CN115449722B - Copper-based amorphous composite coating suitable for marine ship shell, and preparation method and application thereof - Google Patents
Copper-based amorphous composite coating suitable for marine ship shell, and preparation method and application thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 111
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 98
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 39
- 238000005260 corrosion Methods 0.000 claims abstract description 39
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 22
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims abstract description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 18
- 238000005507 spraying Methods 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 238000009689 gas atomisation Methods 0.000 claims abstract description 10
- 238000010288 cold spraying Methods 0.000 claims abstract description 7
- 230000006698 induction Effects 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 14
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 10
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 9
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims description 9
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 230000033001 locomotion Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007788 roughening Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000005488 sandblasting Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/001—Amorphous alloys with Cu as the major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a copper-based amorphous composite coating suitable for a marine ship shell and a preparation method thereof, wherein the coating is formed by compositing 92-94wt.% of copper-based amorphous and 6-8wt.% of nano particles; the weight percentages of the copper-based amorphous components are as follows: 18-22wt.% Zr, 10-12wt.% Ti, 3-5wt.% Ni, 0.5-1.5wt.% Si, the balance Cu; the nanoparticles consist of Graphene Oxide (GO) and Yttria Stabilized Zirconia (YSZ). Adding copper-based amorphous raw materials into an induction electromagnetic oven to heat and melt, and carrying out vacuum gas atomization on molten metal liquid to obtain copper-based amorphous powder; the powder and the nano particles are mixed and applied to preparing the corrosion-resistant and anti-fouling coating, the cold spraying technology is adopted to prepare the coating, and the spraying atmosphere is argon.
Description
Technical Field
The invention belongs to the field of thermal spraying of material processing engineering, and particularly relates to a copper-based amorphous composite coating suitable for a marine ship shell and a preparation method thereof.
Background
The ship shell is often damaged by serious corrosion, biofouling and the like in the marine environment, and the corrosion of the ship shell often causes the damage of a ship body structure and sometimes threatens the life safety of personnel on the ship; biofouling on the one hand aggravates the ship's quality, thereby increasing the energy consumption and economic costs of ship operation, and on the other hand biofouling generally accelerates further the corrosion damage suffered by ship hull materials. Statistics show that corrosion damage and biofouling are main reasons for the occurrence of old ship accidents, and ship shells can lose bearing capacity and even break steel plates under serious corrosion and fouling damage. Therefore, the problems of corrosion and biofouling of the ship shell are reduced or even eliminated, and the method becomes a powerful thought for promoting the safe and stable operation and long-acting service of the ship, and is also an important point and a difficult point of protecting the ship shell.
Because both corrosion damage and biofouling occur on the surface of the material, preparing a high performance protective coating on the surface of an existing material is a more economical and effective means of protection than replacing a high performance bulk material. Copper elements generally endow copper alloy with excellent biofouling resistance due to strong sterilization capability, so that the copper alloy has unique application potential and application prospect in marine environment. However, compared with materials such as stainless steel, the corrosion resistance of the copper alloy is still not ideal, which limits the application of the copper alloy under severe working conditions such as ocean. Copper-based amorphous materials have the advantage of amorphous materials that the atomic structure of which is short-range ordered and long-range disordered makes them free from defects such as grain boundaries, dislocation and the like, thus exhibiting much better corrosion resistance than crystalline states. In addition, when the preferred second phase is added to the amorphous alloy, the corrosion resistance of the composite material can be further improved. The invention designs a novel copper-based amorphous/nano second phase composite material, which has excellent corrosion resistance and antifouling property in marine environment, and can effectively protect marine ship shells and the like from being damaged by corrosion-fouling coupling damage.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the copper-based amorphous composite material suitable for the marine ship shell and the preparation method thereof, and the material can be used for preparing the corrosion-resistant anti-fouling integrated coating on the surface of the marine ship shell.
