CN109135501B - Anti-eccentric wear anticorrosive powder coating and preparation method thereof - Google Patents
Anti-eccentric wear anticorrosive powder coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a powder coating, in particular to an anti-eccentric anti-corrosion powder coating. The invention provides an anti-eccentric wear anticorrosive powder coating in order to improve the anti-eccentric wear performance of an oil pipe inner wall anticorrosive coating in an oil field. The coating comprises the following components: 54.5-68.1% of resin, 9.5-14.8% of curing agent, 10-15% of self-made titanium-molybdenum alloy nano powder, 10-15% of self-made modified wear-resistant anti-friction filler and 0.8% of auxiliary agent; the percentage is mass percentage. The resin is selected from phenolic resin modified epoxy resin; the molecular weight range of the epoxy resin is 2000-2500. The coating solves the problems of eccentric wear, corrosion, high temperature, scaling, short service life and the like which are puzzled for a long time in the petroleum field such as oil extraction pipes and water well pipes. The service life of the oil pipe coated with the coating on the inner wall of the oil pipe is prolonged by 3-5 times compared with the original oil pipe.
Description
Technical Field
The invention relates to a powder coating, in particular to an anti-eccentric anti-corrosion powder coating and a preparation method thereof.
Background
With the continuous deepening of oil field development, the comprehensive water content of produced liquid gradually rises, most oil fields enter a high-water-content development period, the content of chloride ions is high, a large amount of media such as carbon dioxide, hydrogen sulfide, sulfate reducing bacteria and the like exist, and the problem of corrosion of underground oil pipes is serious day by day. In an oil well, due to a well depth structure, the sucker rod is influenced by descending resistance, the friction and abrasion of the sucker rod on the inner wall of the oil pipe are serious, and the mutual action of corrosion and eccentric wear causes a large amount of scrapping of the oil pipe.
In the water injection well, the normal test and allocation of the water injection well are seriously influenced by the scaling and corrosion of the water injection pipe column, the service life of the pipe column is shortened, and the eccentric wear and corrosion problems of the underground oil pipe become bottlenecks which restrict the production of the oil field and reduce the cost and increase the benefit.
The corrosion prevention and eccentric wear prevention process adopted by the prior art comprises the following steps:
1. corrosion prevention of oil pipes of water injection wells:
in order to improve the corrosion and scale prevention capability of the water injection well, the process of a glass fiber reinforced plastic lining, nitriding, epoxy resin powder, a stainless steel lining and the like are mainly applied to the oil field in recent years.
2. Oil well pipe anticorrosion, prevent eccentric wear:
the eccentric wear prevention technology is tested and applied for decades, and the main technology is as follows: HDPE, glass fiber reinforced plastic oil pipe and the like are lined.
The process plays a positive role in the fields of corrosion prevention and eccentric wear prevention of oil fields to different degrees.
Disclosure of Invention
In order to improve the eccentric wear resistance of the oil pipe inner wall anticorrosive paint in the oil field, the invention provides an eccentric wear resistant anticorrosive powder coating, which is a flat, uniform and compact protective layer formed on the inner wall of the oil pipe by the rare earth nano titanium molybdenum eccentric wear resistant anticorrosive powder paint added with self-made titanium molybdenum alloy nano powder and self-made modified wear-resistant anti-friction filler. The coating solves the problems of eccentric wear, corrosion, high temperature, scaling, short service life and the like which are puzzled for a long time in the petroleum field such as oil extraction pipes and water well pipes. The service life of the oil pipe coated with the coating on the inner wall of the oil pipe is prolonged by 3-5 times compared with the original oil pipe.
The technical scheme adopted by the invention is as follows:
the invention provides an anti-eccentric wear anticorrosive powder coating, which comprises the following components: 54.5-68.1% of resin, 9.5-14.8% of curing agent, 10-15% of self-made titanium-molybdenum alloy nano powder, 10-15% of self-made modified wear-resistant anti-friction filler and 0.8% of auxiliary agent; the percentage is mass percentage.
Further, the coating comprises the following components: 59.4 percent of resin, 13.6 percent of curing agent, 13.2 percent of self-made titanium molybdenum alloy nano powder, 13 percent of self-made modified wear-resistant anti-friction filler and 0.8 percent of auxiliary agent; the percentage is mass percentage.
The auxiliary agent comprises one or more of a water repellent, an anti-blocking agent (a loosening agent or a bulking agent), a degassing agent, a defoaming agent, a dispersing agent, an antistatic agent, a frictional electrification auxiliary agent, an accelerator, a powdering rate modifier, a scratch-resistant agent, an anti-sagging agent, a plasticizer and an antioxidant.
The auxiliary agents are selected from powdery auxiliary agents.
Further, the resin is selected from phenolic resin modified epoxy resin; the mass ratio of the epoxy resin to the phenolic resin is 1: 0.1-0.2; the molecular weight range of the epoxy resin is 2000-2500.
