CN115627470A - Protective coating for marine vessel pipeline system and preparation method and application thereof - Google Patents
Protective coating for marine vessel pipeline system and preparation method and application thereof Download PDFInfo
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- CN115627470A CN115627470A CN202211159156.5A CN202211159156A CN115627470A CN 115627470 A CN115627470 A CN 115627470A CN 202211159156 A CN202211159156 A CN 202211159156A CN 115627470 A CN115627470 A CN 115627470A
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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
- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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Abstract
The invention discloses a protective coating for a marine vessel pipeline system and a preparation method thereof, wherein the material is formed by compounding 93-95wt.% of titanium-based amorphous particles and 5-7wt.% of nano particles; the titanium-based amorphous component comprises the following components in percentage by weight: 21-25wt.% Zr, 18-22wt.% Cu, 2-4wt.% Mo, 8-12wt.% Be, the balance being Ti; the nano-particles are made of nano TiO 2 And nano Ag. Adding a titanium-based amorphous raw material into an induction electromagnetic oven for heating and melting, and carrying out vacuum gas atomization on molten metal liquid to obtain titanium-based amorphous powder; the powder and the nano particles are applied to preparing the corrosion-resistant antifouling protective coating, the cold spraying technology is adopted to prepare the coating, and the titanium-based amorphous powder and the nano particles are continuously sprayed by adopting an out-of-circuit powder feeding method in the spraying process. The invention can obtain the protective coating with compact structure, high bonding strength, excellent corrosion resistance and antifouling performance, and is suitable for marine vessel pipesRoad systems and other severe working conditions.
Description
Technical Field
The invention belongs to the field of thermal spraying of material processing engineering, and particularly relates to a titanium-based amorphous/nano-particle composite protective material for a marine ship pipeline system, and a preparation method and application thereof.
Background
A marine pipeline system is a general term for pipelines, machinery and instrumentation that are used exclusively by ships to transport and remove liquids or gases in order to accomplish a certain task. The titanium alloy has the characteristics of high strength and excellent corrosion resistance, so that the prepared pipeline system has obvious advantages compared with the traditional pipeline systems made of carbon steel, stainless steel, copper alloy and the like. In marine environments, however, marine vessel pipe systems often suffer from both severe corrosion damage and marine biofouling damage. The titanium alloy is neither easy to corrode nor toxic in seawater, and thus can be a good attachment site for marine organisms. When the titanium-based alloy pipeline system is seriously polluted in the marine environment, on one hand, the secretion of marine organisms causes serious corrosion damage to metals, so that the pipeline system fails prematurely; on the other hand, the adhesion of fouling organisms causes the blockage of a pipeline system, and huge economic loss and potential safety hazard are brought.
By adding the second phase with excellent antibacterial and anti-biofouling properties into the titanium-based alloy, a composite material with good corrosion resistance and anti-biofouling properties is hopeful to be obtained. In addition, compared with the crystalline material, the amorphous material does not have defects such as grain boundaries and the like, and generally shows more excellent corrosion resistance, which indicates that the titanium-based amorphous/anti-pollution second-phase material has huge application potential in marine vessel pipeline systems. Because corrosion and fouling occur mainly on the surface of the material, preparing a protective coating on the alloy surface of the pipeline system is an economical and effective solution for improving the performance of the component compared with replacing a high-performance block material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the titanium-based amorphous composite material for the marine vessel pipeline system and the preparation method thereof, the material can be used for preparing the corrosion-resistant antifouling integrated coating, the coating has the advantages of compact tissue structure, high amorphous phase content, corrosion resistance and good antifouling performance, the overhaul period and the service life of the marine vessel pipeline system can be effectively prolonged, and the titanium-based amorphous composite material is suitable for industrial popularization.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a protective coating material for a marine vessel pipeline system is formed by compounding 93-95wt.% of titanium-based amorphous particles and 5-7wt.% of nano particles; the titanium-based amorphous component comprises the following components in percentage by weight: 21-25wt.% Zr, 18-22wt.% Cu, 2-4wt.% Mo, 8-12wt.% Be, the balance being Ti; the nano-particles are made of nano TiO 2 And nano Ag. Compared with the copper-based material in the prior art, the novel titanium-based amorphous/nano second-phase composite material has better corrosion resistance and mechanical property, so the protective coating material is prepared by compounding titanium-based amorphous and nano particles. The composite material has excellent corrosion resistance and antifouling performance, and can play a good role in protecting a marine vessel pipeline system.