In order to achieve the aim of the invention, the invention is realized by adopting the following technical scheme:
a copper-based amorphous composite material suitable for marine ship shells and a preparation method thereof, wherein the material is formed by compositing 92-94wt.% of copper-based amorphous and 6-8wt.% of nano particles; the weight percentages of the copper-based amorphous components are as follows: 18-22wt.% Zr, 10-12wt.% Ti, 3-5wt.% Ni, 0.5-1.5wt.% Si, the balance Cu; the nanoparticles consist of Graphene Oxide (GO) and Yttria Stabilized Zirconia (YSZ).
As a preferred technical scheme of the invention: the nano particles consist of GO and YSZ, and the content of GO is 5-10%.
As a preferred technical scheme of the invention: the nanoparticles consist of GO and YSZ, and the content of GO is 10%.
As a preferred technical scheme of the invention: the copper-based amorphous composite material suitable for the marine vessel shell is formed by compounding 93wt.% of copper-based amorphous, 0.7wt.% of GO and 6.3wt.% of YSZ; the weight percentages of the copper-based amorphous components are as follows: 20wt.% Zr, 11wt.% Ti, 4wt.% Ni, 1wt.% Si, the balance Cu.
The invention provides a preparation method of the copper-based amorphous composite material suitable for a marine ship shell, which comprises the following steps:
the first step: weighing copper-zirconium alloy, copper-titanium alloy, pure nickel, monocrystalline silicon and pure copper according to the content of the copper-based amorphous component, sequentially adding the pure nickel, the monocrystalline silicon, the pure copper, the copper-zirconium alloy and the copper-titanium alloy into a vacuum induction electromagnetic oven according to the principle of firstly high melting point and then low melting point, and then heating to enable the pure nickel, the monocrystalline silicon, the pure copper, the copper-zirconium alloy and the copper-titanium alloy to be completely melted;
and a second step of: vacuum gas atomization treatment is carried out on the melted mixed solution, wherein the gas atomization gas is argon, the atomization vacuum degree is 5-10Pa, the argon pressure is 3MPa, and after gas atomization, the powder with the particle size smaller than 30 mu m is vacuum-dried and sieved to obtain copper-based amorphous powder;
and a third step of: and uniformly mixing the copper-based amorphous powder and the nano particles by adopting a three-dimensional motion mixer to obtain the copper-based amorphous composite material.
As a preferred technical scheme of the invention: the heating rate of the induction electromagnetic oven in the first step is 50-60K/s.
As a preferred technical scheme of the invention: the drying temperature in the second step is 80-120 ℃ and the drying time is 2-4h.
The invention also provides application of the copper-based amorphous composite material in preparing a corrosion-resistant and anti-fouling coating.
The application of the copper-based amorphous composite material in preparing the corrosion-resistant anti-fouling coating comprises the following steps:
the first step: after degreasing and rust removal of the surface of the marine ship shell, sand blasting and roughening treatment are carried out on the surface of the marine ship shell by adopting white corundum sand with the granularity of 5-35 meshes;
and a second step of: and (3) spraying a copper-based amorphous composite material on the surface of the ship shell by adopting a cold spraying technology to form a corrosion-resistant and anti-fouling coating, wherein the spraying adopts argon gas, the spraying pressure is 4MPa, the carrier gas temperature is 600 ℃, the spraying distance is 30mm, the spraying speed is 50mm/s, and the powder feeding rotating speed is 1.5r/min.
