CN114314773A - Preparation method of self-coupling copper alloy antifouling anode - Google Patents
Preparation method of self-coupling copper alloy antifouling anode Download PDFInfo
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- CN114314773A CN114314773A CN202210057686.2A CN202210057686A CN114314773A CN 114314773 A CN114314773 A CN 114314773A CN 202210057686 A CN202210057686 A CN 202210057686A CN 114314773 A CN114314773 A CN 114314773A
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Abstract
The invention belongs to the technical field of anode preparation, and particularly relates to a preparation method of a self-coupling copper alloy antifouling anode, wherein titanium or a titanium alloy is selected to accelerate corrosion of copper or the copper alloy, and in order to ensure galvanic activity of the titanium or the titanium alloy, oxide anode activation treatment is carried out on the surface of the titanium or the titanium alloy; the principle is scientific and reliable, the mode of combining activated titanium powder and microcosmic galvanic corrosion is adopted, the activation effect of the galvanic corrosion is maximized, and the prepared self-coupling copper alloy antifouling anode is arranged at each part or stage of a seawater pipeline in a flange or pipe section mode.
Description
The technical field is as follows:
the invention belongs to the technical field of anode preparation, and particularly relates to a preparation method of an antifouling self-coupling copper alloy anode, which is applied to marine environment corrosion and fouling treatment.
Background art:
the seawater pipeline system is a main way for ship fire fighting, power, air conditioning and domestic sewage delivery, and plays an important role. However, the seawater pipeline system is easily affected by fouling of marine organisms, and the marine organisms adhere to the inner wall of the pipeline, so that the problems of blockage, abnormal operation of the valve and the like are caused. Once a blockage occurs, the cooling efficiency of the power system is affected, which may induce accidents such as unexpected engine shutdown.
At present, methods for preventing fouling include controlling the flow rate of seawater, heat treatment, electrolytic chlorine placement, adding chemical agents and coating antifouling coatings, for example, a copper-iron alloy composite anode material for electrolysis disclosed in chinese patent 201610924368.6, which comprises the following components in percentage by weight: 30%, Cr: 1-3%, Mn: 2-5%, Sn: 0.5-2%, Al: 0.4-1.8% and the balance Fe; the manufacturing method of the copper-iron alloy composite anode material for electrolysis comprises the following steps: adding pig iron and electrolytic manganese into a medium-frequency induction furnace at the same time, covering the furnace with perlite, adding micro-carbon ferrochrome into the furnace after the raw materials are completely melted, heating to 1500-; standing to the temperature of 1510 ℃ and 1550 ℃ of molten steel, and casting the formed Fe-Mn-Cr alloy as an intermediate alloy; the intermediate alloy and Cu-Sn-Al copper alloy are fused and cast together at the temperature of 1300 ℃ and 1500 ℃, mixed rare earth RE is weighed according to the mass ratio of 0.04-0.06 percent, and is tightly wrapped by aluminum foil and pressed into alloy melt, and stirring and slagging off are carried out; casting into a round bar in a mould, and naturally cooling; the corrosion-resistant and pollution-resistant device for the seawater pipeline disclosed in the chinese patent 201220017315.3 comprises a pipe body and two flange plates, wherein the two flange plates are respectively connected to two ends of the pipe body, an anode unit is arranged in an inner cavity of the pipe body, the pipe body is directly or indirectly used as a cathode, and the anode units are distributed along the circumferential direction of the pipe body and spaced from the inner wall of the pipe body by a set distance; the titanium alloy seawater pipeline integrated efficient antifouling electrode disclosed in Chinese patent 201610693978.X comprises a base, a safety cap, a cable joint, an anode conductor, a copper-based composite anode body, an aluminum anode body and a cathode body, wherein the base is a flange plate, the base is connected with the safety cap, a wiring cavity is formed between the base and the safety cap, and the cable joint is led out from the wiring cavity; the anode conductor penetrates through the base, one end of the anode conductor extends into the wiring cavity and is connected to the cable joint to provide electrolytic current for the copper-based composite anode body and the aluminum anode body, and the outer side of the other end of the anode conductor is used as a support for the copper-based composite anode body and the aluminum anode body and enables the copper-based composite anode body and the aluminum anode body to be exposed in electrolyte; the section of the cathode body is a closed ring, the closed ring is fixed on the base and surrounds the outer sides of the copper-based composite anode body and the aluminum anode body, the anode conductor, the cathode body and the base are insulated and waterproof and sealed, and the base is insulated from the safety cap and the cathode body and is insulated from the cathode body, the