The specific problem to be solved by the invention is that the corrosion resistance and pollution resistance of the coating material are enhanced by adding the amorphous material in the protective coating used in the marine vessel pipeline system, so that a component system with high amorphous forming capability is prepared, and the prepared amorphous shows better performance than the prior art material in the sea.
Meanwhile, the type and content of elements in the amorphous system directly determine the amorphous forming capability of the whole system. When the types and contents of elements in the amorphous system are different, the degree of mismatch of atomic sizes, enthalpy of mixing, topological structure of formation, and the like of the whole system are changed, and the amorphous forming ability and thermal stability are also changed correspondingly greatly. According to the requirements of corrosion and biological damage, elements are optimized and the content is determined, so that a system with high amorphous forming capability is obtained.
As a preferred technical scheme of the invention: the nano-particles are made of nano TiO 2 And nano Ag and nano TiO 2 Is contained in an amount of 30-70wt.%.
As a preferred technical scheme of the invention: the nano-particles are made of nano TiO 2 And nano Ag, and nano TiO 2 Is 50wt.%.
As a preferred technical scheme of the invention: the protective coating material for the marine vessel pipeline system consists of 94wt.% of titanium-based amorphous material and 3wt.% of nano TiO 2 And 3wt.% of nano Ag; the titanium-based amorphous alloy comprises the following components in percentage by weight: 23wt.% Zr, 20wt.% Cu, 3wt.% Mo, 10wt.% Be, with the balance being Ti.
The invention provides a preparation method of the protective coating material for the marine vessel pipeline system, which comprises the following steps:
the first step is as follows: respectively weighing titanium-zirconium alloy, copper-titanium alloy, pure molybdenum, beryllium and titanium according to the content of the titanium-based amorphous components, adding the weighed raw materials into a vacuum induction electromagnetic oven, and then heating to completely melt the raw materials;
the second step is that: and carrying out vacuum atomization treatment on the molten mixed liquid, wherein the gas atomization gas is argon, the atomization vacuum degree is 5-10Pa, the argon pressure is 3MPa, and after gas atomization, carrying out vacuum drying and screening on the powder with the particle size of less than 30 mu m to obtain the titanium-based amorphous powder.
The invention also provides application of the titanium-based amorphous/nano-particle composite material in preparing a protective coating for a marine vessel pipeline system.
The application of the titanium-based amorphous/nano-particle composite material in preparing the protective coating for the marine vessel pipeline system comprises the following steps:
the first step is as follows: pretreating the surface of the matrix, and after oil and rust removal, carrying out sand blasting and coarsening on the surface of the matrix by adopting brown corundum sand with the granularity of 5-35 meshes under the air pressure of 0.7-0.8 MPa;
the second step: preparing a coating on the surface of a substrate by adopting a cold spraying technology, and respectively continuously and uniformly spraying titanium-based amorphous alloy powder and TiO by adopting two spray guns in the spraying process 2 And (5) obtaining a protective coating by using Ag nano particles, wherein the spraying gas is argon, the pressure is 4MPa, the 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 invention has the following beneficial effects:
1. by designing the types and the contents of elements in the titanium-based alloy, the designed titanium-based alloy system has good amorphous forming capability, excellent mechanical property and corrosion resistance;
2. the raw material part for preparing the titanium-based amorphous alloy adopts the alloy block, and compared with the traditional method adopting pure metal as the raw material, the method has the advantages that the cost for preparing the amorphous alloy is lower;
3. by adding nano TiO 2 And nano Ag, on one hand, the nano particles can play a role in blocking pores in the coating, so that the corrosion resistance of the system is improved, and on the other hand, the nano Ag can play a role in blocking TiO 2 And Ag has excellent sterilization capability, and the anti-biological fouling performance of the composite protective coating is improved;
4. the titanium-based amorphous/nano-particle composite coating is prepared by cold spraying in different ways, the operation is simple, the uniform distribution of nano-particles in the composite coating is facilitated, the cold spraying technology can completely inherit the high amorphous content of amorphous powder into the coating, the coating with compact tissue structure and excellent performance is obtained, and the titanium-based amorphous/nano-particle composite coating is suitable for severe working conditions such as an ocean pipeline system;
5. the composite protective coating has the porosity of less than or equal to 1 percent and the amorphous content of more than or equal to 90 percent, has good corrosion resistance and pollution resistance, and experiments show that the seawater corrosion resistance rate of the coating is less than or equal to 0.05 mm/year, and the monthly biofouling weight loss is less than or equal to 900g/m 2 。
Drawings
Fig. 1 is an XRD spectrum of example 1 of the present invention.