Compared with the prior art, the method has the following beneficial effects:
1. the copper-based amorphous/nanoparticle composite coating prepared by cold spraying has compact structure, high amorphous content, good corrosion resistance and antifouling property, is suitable for severe working conditions such as ship shells and the like in marine environments, is easy to industrialize, and has wide market application prospect;
2. in the copper-based amorphous/nanoparticle composite material, the amorphous raw material part is an alloy, and compared with the traditional process adopting pure metal as the raw material, the amorphous raw material preparation cost is lower;
3. the design of the copper-based amorphous component enables the copper-based amorphous component to have good performance. The designed alloy system has good amorphous forming capability, a complete amorphous material can be prepared by adopting an air atomization process, the process of preparing a base material is omitted, and the process is more convenient;
4. through adding GO and YSZ, on one hand, the GO and the YSZ can effectively shield invasion of corrosive medium, on the other hand, can play a role in blocking a coating pore by nano particles, and effectively improve corrosion resistance of a system;
5. the high amorphous content of the amorphous powder can be completely inherited into the coating by adopting a cold spraying technology, and a protective coating with the porosity less than or equal to 1% and the amorphous content more than or equal to 90% is prepared on the surface of the ship shell;
6. the coating has good corrosion resistance and antifouling property, and experiments show that the corrosion loss of the coating is less than or equal to 0.01mm/a and the biological weight loss of the fouling organisms in the month is less than or equal to 1000g/m 2 。
Drawings
Figure 1 is an XRD pattern of example 1 and comparative example 1.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily understood by those skilled in the art that the specific material ratios, process conditions, and results thereof described in the examples are illustrative of the present invention and should not be construed as limiting the invention described in detail in the claims.
Example 1
A copper-based amorphous composite material suitable for marine vessel shells, formed by compositing 92wt.% copper-based amorphous and 8wt.% nanoparticles (0.8 wt.% GO and 7.2wt.% YSZ); the weight percentages of the copper-based amorphous components are as follows: 18wt.% Zr, 10wt.% Ti, 3wt.% Ni, 0.5% si, the balance Cu.
The copper-based amorphous composite material suitable for the marine ship shell is prepared by the following steps:
the first step: weighing copper-zirconium alloy, copper-titanium alloy, pure nickel, monocrystalline silicon and pure copper according to the content of the copper-based amorphous components, sequentially adding the pure nickel, the monocrystalline silicon, the pure copper, the copper-zirconium alloy and the copper-titanium alloy into a vacuum induction electromagnetic oven according to the principle of high melting point and low melting point, and then heating to enable the copper-zirconium alloy, the monocrystalline silicon, the pure copper, the copper-zirconium alloy and the copper-titanium alloy to be completely melted, wherein the heating rate of induction electromagnetic rate is 50K/s;
and a second step of: vacuum gas atomization treatment is carried out on the melted mixed solution, wherein the gas atomization gas is argon, the vacuum degree of atomization is 5-10Pa, the argon pressure is 3MPa, the vacuum drying is carried out for 4 hours at 100 ℃ after gas atomization, and the powder with the particle size smaller than 30 mu m is sieved to obtain copper-based amorphous powder;
and a third step of: and uniformly mixing the copper-based amorphous powder and the nano particles by adopting a three-dimensional motion mixer to obtain the copper-based amorphous composite material.
The application of the copper-based amorphous composite material suitable for the marine ship shell in preparing the corrosion-resistant anti-fouling coating comprises the following specific application steps:
the first step: after degreasing and rust removal of the surface of the marine ship shell, sand blasting and roughening treatment are carried out on the surface of the marine ship shell by adopting white corundum sand with the granularity of 5-35 meshes;
and a second step of: and (3) spraying a copper-based amorphous composite material on the surface of the ship shell by adopting a cold spraying technology to form a corrosion-resistant and anti-fouling coating, wherein the spraying adopts argon gas, the spraying pressure is 4MPa, the carrier gas temperature is 600 ℃, the spraying distance is 30mm, the spraying speed is 50mm/s, and the powder feeding rotating speed is 1.5r/min.
Example 2
A copper-based amorphous composite material suitable for marine vessel shells, formed by compounding 93wt.% copper-based amorphous and 7wt.% nanoparticles (0.7 wt.% GO and 6.3wt.% YSZ); the weight percentages of the copper-based amorphous components are as follows: 18wt.% Zr, 10wt.% Ti, 3wt.% Ni, 0.5% si, the balance Cu.
The preparation method of the corrosion-resistant and anti-fouling material in this embodiment, and the application and construction method of the corrosion-resistant and anti-fouling material in the coating are the same as in embodiment 1.
