CN108707895B - Composite coating material for underwater laser repairing of copper-based metal and preparation method thereof - Google Patents
Composite coating material for underwater laser repairing of copper-based metal and preparation method thereof Download PDFInfo
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- CN108707895B CN108707895B CN201810622272.3A CN201810622272A CN108707895B CN 108707895 B CN108707895 B CN 108707895B CN 201810622272 A CN201810622272 A CN 201810622272A CN 108707895 B CN108707895 B CN 108707895B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- C22C9/00—Alloys based on copper
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Abstract
The invention provides a composite coating material for underwater laser repair of copper-based metal and a preparation method thereof, wherein the composite coating material comprises 62-64 wt.% of Cu, 7-9 wt.% of Al, 3-4 wt.% of Fe, 4-5 wt.% of Ni, 2-4 wt.% of Mn, 11-12 wt.% of Mo, 1-2 wt.% of Si, 1-1.5 wt.% of B and 2.5-3 wt.% of CaF2And (4) forming. The special composite coating material for on-line repairing of the damaged surface of the copper alloy by using the underwater laser and the preparation method thereof have the advantages of simple process and low cost of the used material; the process method is easy to realize automation, and the consumable material form is very suitable for underwater environment, which is caused by the excellent waterproof performance before melting of the consumable material; the special composite coating material for online repairing of the damaged surface of the copper alloy by underwater laser can well play roles in draining water and alloying in the laser processing process, and is beneficial to realization of underwater in-situ laser cladding; the special composite coating material for online repairing of the damaged surface of the copper alloy by using the underwater laser can overcome the defect of poor forming quality of the copper alloy in water environment.
Description
Technical Field
The invention relates to a composite coating material and a preparation method thereof, in particular to a composite coating material for repairing copper-based metal by underwater laser and a preparation method thereof, belonging to the technical field of material science and processing.
Background
Deep sea is one of important fields that people are looking for and hope to develop, and in recent years, various deep sea equipments such as deep sea oil and gas pipelines, deep sea robots, deep submergence vehicles and the like are presented in front of people. In addition, the concept of deep ocean space stations has begun to be of widespread interest in recent years. The problem of repairing these deep sea installations is then naturally felt, the most significant and challenging of which is the in situ repair in a deep sea environment. Today, underwater welding technology, which is a technology for directly welding underwater by using an electric arc, has appeared in the world, and the appearance of the technology makes people look at the hope of underwater in-situ repair. Since then, people have developed underwater laser welding and cladding technology, which is characterized by creating the atmosphere as same as the atmospheric environment as possible in water environment, that is, it needs auxiliary equipment, which can be realized and is unique in shallow water area, but the disadvantage of the technology is highlighted with the increase of water depth, and it is severely restricted by the auxiliary equipment. In order to overcome this limitation, the idea of laser remediation directly in a totally humid water environment has been followed. The most critical link of the laser processing technology for directly carrying out online repair in water environment is the use of repair materials.
Copper material is an important material in ocean engineering application, and copper-based metal material plays an important role in various application environments. In recent years, the demand for on-line repair of copper-based metal materials has been pressing. In early practice, the research team performs experimental research on underwater laser on-line repair by using a semi-soluble coating as a second protective layer and a preset copper alloy powder layer as a cladding precursor, and the result shows that the method is very effective. But also has a plurality of problems, such as high porosity of the prepared repairing layer, serious external pollution, serious limitation of forming quality by laser power, and the like. Finally, the following results are obtained through research and summary: this result is due to the strong absorption of the laser and the large impact on the laser bath by the plasma component of the photo-pharmaceutical gas envelope, as well as the co-action of the physicochemical properties of the copper material itself. Therefore, the improvement of the components of the medicament and the upgrading of the cladding material are effective ways for further realizing the underwater in-situ repair of the copper alloy parts.
Disclosure of Invention
The invention aims to provide a composite coating material for repairing copper-based metal by underwater laser and a preparation method thereof, aiming at solving the problem of poor forming quality of the existing consumable material.
The purpose of the invention is realized as follows:
a composite coating material for underwater laser repairing of copper-based metals consists of 62-64 wt.% of Cu, 7-9 wt.% of Al, 3-4 wt.% of Fe, 4-5 wt.% of Ni, 2-4 wt.% of Mn, 11-12 wt.% of Mo, 1-2 wt.% of Si, 1-1.5 wt.% of B and 2.5-3 wt.% of CaF2And (4) forming.