Detailed Description
The invention will be better understood from the following examples. However, it is readily understood by those skilled in the art that the specific material proportions, process conditions, and results thereof, as described in the examples, are illustrative only and should not be taken as limiting the invention as described in detail in the claims.
Example 1
A protective coating material for a marine vessel pipeline system comprises 95wt.% of titanium-based amorphous material and 2.5wt.% of nano TiO 2 And 2.5wt.% of nano Ag; the titanium-based amorphous component comprises the following components in percentage by weight: 23wt.% Zr, 20wt.% Cu, 3wt.% Mo, 10wt.% Be, with the balance being Ti.
Wherein, the titanium-based amorphous powder is prepared by the following steps:
the first step is as follows: respectively weighing titanium-zirconium alloy, copper-titanium alloy, pure molybdenum, beryllium and titanium according to the content of the titanium-based amorphous components, adding the weighed raw materials into a vacuum induction electromagnetic oven, and then heating to completely melt the raw materials;
the second step: and carrying out vacuum gas atomization treatment on the molten mixed liquid, wherein the gas atomization gas is argon, the atomization vacuum degree is 5-10Pa, the argon pressure is 3MPa, and after gas atomization, carrying out vacuum drying and screening on the powder with the particle size of less than 30 mu m to obtain the titanium-based amorphous powder.
The application of the titanium-based amorphous/nano-particle composite material in preparing the protective coating for the marine vessel pipeline system comprises the following specific construction method:
the first step is as follows: pretreating the surface of the matrix, and after oil and rust removal, carrying out sand blasting and coarsening on the surface of the matrix by adopting brown corundum sand with the granularity of 5-35 meshes under the air pressure of 0.7-0.8 MPa;
the second step is that: preparing a coating on the surface of a substrate by adopting a cold spraying technology, and respectively and continuously and uniformly spraying titanium-based amorphous alloy powder and TiO by adopting two spray guns in the spraying process 2 And (5) obtaining a protective coating by using Ag nano particles, wherein the spraying gas is argon, the pressure is 4MPa, the temperature is 600 ℃, the spraying distance is 30mm, the spraying speed is 50mm/s, and the powder feeding rotating speed is 1.5r/min.
The titanium-based amorphous powder prepared in this example was subjected to XRD test, and the test pattern is shown in FIG. 1, wherein the abscissa of the XRD pattern is angle and the ordinate is intensity. As can be seen from the XRD pattern, the pattern only has a wide diffuse scattering peak, which indicates that the titanium-based amorphous prepared by the invention has good amorphous forming capability, and the amorphous content of the powder is close to 100 percent.
Example 2
A protective coating material for a marine vessel pipeline system comprises 94wt.% of titanium-based amorphous material and 3wt.% of nano TiO 2 And 3wt.% of nano Ag; the titanium-based amorphous component comprises the following components in percentage by weight: 23wt.% Zr, 20wt.% Cu, 3wt.% Mo, 10wt.% Be, with the balance being Ti.
The preparation method of the titanium-based amorphous material, the application of the amorphous/nanoparticle composite material in the coating and the construction method in the embodiment are the same as those in the embodiment 1.
Example 3
A protective coating material for a marine vessel pipeline system comprises 93wt.% of titanium-based amorphous material and 3.5wt.% of nano TiO 2 And 3.5wt.% of nano Ag; the titanium-based amorphous component comprises the following components in percentage by weight: 23wt.% Zr, 20wt.% Cu, 3wt.% Mo, 10wt.% Be, the balance being Ti.
The preparation method of the titanium-based amorphous material, the application of the amorphous/nanoparticle composite material in the coating and the application method in the embodiment are the same as those in embodiment 1.