Example 3
A copper-based amorphous composite material suitable for marine vessel shells, formed by compounding 94wt.% copper-based amorphous and 6wt.% nanoparticles (0.6 wt.% GO and 5.4wt.% YSZ); the weight percentages of the copper-based amorphous components are as follows: 18wt.% Zr, 10wt.% Ti, 3wt.% Ni, 0.5% si, the balance Cu.
The preparation method of the corrosion-resistant and anti-fouling material in this embodiment, and the application and construction method of the corrosion-resistant and anti-fouling material in the coating are the same as in embodiment 1.
Example 4
The preparation method of the prior Cu-Zr-Ti-Ni copper-based amorphous material is characterized by comprising the following specific components: 53wt.% Cu, 25wt.% Zr, 13wt.% Ti and 9wt.% Ni.
The preparation method of the copper-based amorphous powder, the application of the powder in the coating layer and the construction method in this example are the same as those in example 1.
Comparative example 1
Preparing a copper-based amorphous/nanoparticle composite material as a comparison material, wherein the copper-based amorphous/nanoparticle composite material is formed by compositing 92wt.% of copper-based amorphous and 8wt.% of nanoparticles; the nanoparticles were 0.8wt.% GO and 7.2wt.% YSZ; the weight percentages of the copper-based amorphous components are as follows: 18wt.% Zr, 10wt.% Ti, 0.5% si, the balance Cu.
The preparation method of the copper-based amorphous/nanoparticle composite material, the application of the composite material in the coating and the construction method in this comparative example are the same as in example 1.
Comparative example 2
Preparing a copper-based amorphous/nanoparticle composite material as a comparison material, wherein the copper-based amorphous/nanoparticle composite material is formed by compositing 92wt.% of copper-based amorphous and 8wt.% of nanoparticles; the nanoparticles were 0.8wt.% GO and 7.2wt.% YSZ; the weight percentages of the copper-based amorphous components are as follows: 25wt.% Zr, 10wt.% Ti, 3wt.% Ni, 0.5% si, the balance Cu.
The preparation method of the copper-based amorphous/nanoparticle composite material, the application of the composite material in the coating and the construction method in this comparative example are the same as in example 1.
Comparative example 3
Preparing a copper-based amorphous/nanoparticle composite material as a comparison material, wherein the copper-based amorphous/nanoparticle composite material is formed by compositing 92wt.% of copper-based amorphous and 8wt.% of nanoparticles; the nanoparticles were 0.8wt.% GO and 7.2wt.% YSZ; the weight percentages of the copper-based amorphous components are as follows: 18wt.% Zr, 20wt.% Ti, 3wt.% Ni, 0.5% si, the balance Cu.
The preparation method of the copper-based amorphous/nanoparticle composite material, the application of the composite material in the coating and the construction method in this comparative example are the same as in example 1.
The phases of the powders of examples 1-3 and comparative examples 1-3 were characterized by XRD, and FIG. 1 is the XRD diffraction patterns of the powders of example 1 and comparative example 1. As can be seen from fig. 1, the powder of example 1 had only one broad diffuse scattering peak, i.e., it had a completely amorphous structure within the XRD detection accuracy, whereas the powder of comparative example 1 had more crystallization peaks in the XRD pattern, i.e., its amorphous content was significantly reduced.