copper-based composite anode body and the aluminum anode body; chinese patent 201711469170.4 discloses an automatic operation-controlled seawater pipeline electrolysis anti-fouling device, which comprises: the electrolysis electrode is arranged in a seawater pipeline system filter or a seabed valve box and comprises an electrolysis anode and an electrolysis cathode; the seawater flow monitoring equipment is arranged on a water outlet pipeline of the seawater pipeline system; and an electric control system connected with the electrolysis electrode and the seawater flow monitoring equipment; the electric control system outputs electrolysis current to the electrolysis anode and the electrolysis cathode, seawater is electrolyzed on the surface of the electrolysis anode to generate effective chlorine, and the effective chlorine flows along with the seawater and enters each part of the water outlet pipeline of the seawater pipeline system; the electric control system adjusts the output electrolytic current according to the monitoring signal fed back by the seawater flow monitoring equipment, and controls the chlorine yield, so that the effective chlorine concentration in the seawater pipeline system is always in an effective range. The above patent cannot be effectively applied to the actual seawater pipeline system because the seawater pipeline system is narrow and long. The chlorine and the electrolytic copper aluminum anode are put in the electrolysis in the prior art and are attenuated quickly in the seawater pipeline, the whole seawater pipeline cannot be ensured to be in a protection state, and the problem can be solved by installing the antifouling device in a segmented mode, however, the installation quantity of equipment is too much, and the ship structure is too complex and not practical.
Therefore, on the premise of not depending on an electrolytic device, the self-release of the antifouling components is realized, the release concentration achieves a broad-spectrum antifouling effect, the adhesion of marine organisms in a seawater pipeline is effectively prevented, and the device has positive social and economic benefits.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and develops and designs a high-efficiency self-coupling copper alloy antifouling anode preparation method based on galvanic corrosion, so as to meet the requirement of marine organism fouling treatment on the inner wall of a seawater pipeline.
In order to achieve the aim, the specific process of the preparation method of the self-coupling copper alloy antifouling anode comprises six steps of titanium powder pretreatment, titanium powder activation, copper powder pretreatment, metal matrix pretreatment, cold spraying and heat treatment:
firstly, titanium powder pretreatment:
putting titanium powder into NaOH aqueous solution, removing oil, washing with tap water, and putting into distilled water for ultrasonic treatment;
placing titanium powder in a boiling oxalic acid water solution, etching in a boiling state, and washing with tap water;
placing titanium powder in distilled water, ultrasonically cleaning, drying, and placing in ethanol for later use;
(II) titanium powder activation:
activating titanium powder by using an oxide anode, wherein the oxide anode comprises IrRu, PtTi and PrRhIr;
SnCl is added under ultrasonic condition4Dissolving in n-butanol, adding chloroiridic acid (H) after completely dissolving2IrC16·xH2O) n-butanol solution and ruthenium trichloride (RuC 1)3·3H2O) to obtain a mixed solution;
adding 5-15 drops of hydrochloric acid into the mixed solution, and stirring to completely dissolve ruthenium to obtain Ru-Ir-Sn masking liquid;
pouring the Ru-Ir-Sn coating solution into titanium powder, coating the titanium powder with the Ru-Ir-Sn coating solution, and drying;
sintering in a muffle furnace, taking out, and naturally cooling to room temperature;
sintering in a muffle furnace, taking out, and naturally cooling to room temperature to obtain activated titanium powder;
(III) copper powder pretreatment:
mixing copper powder with activated titanium powder to form mixed powder;
the copper powder comprises electrolytic copper powder, red copper powder or ion atomized copper alloy powder;
(IV) pretreating the metal matrix:
carrying out sand blasting activation on the surface of the metal matrix to enable the roughness to reach 20-80um, and carrying out dust removal treatment on the surface of the metal matrix;
(V) cold spraying:
spraying the mixed powder on the pretreated metal substrate by a cold spraying process to form a coating with a single-layer thickness of no more than 500 mu m and a total thickness (or sizes in all directions) of no more than 3-5mm of a target product;
(VI) heat treatment:
and (3) carrying out heat treatment on the metal substrate coated with the coating, and naturally cooling to room temperature under a vacuum condition to obtain the self-coupling copper alloy antifouling anode.
The structure of the self-coupling copper alloy antifouling anode prepared by the invention is shown in figure 1, the structure can also be a flange, a sleeve and a welding form which meet the flow state and circulation requirements of a pipeline in a seawater pipeline, and the water receiving area of titanium or titanium alloy in the structure is more than 1.2 times of that of copper or copper alloy.