A preparation method of a composite coating for underwater laser repair of copper-based metal comprises the following steps:
the method comprises the following steps: according to 62-64 wt.% Cu, 7-9 wt.% Al, 3-4 wt.% Fe, 4-5 wt.% Ni, 2-4 wt.% Mn, 11-12 wt.% Mo, 1-2 wt.% Si, 1-1.5 wt.% B and 2.5-3 wt.% CaF2Weighing metal powder according to the component ratio, wherein the particle size of the metal powder is 50-70 μm, and uniformly mixing the metal powder by using a ball mill to obtain a prepared composite coating material;
step two: taking the prepared composite coating material as a first preset layer, and presetting the composite coating material on the damaged copper alloy surface by adopting a binder;
step three: taking Sn metal powder as a second preset layer, and presetting the Sn metal powder on the first preset layer by adopting a binder;
step four: and cladding by adopting a laser cladding system.
The invention also includes such features:
1. in the first step, the ball milling time is 2-3 hours, the ball material ratio is 2-3:1, and the rotating speed of the ball mill is 300-;
2. the adhesive in the second step and the third step is α -ethyl cyanoacrylate, epoxy resin or polyvinyl alcohol;
3. in the third step, the purity of the Sn metal powder is more than 99.95 percent;
4. YAG laser is used as a laser source of the laser cladding system in the fourth step, the laser power is 3000W, the scanning speed is 10mm/s, the laser diameter is 4mm, and the laser is negatively defocused.
In daily researches, the harmless low-melting-point metal has good drainage and alloying effects under the action of laser, for example, the Sn-based metal material adopted in the invention can play a good drainage and alloying effect in underwater repair of Cu-based metal. In addition, the absorption effect of the laser on the light-induced plasma generated by adopting the low-melting-point metal as the intermediate protective material is not strong, so that the processing quality of the coating cannot be excessively influenced by adopting the Sn-based metal material as a water drainage medicament, and therefore, the Sn-based metal material is a good intermediate protective material for underwater laser repair of the copper alloy. In addition, the copper alloy material has the characteristic of rapid heat conduction, the characteristics of a molten pool in the laser processing process are different from those of steel, nickel, cobalt and other materials, the stirring motion is violent, and the copper alloy molten pool is very easy to cool and solidify in the overturning process of the molten pool under the ultra-rapid cooling speed in a water environment, so that a large number of air holes are formed. In the invention, the effect of stabilizing the copper alloy laser molten pool is achieved by adding a proper amount of Mo, Si and B elements into the coating material, and the prepared copper alloy coating has good forming quality.
The composite coating material has the functions of stabilizing a laser processing molten pool and slagging and removing dirt after melting, wherein the purpose of adding Mo element is to stabilize a copper alloy molten pool under laser irradiation; b is added, so that the heat resistance of the copper alloy coating is increased, and the heat dissipation speed of the coating is reduced; the addition of Si powder aims at slagging and decontaminating and ensures the cleaning quality of the coating; CaF2The purpose of (a) is to react with hydrogen generated during laser machining so as to reduce the content of hydrogen pores in the coating layer.
Compared with the prior art, the invention has the beneficial effects that:
1. the special composite coating material for on-line repairing of the damaged surface of the copper alloy by using the underwater laser and the preparation method thereof have the advantages of simple process and low cost of the used material;
2. the process method is easy to realize automation, and the consumable material form is very suitable for underwater environment, which is caused by the excellent waterproof performance before melting of the consumable material;
3. the special composite coating material for repairing the damaged surface of the copper alloy on line by using the underwater laser can well play roles in draining water and alloying in the laser processing process, and is favorable for realizing underwater in-situ laser cladding;
4. the special composite coating material for online underwater laser repair of the damaged surface of the copper alloy can overcome the defect of poor forming quality of the copper alloy in water environment;
5. the special composite coating material for online underwater laser repair of the damaged surface of the copper alloy and the preparation method thereof can provide a material design idea for further underwater laser cladding research.
Drawings
FIGS. 1 a-1 d are schematic views of a lower laser cladding process coating;
FIGS. 2a-2b are microstructure views of a process coating.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention relates to a special composite coating material for underwater laser on-line repair of damaged surfaces of copper alloys and a using method thereof, which are realized by the following steps:
63 wt.% Cu, 9 wt.% Al, 4 wt.% Fe, 4 wt.% Ni, 2 wt.% Mn, 12 wt.% Mo, 2 wt.% Si, 1 wt.% B, 3 wt.% CaF according to the invention2Weighing powder according to the component ratio, wherein the diameter of the metal powder is 50 mu m, and fully and uniformly mixing the metal powder by using a ball mill;
secondly, pre-placing the mixed powder material on the damaged copper alloy surface by adopting waterproof organic glue as a bonding agent (comprising α -ethyl cyanoacrylate, epoxy resin, polyvinyl alcohol and the like);
thirdly, Sn metal powder is used as a second preset layer, and waterproof organic glue is also used as a binder;
and fourthly, performing online repair on the damaged surface of the underwater copper alloy by adopting a laser cladding system.