From the comparison of examples and comparative examples, it is found that when the kind of element or the content of element in the copper-based amorphous system is changed, the amorphous forming ability of the system is significantly reduced. The copper-based alloy system has excellent amorphous forming capability, can prepare powder with high amorphous content through an air atomization process, and adopts a cold spraying technology to completely inherit the high amorphous content into a coating. The Zr is taken as a large atom, so that the atom mismatch degree of the system can be increased, the amorphous forming capability of the system is improved, and the impurity elements which are inevitably existed in the smelting process of the Cu-based alloy can be removed by the good deoxidizing, nitrogen removing and sulfur removing capabilities of the Zr; the Ti has excellent corrosion resistance to wet chlorine and chloride solution, and the oxide of Ti has excellent sterilization capability, so that the corrosion resistance and biofouling resistance of the system can be improved; the Ni can obviously improve the strength, toughness and corrosion resistance of the alloy, and endows the copper-based alloy system with excellent corrosion resistance, mechanical property and machinability; si is used as a metalloid element, so that the critical cooling speed of the amorphous alloy can be reduced, and the fluidity of molten metal and the amorphous forming capacity of the system can be improved. In addition, by blending the ratio of amorphous macro atoms (Zr), intermediate atoms (Cu, ti, ni), and small atoms (Si), a large degree of atomic mismatch can be provided between atoms of the system, which leads to a decrease in free volume of the system and inhibition of diffusion of elements, thereby improving amorphous forming ability and stability of the system.
Example 5
Corrosion-resistant anti-fouling coating prepared from copper-based amorphous composite material applicable to marine vessel shells in examples 1-3 and example 4 existing Cu 53 Zr 25 Ti 13 Ni 9 The porosity, microhardness, corrosion resistance and biofouling resistance of the coating are tested, and in the embodiment, DT-2000 image analysis software is adopted to measure the porosity of the coating according to a gray scale method; measuring microhardness of the coating by adopting an HXD-1000TC microhardness tester, wherein the test load is 300g, and the retention time is 15s; the corrosion resistance of the coating is tested by adopting a Korset CS2350H electrochemical workstation, and the test solution is simulated seawater; the anti-biofouling properties of the coatings were tested according to GB/T5370-2007 standard. The specific detection results are as follows:
| examples | Porosity/% | microhardness/HV 0.3 | Corrosion rate/mm 3 ·h -1 | Loss of weight at offset/g.m -2 |
| 1 | 0.83 | 644 | 0.07 | 763 |
| 2 | 0.77 | 608 | 0.07 | 468 |
| 3 | 0.67 | 675 | 0.08 | 875 |
| 4 | 1.44 | 568 | 0.15 | 1384 |
Compared with the existing copper-based amorphous material, the copper-based amorphous/nanoparticle composite material provided by the invention has the advantages that the blocking effect of the nanomaterial on pores in the coating is exerted by adding GO and YSZ, and the corrosion resistance of the system is further improved. The composite material of the invention has lower corrosion rate and fouling weight loss, namely the copper-based amorphous/nanoparticle composite material of the invention has excellent corrosion resistance and antifouling property, and has outstanding substantive characteristics and remarkable progress.
Claims (9)
1. The utility model provides a copper base amorphous composite suitable for ocean warship hull which characterized in that: the material is formed by compositing 92-94wt.% of copper-based amorphous and 6-8wt.% of nanoparticles; the weight percentages of the copper-based amorphous components are as follows: 18-22wt.% Zr, 10-12wt.% Ti, 3-5wt.% Ni, 0.5-1.5wt.% Si, the balance Cu; the nanoparticles consist of Graphene Oxide (GO) and Yttria Stabilized Zirconia (YSZ).
2. The copper-based amorphous composite material suitable for use in marine vessel shells according to claim 1, wherein: the nano particles consist of GO and YSZ, and the content of GO is 5-10%.
3. The copper-based amorphous composite material suitable for use in marine vessel shells according to claim 1, wherein: the nanoparticles consist of GO and YSZ, and the content of GO is 10%.
4. The copper-based amorphous composite material suitable for use in marine vessel shells according to claim 1, wherein: the material is formed by compounding 93wt.% copper-based amorphous, 0.7wt.% GO, and 6.3wt.% YSZ; the weight percentages of the copper-based amorphous components are as follows: 20wt.% Zr, 11wt.% Ti, 4wt.% Ni, 1wt.% Si, the balance Cu.