The leaching rate of copper of the self-coupling copper alloy antifouling anode prepared by the invention is 110 mu g/cm2D, higher than 50 μ g/cm required for marine organism spectral sterilization2D, the copper and the copper alloy have better antifouling performance, but the antifouling effect is obviously reduced due to the reduction of the corrosion rate along with the lapse of time, the release efficiency of copper ions in the copper and the copper alloy can be greatly improved through the electrode material with corrected coupling potential, and the structural complexity of the antifouling material is reducedAnd a new antifouling mode can be provided for marine biofouling in special environments such as ship pipelines.
Compared with the prior art, the invention designs a macroscopic and microscopic combined double-couple corrosion self-coupling antifouling anode for long pipeline antifouling aiming at the problem of low self dissolution rate of copper alloy in a seawater pipeline, selects titanium or titanium alloy for accelerating the corrosion of the copper or copper alloy, carries out oxide anode activation treatment on the surface of the titanium or titanium alloy in order to ensure the galvanic activity of the titanium or titanium alloy, deposits and forms copper powder and titanium powder activated by the oxide anode on a pretreated metal matrix through a cold spraying process to form the self-coupling copper alloy antifouling anode, wherein the oxide anode polarizes copper components, accelerates the dissolution corrosion of the copper, greatly improves the antifouling effect of the copper, and the activated titanium powder further increases the galvanic corrosion current so that the galvanic corrosion current between the copper and the titanium cannot be reduced due to the passivation of the titanium; the principle is scientific and reliable, the mode of combining activated titanium powder and microcosmic galvanic corrosion is adopted, the activation effect of the galvanic corrosion is maximized, the prepared self-coupling copper alloy antifouling anode is arranged at each part or stage of the seawater pipeline in a flange or pipe section mode, the nondestructive treatment requirement of marine organisms on the inner wall of the seawater pipeline is met, and effective antifouling can be carried out on the long seawater pipeline.
Description of the drawings:
FIG. 1 is a schematic structural view of a self-coupling copper alloy anti-fouling anode according to the present invention.
FIG. 2 is a schematic structural view of an anti-fouling anode made from a copper alloy according to example 2 of the present invention.
FIG. 3 is a microscopic SEM image of an anti-fouling anode made from a copper alloy of example 2 of the present invention.
FIG. 4 is a table of the components of the self-coupling copper alloy anti-fouling anode prepared in example 2 of the present invention.
FIG. 5 is a schematic structural view of an anti-fouling anode made from a copper alloy according to example 3 of the present invention.
Fig. 6 is a schematic diagram showing the copper ion elution rate of the self-coupling copper alloy anti-fouling anode prepared in example 3 of the present invention.
FIG. 7 is a schematic diagram showing the time-dependent comparison of the dual current of the self-coupling copper alloy anti-fouling anode prepared in example 3 of the present invention and the titanium oxide anode.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example 1:
the specific process of the preparation method of the self-coupling copper alloy antifouling anode related to the embodiment comprises six steps of titanium powder pretreatment, titanium powder activation, copper powder pretreatment, metal matrix pretreatment, cold spraying and heat treatment:
firstly, titanium powder pretreatment:
placing titanium or titanium alloy powder with the particle size of 5-65 μm in NaOH aqueous solution with the mass percentage concentration of 5-15% at the temperature of 65-85 ℃, removing oil for 0.5-1h, washing with tap water, placing in distilled water, and performing ultrasonic treatment for 10-15min, wherein the titanium alloy is pure titanium, TC4, Ti80 or Ta 2;
placing titanium or titanium alloy powder into a boiled oxalic acid water solution with the mass percentage concentration of 5-15%, etching for 2-5h in a boiling state, and washing with tap water;
placing titanium or titanium alloy powder in distilled water, ultrasonically cleaning for 10-15min, blow-drying, and placing in a crucible containing ethanol for later use;
(II) titanium powder activation:
SnCl is added under ultrasonic condition4Dissolving in n-butanol, adding chloroiridic acid (H) after completely dissolving2IrC16·xH2O) n-butanol solution and ruthenium trichloride (RuC 1)3·3H2O) to obtain a mixed solution, wherein the molar ratio of Ru, Ir and Sn is 15-20:20-25: 55-65;
adding 5-15 drops of hydrochloric acid into the mixed solution by a dropper to play a role of surface wetting, and stirring for 30-60min by a magnetic stirrer to completely dissolve ruthenium to obtain Ru-Ir-Sn coating solution;