Further, the curing agent is a latent curing agent.
Further, the latent curing agent is selected from one of dicyandiamide, dicyandiamide modified imidazole, cyanate ester modified imidazole, organic acid modified imidazole, metal inorganic salt modified imidazole, acid anhydride modified imidazole, organic hydrazide, lewis acid-amine complex, and acetylacetone transition metal complex.
Further, the self-made titanium molybdenum alloy nano powder comprises: 50-55% of titanium-containing coarse powder, 37-42% of molybdenum-containing coarse powder, 3% of a dispersing agent and 5% of a bonding agent; the percentage is mass percentage; the self-made titanium molybdenum alloy nano powder is prepared by a mechanochemical method, and the steps are as follows:
1) premixing: adding the raw material coarse powder into a ball mill according to the formula amount for mixing;
2) primary grinding: filling inert gas into the ball milling tank, and performing dry milling to fully ball mill the materials, keeping the inert gas environment, and performing primary refining;
3) high-energy ball milling: under the inert gas environment, the rotating speed is increased to further refine the materials, so that the materials react with the added bonding agent; performing high-energy ball milling to obtain slurry;
4) milling: the powder process comprises two steps: a. separating the dispersant and the solid powder in the slurry by using a high-speed centrifuge; b. drying the solid powder under the protection of inert gas or under a certain vacuum degree; the obtained dried product is the titanium molybdenum alloy nano powder.
The inert gas is nitrogen.
Further, the self-made titanium molybdenum alloy nano powder is in a spherical net connection state, and the average grain diameter is 18 +/-2 nm.
Furthermore, the self-made modified wear-resistant anti-friction filler selects metal oxide as wear-resistant aggregate, wear-resistant ceramic powder as filler, directional and non-directional reinforced ceramic fiber powder as internal force reinforcement, spherical graphite powder and molybdenum powder as surface smoothing agent; the metal oxide comprises 15-20% of magnesium oxide, 20-25% of aluminum oxide, 30-35% of silicon oxide and 25-30% of zirconium oxide; premixing the raw materials; the percentage is mass percentage.
Further, the coating is formed by coating and curing rare earth nano titanium molybdenum eccentric wear prevention anticorrosion powder paint; the preparation method of the rare earth nano titanium molybdenum eccentric wear-resistant anticorrosive powder coating comprises the following steps: weighing raw materials, premixing the raw materials, melting, extruding, cooling, grinding and sieving.
Further, the coating is coated on the inner wall of the oil pipe; the construction steps of the coating are as follows: processing a raw pipe, preheating the raw pipe, coating paint and curing the paint; the original pipe treatment comprises original pipe thread protection cleaning, original pipe pretreatment, high-temperature cleaning, sand blasting and rust removing, demagnetization treatment, primary purging, thread protection anchoring and secondary purging; the primary tube is preheated by intermediate frequency heating; the coating adopts spray coating; the coating curing is a rotational curing.
Further, the coating comprises preheating a pipe body of the original pipe and spraying the coating; the preheating temperature of the tube body is 220-260 ℃; the preheating time of the pipe body is less than or equal to 3 h; the thickness of the coating is uniform, and the thickness of a dry film of the coating is not less than 600 microns; the curing temperature of the coating is 190-230 ℃; the curing time of the coating is not less than 1 h.
Further, the abrasion resistance of the coating was tested according to the method of standard SY/T6717-2016 appendix D, reaching 4.9L/μm.
The coating is a flat, uniform and dense protective layer.
The anti-eccentric wear anticorrosive powder coating provided by the invention has the following advantages:
1) the coating has excellent anti-corrosion performance;
2) the coating has good adhesive force and does not fall off after being used for a long time in a wet and hot state in the pit;
3) the self-lubricating oil has a unique self-lubricating function and plays a role in protecting a grinding piece;
4) the descending resistance is reduced, and the energy-saving effect is achieved;
5) the dry film thickness of the coating can be controlled at 800-;
6) the damaged external thread of the oil pipe can be turned and buckled again or the short section can be changed.
Drawings
FIG. 1 is a process for preparing self-made titanium molybdenum alloy nano powder provided by the invention;
FIG. 2 illustrates the curing mechanism of the epoxy resin of the present invention.
