the ring-shaped titanium nitride cathode with a width of 50mm on the supporting rotating roller, install the graphite guide roller close to the outer surface of the cathode, put the anode conductive device into the anode groove, the length, width and thickness are 100mm*50mm*10mm Soluble iron anodes and nickel anodes are alternately arranged on the anode conductive device, and the distance between cathode and anode is 35mm.

(3) Turn on the circulating water pump and adjust the flow rate of the water pump to 13L/min; turn on the temperature control device and adjust the temperature to 55°C; turn on the filter device. After a while, the plating solution reached 55°C.

(4) Turn on the high-frequency electroplating power supply, set the cathode current density to 3.5A/dm ² , and adjust the current ratio of the iron anode to the nickel anode to 1:5.5. Static electroplating for a period of time, so that the coating can be peeled off.

(5) Connect the stepper motor with the support roller, turn on the motor, and set the parameters so that the ring cathode rotates at a speed of 2m/h.

(6) When the coating reaches the peeling roller, the coating is peeled off, and the coating is cleaned, passivated, and dried to obtain a dry and clean coating. Finally, the winding speed is adjusted by the tension controller device, and the material is wound on the winding device. .

By adopting the method of the present invention for dissolving and separating anode electrodeposited soft magnetic alloy continuous films, an alloy continuous film containing 85% nickel is prepared, the width of the alloy film is 50 mm, the thickness is 20 μm, the saturation magnetization is 0.7 T, and the hardness is 460 Hv.

Claims (4)

1. A device for preparing a continuous thin film of soft magnetic alloy by electrodeposition of a soluble separated anode, comprising an electroplating tank for containing electroplating solution; a circular metal cathode that can be rotated circularly; a soluble anode; a power supply device; a motor transmission device; a circulation device and a filter device; Temperature control device; Stripping device; Cleaning device; Passivation device; Drying device; The thin film is bonded to the stainless steel belt forming the insulating layer, and the annular thin belt formed by the titanium belt. 2. The device according to claim 1, characterized in that in the electrodeposition process, the anode material is any two of pure iron, pure nickel, and pure cobalt, and different metal anodes form separate anodes, arranged alternately, and each anode forms An independent anode, different metal anodes are connected in parallel to form a comprehensive anode; separate anodes are controlled by a single power supply or multiple power supplies, and the current and voltage of different branch anodes are adjustable. 3. The device according to claim 1 or 2, characterized in that an ion-permeable isolation membrane is arranged between the cathode and the anode, and the membrane is arranged in parallel with the cathode belt; the plating solution is separated between the cathode and the ion-permeable through a circulating pump. Horizontal flow between separator membranes. 4. A method utilizing the device described in claim 2 or 3 to prepare a continuous thin film of soft magnetic alloy is characterized in that the annular titanium nitride cathode lower end of the cyclical movement is immersed in the plating solution, and the parallel branch soluble anode current, voltage are adjusted , control the branch anode to dissolve according to the metal ratio of the coating, the metal ions are mixed evenly under the action of the ion-permeable isolation membrane and the circulating pump, and a layer of alloy film is deposited on the cathode, and the film is rewound after stripping, cleaning, passivation, and drying Become useful.