pouring the Ru-Ir-Sn coating solution into a crucible to immerse the titanium or titanium alloy powder by 1-10mm, drying for 10min at the temperature of 120 ℃, and continuously stirring in the drying process to prevent the titanium or titanium alloy powder from agglomerating;
placing the crucible in a muffle furnace at the temperature of 450-550 ℃ for sintering for 10-30min, taking out, and naturally cooling to room temperature;
then placing the crucible in a muffle furnace at the temperature of 470-520 ℃ for sintering for 1h, taking out, and naturally cooling to room temperature to obtain activated titanium or titanium alloy powder;
(III) copper powder pretreatment:
mixing copper or copper alloy powder with the grain diameter of 5-45 mu m and activated titanium or titanium alloy powder according to the proportion of 1: 3-19, and forming mixed powder;
the copper or copper alloy powder comprises electrolytic copper powder, red copper powder or ion atomized copper alloy powder;
(IV) pretreating the metal matrix:
based on the properties of easy melting, low price and easy cutting of the aluminum alloy, the aluminum alloy is selected as a metal matrix, brown corundum is adopted to carry out sand blasting activation on the surface of the metal matrix, the roughness reaches 20-80 mu m, the appearance surface of the metal matrix is visually observed to be uniform and consistent, no visible attachments such as grease, dirt, oxide skin, paint coating and the like exist, the pressure of compressed air adopted during sand blasting is not lower than 0.6MPa, the compressed air enters a spray gun after passing through an oil-water separator and a buffer tank with good properties, and a dust collector is adopted to carry out dust removal treatment on the surface of the metal matrix after sand blasting is carried out to remove rust;
because the turning can remove part of the thickness when in leveling, the shrinkage can be generated during the heat treatment, before the deposition and the manufacturing and the forming of the self-coupling copper alloy antifouling anode, the outer diameter of the metal matrix is 3-5mm smaller than the inner diameter of the self-coupling copper alloy antifouling anode or each dimension direction of the metal matrix is 3-5mm larger than the self-coupling copper alloy antifouling anode, and enough tolerance is reserved for the turning and the heat treatment;
(V) cold spraying:
in a workshop or a construction site, spraying the mixed powder on the pretreated metal matrix by a low-pressure cold spraying process to form a coating with the thickness of 200 mu m;
before cold spraying, preheating a metal matrix to 90-120 ℃, wherein in the cold spraying process, the spraying temperature is 550-;
(VI) heat treatment:
and (2) placing the metal matrix coated with the coating in a heat treatment furnace for heat treatment, wherein the heat treatment can eliminate stress, improve the bonding performance and the air tightness, reduce the brittleness and meet a withstand voltage test, keeping the temperature for 1-5h after the temperature rises to 600 ℃ plus materials at the temperature rise rate of 10 ℃/min, closing the heat treatment furnace, naturally cooling the metal matrix in a vacuum box to room temperature, taking out the metal matrix to obtain the self-coupling copper alloy antifouling anode, and during subsequent turning, the feed amount of each circle is not more than 10 mu m.
Example 2:
the preparation method of the self-coupling copper alloy antifouling anode adopts TC4 powder with the grain diameter of 5-45 mu m, copper alloy powder with the grain diameter of 5-45 mu m, and when the MMO anode activates the titanium alloy powder: the molar ratio of Ru to Ir to Sn is 15:20:55, the drying temperature is 120 ℃, the time is 15min, the sintering temperature is 500 ℃, and the time is 1.5 h; the parameters of the cold spraying process are as follows: the carrier gas is nitrogen, the pressure is 5.5MPa, the temperature is 700 ℃, and the spraying distance is 25 mm; the heat treatment temperature is 450 ℃ and the time is 30 min.
The self-coupling copper alloy antifouling anode prepared by the embodiment has good appearance and appearance as shown in figure 2, and the microstructure and the components are shown in figures 3 and 4, and the MMO activated titanium powder is uniformly dispersed in the self-coupling copper alloy antifouling anode.
Example 3:
the preparation method of the self-coupling copper alloy antifouling anode adopts TC4 powder with the grain diameter of 5-45 mu m, copper alloy powder with the grain diameter of 5-45 mu m, and when the MMO anode activates the titanium alloy powder: the molar ratio of Ru to Ir to Sn is 15:20:55, the drying temperature is 120 ℃, the time is 15min, the sintering temperature is 500 ℃, and the time is 1.5 h; the parameters of the cold spraying process are as follows: the carrier gas is nitrogen, the pressure is 4.5MPa, the temperature is 800 ℃, and the spraying distance is 25 mm; the heat treatment temperature is 450 ℃ and the time is 30 min.