Detailed Description
In order to make it easier to understand the anti-eccentric anti-corrosion powder coating provided by the present invention, the following detailed description is made in conjunction with fig. 1-2 and specific examples of the present invention as follows:
the wear-resistant coating is based on general organic resin, if special measures such as nano filling and the like are not considered, the high hardness of the whole cured film means that the glass transition temperature is high, the high crosslinking degree is indicated, or a sufficient long flexible chain segment is lacked in a crosslinking network, so that the brittleness is easily increased, stress concentration is easily caused under the shearing friction of external force, the stress cannot be transmitted and dispersed through a surrounding structure, and the stress point of the film layer is subjected to brittle collapse. On the contrary, if one pursues flexibility of the cured film, neglecting the crosslinking density tends to result in insufficient mechanical strength of the crosslinked network itself, and the crosslinked network of dilute sulfur may be broken under external force friction shear, and the abrasion resistance is also poor. From the viewpoint of forensics, it is desirable that the cured film have a good balance of hardness and flexibility, which is generally understood as a balance of high crosslinking density and high flexibility. For a cured film with micro-cross-linking or a more uniform microstructure (ideal situation of equidistant cross-linking points), if the two systems which are seemingly contradictory to each other are almost non-uniform and cannot simultaneously obtain high hardness and high flexibility, then the cross-linking system is made into a micro-non-uniform structure, namely a micro-phase separation which is commonly called a micro-phase separation, and has a 'hard micro-phase' with high cross-linking degree and a cross-linking 'soft micro-phase' meeting the high flexibility. The phase is connected with the phase through chemical bond. Under external force shearing, if the 'soft micro-phase' is stressed, the stress can be dispersed by the adjacent high-crosslinking 'hard micro-phase', so that the soft chain is protected from being broken: if the 'hard micro-phase' is stressed, the stress can be transmitted and dispersed to the adjacent 'soft micro-phase'. In conclusion, this microphase separation allows better stress dispersion and improved wear resistance.
By adopting the principle, epoxy resin and phenolic resin are used as main film forming resins, the two resins not only have excellent heat resistance and corrosion resistance, the epoxy resin is used as a soft phase, the phenolic resin is used as a hard phase, certain hard and soft phases are alternated, the crosslinking density is high, the soft micro-phase is sufficient, inorganic particles and organic resin are two phases with completely different performances, and basic problems to be solved for fully exerting the reinforcing and wear-resisting effects of inorganic fillers in the coating comprise: the three problems of wetting and penetration of inorganic particles, stable dispersion and firm combination of the particles and a paint film matrix are different in side weight surface and closely related, and the wear resistance and the friction resistance of the paint film matrix can be greatly improved by filling specially modified compression-resistant high-hardness fillers with certain particle size (including but not limited to) such as magnesium oxide, aluminum oxide, silicon oxide, zirconium oxide and the like as bone spots.
The invention adopts a mechanochemical method for the first time at home and abroad to prepare the titanium-molybdenum alloy nano powder with uniform tissue and component distribution at high efficiency and low cost, and the titanium-molybdenum alloy nano powder has high activity combined with high molecular organic and becomes a special excellent coating modifier. The detection of SEM, TEM, XRD, laser particle size distribution instrument and the like proves that the titanium-molybdenum alloy nano powder is in a spherical net connection state, and the average particle size is about 18 nm. The metal such as titanium, molybdenum, etc. has excellent corrosion resistance which is difficult to compare with other elements, and the high-strength corrosion-resistant titanium alloy has the following characteristics in most media except the corrosion resistance similar to that of pure titanium, etc.:
the specific strength (tensile strength/density) is high in the temperature range of-100 to 300 ℃, and the tensile strength can reach over 1000 Mpa;
secondly, the hardness can reach more than HV300 and even higher through proper component control;
good heat resistance;
and fourthly, the low temperature resistance is good.
In addition, the super corrosion-resistant titanium-molybdenum alloy also has good corrosion resistance in high temperature, special marine environment and occasions with strong corrosivity. Through the adjustment of the adaptive components, the alloy also has excellent wear resistance.
The special properties of the nano particles, such as surface effect, small-size effect, quantum size effect, macroscopic quantum tunneling effect and the like, due to the characteristics of the nano particles show great superiority in the development of new materials: the nano coating modifier enables the coated surface to be more uniform due to small-size effect than the traditional modifier, does not generate surface defect, generates permeation and filling effect due to the interaction of nano particles and a substrate interface, enhances the interface combination of a coating substrate, enables the coating substrate to be connected into a whole, can effectively overcome the defects of compactness, poor adhesion and the like of the traditional coating, greatly improves the properties of permeability resistance, chemical resistance, thermal stability, oxidation resistance, low temperature resistance and the like of a coating film, prevents corrosion medium from permeating, and endows the coating with excellent corrosion-resistant comprehensive performance; in addition, the huge interface of the nano-particles has very high surface energy, so that the mechanical properties of the coating, such as tensile strength, hardness, wear resistance and the like, are improved by times compared with those of the conventional coating, and the interface shows good toughness and ductility due to the migration of atoms which are flocculated by the interface.
In the embodiment of the invention, the self-made titanium molybdenum nano powder comprises the following components in percentage by weight: 52% of titanium coarse powder, 40% of molybdenum coarse powder, 3% of a dispersing agent and 5% of a bonding agent; the percentage is mass percentage.