Example 4
Protective coatings for marine vessel pipeline systems with a thickness of 500 μm were prepared according to examples 1 to 3, respectively, and tested for porosity, seawater corrosion resistance rate, and weight loss against biofouling. Measuring the porosity of the coating by using DT-2000 image analysis software; testing the seawater corrosion resistance rate of the coating by using a Conster CS2350H electrochemical workstation; the biofouling weight loss of the coatings was tested according to GB/T5370-2007 standard. The specific detection results are as follows:
| examples | Porosity/% | Corrosion rate/mm 3 ·h -1 | Fouling weight loss/g.m -2 |
| 1 | 0.83 | 0.03 | 889 |
| 2 | 0.77 | 0.04 | 843 |
| 3 | 0.67 | 0.04 | 755 |
Compared with the existing titanium-based alloy, the titanium-based amorphous/nano-particle composite coating prepared by the invention has remarkably excellent corrosion resistance, and is suitable for components working in marine environment. The titanium-based amorphous alloy consists of 5 elements, and Zr and Ti have larger atomic size mismatching degree, so that the amorphous forming capability of a system can be improved; cu can effectively improve the anti-biofouling performance of the system; mo can improve the pitting corrosion resistance of the alloy; be can play a role in improving the amorphous forming capability of a system and improving the mechanical property of the system. Furthermore, by adding nano TiO 2 And the nano Ag can play a role in blocking pores in the coating by the nano material, so that the corrosion resistance of the system is further improved; simultaneous nano TiO 2 2 Has good sterilization capability with nano Ag, and can effectively make up for the titanium-based alloy antibioticThe fouling performance is poor. In conclusion, the titanium-based amorphous/nanoparticle composite material disclosed by the invention has the advantages of lower corrosion rate and fouling weight loss, excellent corrosion resistance and anti-biofouling performance, outstanding substantive characteristics and remarkable progress.
Claims (7)
1. The utility model provides a marine vessel pipeline system is with protective coating material which characterized in that: the material is compounded by 93-95wt.% of titanium-based amorphous particles and 5-7wt.% of nano particles; the titanium-based amorphous component comprises the following components in percentage by weight: 21-25wt.% Zr, 18-22wt.% Cu, 2-4wt.% Mo, 8-12wt.% Be, the balance being Ti; the nano-particles are made of nano TiO 2 And nano Ag.
2. The protective coating material for marine vessel pipeline systems according to claim 1, wherein: the nano-particles are made of nano TiO 2 And nano Ag, and nano TiO 2 Is present in an amount of 30-70wt.%.
3. The protective coating material for marine vessel pipeline systems according to claim 1, wherein: the nano-particles are made of nano TiO 2 And nano Ag, and nano TiO 2 Is 50wt.%.
4. The protective coating material for marine vessel pipeline systems according to claim 1, wherein: the material consists of 94wt.% of titanium-based amorphous material and 3wt.% of nano TiO 2 And 3wt.% of nano Ag; the titanium-based amorphous alloy comprises the following components in percentage by weight: 23wt.% Zr, 20wt.% Cu, 3wt.% Mo, 10wt.% Be, with the balance being Ti.
5. The method for preparing the protective material for the marine vessel pipeline system according to any one of claims 1 to 4, wherein the titanium-based amorphous alloy is prepared by the following steps:
the first step is as follows: respectively weighing titanium-zirconium alloy, copper-titanium alloy, pure molybdenum, beryllium and titanium according to the content of the titanium-based amorphous components, adding the weighed raw materials into a vacuum induction electromagnetic oven, and then heating to completely melt the raw materials;
the second step: and carrying out vacuum atomization treatment on the molten mixed liquid, wherein the gas atomization gas is argon, the atomization vacuum degree is 5-10Pa, the argon pressure is 3MPa, and after gas atomization, carrying out vacuum drying and screening on the powder with the particle size of less than 30 mu m to obtain the titanium-based amorphous powder.
6. Use of the titanium-based amorphous/nanoparticle composite material according to any one of claims 1 to 4 for the preparation of a protective coating for marine vessel piping systems, characterized in that: the construction method of the composite protective coating comprises the following steps:
the first step is as follows: pretreating the surface of the matrix, after deoiling and derusting, performing sand blasting and coarsening on the surface of the matrix by adopting brown corundum sand with the granularity of 5-35 meshes under the air pressure of 0.7-0.8 MPa;
the second step is that: preparing a coating on the surface of a substrate by adopting a cold spraying technology, and respectively continuously and uniformly spraying titanium-based amorphous alloy powder and TiO by adopting two spray guns in the spraying process 2 And (4) adding Ag nano particles to obtain a protective coating, wherein the spraying gas is argon, the pressure is 4MPa, the temperature is 600 ℃, the spraying distance is 30mm, the spraying speed is 50mm/s, and the powder feeding speed is 1.5r/min.
7. Use according to claim 6, characterized in that: the seawater corrosion resistant rate of the protective coating for the marine vessel pipeline system is less than or equal to 0.05 mm/year, and the monthly mean biofouling weight loss is less than or equal to 900g/m 2 。
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| CN202211159156.5A CN115627470A (en) | 2022-09-22 | 2022-09-22 | Protective coating for marine vessel pipeline system and preparation method and application thereof |
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| CN202211159156.5A CN115627470A (en) | 2022-09-22 | 2022-09-22 | Protective coating for marine vessel pipeline system and preparation method and application thereof |
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