The self-coupling copper alloy antifouling anode prepared by the embodiment has good appearance and appearance as shown in fig. 5, the copper ion dissolution rate and the change of the dual current of the self-coupling copper alloy antifouling anode and the titanium oxide anode with time are shown in fig. 6 and 7, and the copper ion release test results are shown in the following table:
it can be seen that the dissolution of copper ions is much higher than that of red copper itself.
Claims (9)
1. A preparation method of an antifouling self-coupling copper alloy anode is characterized in that the specific process comprises three steps of titanium powder activation, cold spraying and heat treatment:
activating titanium powder:
activating titanium powder by using an oxide anode;
(II) cold spraying:
spraying mixed powder formed by mixing copper powder and activated titanium powder on the pretreated metal substrate by a cold spraying process to form a coating with a single-layer thickness of no more than 500 mu m and a total thickness of no more than 3-5 mm;
(III) heat treatment:
and (3) carrying out heat treatment on the metal substrate sprayed with the coating, and naturally cooling to room temperature under a vacuum condition to obtain the self-coupling copper alloy antifouling anode.
2. The method for preparing the self-coupling copper alloy antifouling anode according to claim 1, wherein the titanium powder is pretreated before being activated, and the specific process is as follows:
putting titanium powder into NaOH aqueous solution, removing oil, washing with tap water, and putting into distilled water for ultrasonic treatment;
placing titanium powder in a boiling oxalic acid water solution, etching in a boiling state, and washing with tap water;
and putting the titanium powder into distilled water, ultrasonically cleaning, blow-drying and putting into ethanol for later use.
3. The method of claim 1, wherein the oxide anode comprises IrRu, PtTi, and PrRhIr.
4. The method for preparing the self-coupling copper alloy antifouling anode according to claim 1, wherein the specific process of activating titanium powder is as follows:
SnCl is added under ultrasonic condition4Dissolving in n-butyl alcohol, and adding n-butyl chloroiridate solution and ruthenium trichloride after complete dissolution to obtain a mixed solution;
adding 5-15 drops of hydrochloric acid into the mixed solution, and stirring to completely dissolve ruthenium to obtain Ru-Ir-Sn masking liquid;
pouring the Ru-Ir-Sn coating solution into titanium powder, coating the titanium powder with the Ru-Ir-Sn coating solution, and drying;
sintering in a muffle furnace, taking out, and naturally cooling to room temperature;
and sintering in a muffle furnace, taking out, and naturally cooling to room temperature to obtain the activated titanium powder.
5. The method for preparing the self-coupling copper alloy antifouling anode according to claim 1, wherein a metal matrix is pretreated before cold spraying, and the specific process is as follows: and (3) carrying out sand blasting activation on the surface of the metal matrix, and carrying out dust removal treatment after the roughness of the metal matrix reaches 20-80 um.
6. The method for preparing the self-coupling copper alloy antifouling anode according to the claim 1, wherein the heat treatment comprises the following specific processes: raising the temperature to 380-600 ℃ according to the heating rate of 10 ℃/min, and then preserving the heat for 1-5 h.
7. The method for preparing the self-coupling copper alloy antifouling anode according to claim 4, wherein the molar ratio of Ru, Ir and Sn in the mixed solution is 15-20:20-25: 55-65; in the mixed powder, the mass ratio of the copper powder to the activated titanium powder is 1: 3-19.
8. The method for preparing the self-coupling copper alloy anti-fouling anode according to any one of claims 1 to 6, wherein the self-coupling copper alloy anti-fouling anode is prepared to meet the flow state and circulation requirements of pipelines in seawater pipelines and comprises a flange mode, a sleeve mode and a welding mode, wherein the water receiving area of titanium or titanium alloy is more than 1.2 times of that of copper or copper alloy.
9. A method of producing an antifouling self-coupling copper alloy anode according to any of claims 1 to 6, characterised in that the produced antifouling self-coupling copper alloy anode has a copper leaching rate of 110 μ g/cm2.d。
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| CN112662222A (en) * | 2020-11-13 | 2021-04-16 | 西安交通大学 | Anti-biological fouling coating based on micron-sized primary battery with double-metal-layer sheet structure and preparation method thereof |
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