The ball milling time in the step one is 2 hours, the ball milling ball material ratio is 2:1, and the rotating speed of the ball mill is 300 r/min.
And the preset coating in the step two is finished by adopting a self-made slurry laying device.
And step three, the purity of the Sn metal powder is more than 99.99 percent, and the laying process is also finished by adopting a self-made slurry laying device.
YAG laser is used as the laser source of the laser cladding system in the step four, the whole system is controlled by the central controller to operate, and automation of a cladding path can be realized.
The first embodiment is as follows:
the preparation method of the copper-based alloy coating for underwater laser cladding is implemented according to the following steps:
firstly, roughening the surface of an aluminum bronze plate by using No. 60 abrasive paper, cleaning the surface by using acetone, and naturally drying to obtain a roughened copper alloy matrix;
secondly, coating an alloy powder layer (element powder which is not optimized in design) with the thickness of 1mm on the surface of the roughened copper alloy substrate, standing for 15min, coating a cladding protective coating with the thickness of 0.5mm on the surface of the alloy powder layer, and standing for 10min to obtain the copper alloy substrate with the preset coating;
thirdly, water with the depth of 21mm is placed in a water tank, a copper alloy matrix with a preset coating is placed in an underwater environment (8 mm deep into the water surface), a laser cladding gun head is adjusted to a position 50mm away from the water surface, the laser focal length is adjusted to enable a light-gathering spot to fall on the preset coating, cladding is carried out by adopting a laser, the laser power in the cladding process is controlled to be 3000W, the traveling speed of a cladding head is 4-11 mm/s, and the cladding path adopts a reciprocating double path of forward cladding and reverse remelting to complete the preparation of the laser cladding layer under the water environment;
the alloy powder layer in the second step is formed by mixing aluminum bronze alloy powder and α -ethyl cyanoacrylate adhesive in a mass ratio of 400:1, the cladding protective coating is composed of, by mass, 45% of CaF2, 26% of C, 1.5% of CuO, 11.2% of TiO2, 7.1% of Si, 8.2% of α -ethyl cyanoacrylate and the balance of active carbon, and the components of the coating are common protective coatings for underwater welding.
The dimensions of the aluminum bronze plate in this example were 130mm × 100mm × 14mm in length × width × height.
The copper alloy coating prepared by the embodiment is high in apparent porosity and poor in cladding effect as shown in fig. 1a, b and 2 a.
Example two:
the preparation method of the copper-based alloy coating for underwater laser cladding is implemented according to the following steps:
the method comprises the following steps of firstly, roughening the surface of an aluminum bronze plate by using No. 60 abrasive paper, cleaning the surface by using acetone, and naturally drying to obtain a roughened copper alloy matrix;
secondly, the step is similar to the second step of the embodiment, the optimized alloy powder layer with the thickness of 1mm is coated on the surface of the roughened copper alloy matrix, the Sn metal powder layer with the thickness of 0.5mm is coated on the surface of the alloy powder layer after standing for 15min, and the copper alloy matrix with the preset coating is obtained after standing for 10 min.
Thirdly, the step is similar to the third step of the embodiment, water with the depth of 21mm is placed in a water tank, a copper alloy substrate is placed in an underwater environment (8 mm deep into the water surface), a laser cladding gun head is adjusted to a position 50mm away from the water surface, the laser focal length is adjusted to enable a light condensing spot to fall on a preset coating, cladding is carried out by adopting a laser, the laser power is controlled to be 3000W in the cladding process, the traveling speed of a cladding head is 10mm/s, the laser diameter is 4mm, laser negative defocusing is carried out, and the preparation of a laser cladding layer in the water environment is completed;
the difference between the second step of the present embodiment and the second step of the present embodiment is that the optimized composite coating material of the present invention is used.
Step three of this embodiment is different from step three of this embodiment in that a Sn metal powder layer is used as the second pre-layer.
The copper alloy underwater environment laser cladding process effectively avoids the problem of excessive defects such as impurities, air holes and cracks of a cladding layer, and the appearance of the cladding layer is shown as a right coating in figures 1c and d and 2 b.
Because the optimized coating material is adopted in the embodiment, the copper alloy coating obtained through the laser processing process has low porosity and excellent apparent formability.
The embodiment adopts the effective composite coating material, the components of the composite coating material have the characteristics of stabilizing a molten pool, promoting forming and strengthening alloy, and the prepared copper alloy has improved structure performance compared with the coating prepared by other preparation methods.