5. The method for preparing a copper-based amorphous composite material suitable for a marine vessel shell according to any one of claims 1 to 4, comprising the steps of:
the first step: weighing copper-zirconium alloy, copper-titanium alloy, pure nickel, monocrystalline silicon and pure copper according to the content of the copper-based amorphous component, sequentially adding the pure nickel, the monocrystalline silicon, the pure copper, the copper-zirconium alloy and the copper-titanium alloy into a vacuum induction electromagnetic oven according to the principle of firstly high melting point and then low melting point, and then heating to enable the pure nickel, the monocrystalline silicon, the pure copper, the copper-zirconium alloy and the copper-titanium alloy to be completely melted;
and a second step of: vacuum gas atomization treatment is carried out on the melted mixed solution, wherein the gas atomization gas is argon, the atomization vacuum degree is 5-10Pa, the argon pressure is 3MPa, and after gas atomization, the powder with the particle size smaller than 30 mu m is vacuum-dried and sieved to obtain copper-based amorphous powder;
and a third step of: and uniformly mixing the copper-based amorphous powder and the nano particles by adopting a three-dimensional motion mixer to obtain the copper-based amorphous composite material.
6. The method for preparing the copper-based amorphous composite material applicable to marine vessel shells according to claim 5, wherein the method comprises the following steps of: the heating rate of the induction electromagnetic oven in the first step is 50-60K/s.
7. The method for preparing the copper-based amorphous composite material applicable to marine vessel shells according to claim 5, wherein the method comprises the following steps of: the drying temperature in the second step is 80-120 ℃ and the drying time is 2-4h.
8. Use of a copper-based amorphous composite according to any one of claims 1-4 for the preparation of a corrosion-resistant and anti-fouling coating.
9. The use according to claim 8, characterized by the steps of:
the first step: after degreasing and rust removal of the surface of the marine ship shell, sand blasting and roughening treatment are carried out on the surface of the marine ship shell by adopting white corundum sand with the granularity of 5-35 meshes;
and a second step of: and (3) spraying a copper-based amorphous composite material on the surface of the ship shell by adopting a cold spraying technology to form a corrosion-resistant and anti-fouling coating, wherein the spraying adopts argon gas, the spraying pressure is 4MPa, the carrier gas temperature is 600 ℃, the spraying distance is 30mm, the spraying speed is 50mm/s, and the powder feeding rotating speed is 1.5r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0372055A (en) * | 1989-08-11 | 1991-03-27 | Mitsui Eng & Shipbuild Co Ltd | Highly corrosion resistant amorphous alloy |
| CN110205567A (en) * | 2019-06-18 | 2019-09-06 | 河海大学 | A kind of piston ring Fe-based amorphous/MAX phase composite materials and its preparation method and application |
| CN111719107A (en) * | 2020-06-03 | 2020-09-29 | 河海大学 | Cavitation-corrosion-resistant anti-fouling material for propeller blades and preparation method thereof |
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| WO2013157596A1 (en) * | 2012-04-19 | 2013-10-24 | トピー工業株式会社 | PROCESS FOR PRODUCING AMORPHOUS SPRAYED COATING CONTAINING α-Fe NANOCRYSTALS DISPERSED THEREIN |
| US9815743B2 (en) * | 2012-05-09 | 2017-11-14 | Michelene Hall | Metal detectible ceramic material and method for making the same |
| US11814711B2 (en) * | 2019-12-31 | 2023-11-14 | Liquidmetal Coatings Enterprises, Llc. | System and method for applying high temperature corrosion resistant amorphous based coatings |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0372055A (en) * | 1989-08-11 | 1991-03-27 | Mitsui Eng & Shipbuild Co Ltd | Highly corrosion resistant amorphous alloy |
| CN110205567A (en) * | 2019-06-18 | 2019-09-06 | 河海大学 | A kind of piston ring Fe-based amorphous/MAX phase composite materials and its preparation method and application |
| CN111719107A (en) * | 2020-06-03 | 2020-09-29 | 河海大学 | Cavitation-corrosion-resistant anti-fouling material for propeller blades and preparation method thereof |
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