In summary, the following steps: the invention provides a novel composite coating material for wet-process underwater laser online maintenance and a preparation method thereof, aiming at the consumable material requirement of the wet-process underwater laser online maintenance technology and solving the problem of poor forming quality of a copper-based metal material coating processed by underwater laser. According to the invention, a proper amount of Mo, Si and B elements are introduced on the basis of a copper-based metal material system, and meanwhile, a Sn metal powder layer is adopted as a second preset protective layer. The coating prepared by the material system and the preparation method has good forming quality, low internal porosity and good performance, and greatly improves the quality and efficiency of the underwater laser on-line repair of the copper-based metal material coating.
Claims (10)
1. A composite coating material for underwater laser repairing of copper-based metal is characterized by comprising two preset layers: the first pre-layer consists of 62-64 wt.% Cu, 7-9 wt.% Al, 3-4 wt.% Fe, 4-5 wt.% Ni, 2-4 wt.% Mn, 11-12 wt.% Mo, 1-2 wt.% Si, 1-1.5 wt.% B, and 2.5-3 wt.% CaF2Composition is carried out; the second pre-layer is Sn metal powder.
2. A preparation method of a composite coating for underwater laser repairing of copper-based metal is characterized by comprising the following steps:
the method comprises the following steps: according to 62-64 wt.% Cu, 7-9 wt.% Al, 3-4 wt.% Fe, 4-5 wt.% Ni, 2-4wt.% Mn, 11-12 wt.% Mo, 1-2 wt.% Si, 1-1.5 wt.% B and 2.5-3 wt.% CaF2Weighing metal powder according to the component ratio, wherein the particle size of the metal powder is 50-70 μm, and uniformly mixing the metal powder by using a ball mill to obtain a prepared composite coating material;
step two: taking the prepared composite coating material as a first preset layer, and presetting the composite coating material on the damaged copper alloy surface by adopting a binder;
step three: taking Sn metal powder as a second preset layer, and presetting the Sn metal powder on the first preset layer by adopting a binder;
step four: and cladding by adopting a laser cladding system.
3. The method for preparing the composite coating for the underwater laser repair of the copper-based metal according to claim 2, wherein in the step one, the ball milling time is 2-3 hours, the ball-material ratio is 2-3:1, and the rotating speed of the ball mill is 300-500 r/min.
4. The method for preparing a composite coating for underwater laser repair of copper-based metals according to claim 2 or 3, wherein the binder in the second step and the third step is α -ethyl cyanoacrylate, epoxy resin or polyvinyl alcohol.
5. The method for preparing the composite coating for underwater laser repair of the copper-based metal according to claim 2 or 3, wherein the purity of the Sn metal powder in the step three is more than 99.95%.
6. The method for preparing the composite coating for underwater laser repair of the copper-based metal according to claim 4, wherein the purity of the Sn metal powder in the third step is more than 99.95%.
7. The method for preparing the composite coating for the underwater laser repair of the copper-based metal according to claim 2 or 3, wherein a laser light source of the laser cladding system in the fourth step is Nd, YAG laser, laser power is 3000W, scanning speed is 10mm/s, laser diameter is 4mm, and laser negative defocusing is performed.
8. The method for preparing the composite coating for underwater laser repair of the copper-based metal according to claim 4, wherein a laser light source of the laser cladding system in the fourth step is Nd-YAG laser, the laser power is 3000W, the scanning speed is 10mm/s, the laser diameter is 4mm, and the laser is negatively defocused.
9. The method for preparing the composite coating for underwater laser repair of the copper-based metal according to claim 5, wherein a laser light source of the laser cladding system in the fourth step is Nd, YAG laser, laser power is 3000W, scanning speed is 10mm/s, laser diameter is 4mm, and laser negative defocusing is performed.
10. The method for preparing the composite coating for underwater laser repair of the copper-based metal according to claim 6, wherein a laser light source of the laser cladding system in the fourth step is Nd, YAG laser, laser power is 3000W, scanning speed is 10mm/s, laser diameter is 4mm, and laser negative defocusing is performed.
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| CN109735840A (en) * | 2018-12-25 | 2019-05-10 | 阳江市高功率激光应用实验室有限公司 | Method of inhibiting corrosion for oceanic winds conductance pipe support |
| CN111850546B (en) * | 2020-06-28 | 2021-11-02 | 华中科技大学 | Method for repairing nickel-aluminum bronze part through laser cladding and product thereof |
| CN112122607B (en) * | 2020-10-10 | 2023-05-09 | 哈尔滨工程大学 | Material adding and repairing material suitable for ocean oscillation working condition and stability-shape regulation and control method of molten pool |
| CN112430811B (en) * | 2020-11-23 | 2022-02-25 | 浙江大学 | Method for laser cladding of copper alloy powder on surface of copper matrix |
| CN113718247B (en) * | 2021-09-09 | 2024-02-02 | 中国人民解放军陆军装甲兵学院 | Plasma cladding repair method for copper alloy damaged part |
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