The self-made titanium molybdenum alloy nano powder is prepared by a mechanochemical method, and the steps are as follows:
1) premixing: adding the raw material coarse powder into a ball mill according to the formula amount for mixing;
2) primary grinding: filling inert gas into the ball milling tank, and performing dry milling to fully ball mill the materials, keeping the inert gas environment, and performing primary refining;
3) high-energy ball milling: under the inert gas environment, the rotating speed is increased to further refine the materials, so that the materials react with the added bonding agent; performing high-energy ball milling to obtain slurry;
4) milling: the powder process comprises two steps: a. separating the dispersant and the solid powder in the slurry by using a high-speed centrifuge; b. drying the solid powder under the protection of inert gas or under a certain vacuum degree; the obtained dried product is the titanium molybdenum alloy nano powder.
The inert gas is nitrogen.
The self-made modified wear-resistant anti-friction filler comprises the following components: 10% of magnesium oxide, 12% of aluminum oxide, 18% of silicon oxide and 15% of zirconium oxide; 25% of wear-resistant ceramic powder, 10% of ceramic fiber powder, 5% of spherical graphite powder and 5% of molybdenum powder; the components are premixed according to the proportion; the percentage is mass percentage.
The metal oxide is used as wear-resistant aggregate, the wear-resistant ceramic powder is used as filler, the directional and non-directional reinforced ceramic fiber powder is used as internal force reinforcement, and the spherical graphite powder and the molybdenum powder are used as surface smoothing agents.
The auxiliary agent comprises one or more of a water repellent, an anti-caking agent (a loosening agent or a bulking agent), a degassing agent, a defoaming agent, a powdering rate modifier and a scratch-proof agent.
The auxiliary agents are selected from powdery auxiliary agents.
The resin is selected from phenolic resin modified epoxy resin; the mass ratio of the epoxy resin to the phenolic resin is 1: 0.1-0.2; the molecular weight range of the epoxy resin is 2000-2500.
The curing agent is a latent curing agent.
The latent curing agent is selected from one of dicyandiamide, dicyandiamide modified imidazole, cyanate ester modified imidazole, organic acid modified imidazole, metal inorganic salt modified imidazole, anhydride modified imidazole, organic hydrazide, Lewis acid-amine complex and acetylacetone transition metal complex.
The preparation method of the rare earth nano titanium molybdenum eccentric wear-resistant anticorrosive powder coating comprises the following steps: weighing raw materials, premixing the raw materials, melting, extruding, cooling, grinding and sieving.
The coating is formed by coating and curing rare earth nano titanium molybdenum eccentric wear prevention anticorrosion powder paint; the coating is coated on the inner wall of the oil pipe; the construction steps of the coating are as follows: processing a raw pipe, preheating the raw pipe, coating paint and curing the paint;
the original pipe treatment comprises original pipe thread protection cleaning, original pipe pretreatment, high-temperature cleaning, sand blasting and rust removing, demagnetization treatment, primary purging, thread protection anchoring and secondary purging;
the primary tube is preheated by intermediate frequency heating;
the coating adopts spray coating;
the coating curing is a rotational curing.
The coating comprises preheating a pipe body of a primary pipe and spraying the coating; the preheating temperature of the tube body is 220-260 ℃; the preheating time of the pipe body is less than or equal to 3 h; the thickness of the coating is uniform, and the thickness of a dry film of the coating is not less than 600 microns; the curing temperature of the coating is 190-230 ℃; the curing time of the coating is not less than 1 h.
The wear resistance of the coating formed by the construction method of the anti-eccentric wear anticorrosive powder coating is tested according to the method of standard SY/T6717-2016 appendix D and reaches 4.9L/mum.
The coating is a flat, uniform and dense protective layer.
Example 1:
59.4 percent of resin, 13.6 percent of curing agent, 13.2 percent of self-made titanium molybdenum alloy nano powder, 13 percent of self-made modified wear-resistant anti-friction filler and 0.8 percent of auxiliary agent.
The resin is phenolic resin modified epoxy resin (molecular weight 2000-2500); the mass ratio of the epoxy resin to the phenolic resin is 1: 0.1.
The curing agent adopts dicyanodiamine.
The auxiliary agent comprises 0.3% of organosilicon powder water repellent, 0.2% of Lanco TM A1601 defoaming agent and 0.3% of nano aluminum oxide anti-caking agent.
Example 2:
in the same way as in example 1, the mass ratio of the epoxy resin to the phenolic resin is 1: 0.2; the curing agent adopts acid anhydride modified imidazole.
Example 3:
in the same way as in example 1, 54.5% of resin, 14.8% of curing agent, 15% of self-made titanium-molybdenum alloy nano powder and 14.9% of self-made modified wear-resistant anti-friction filler.
Example 4:
in the same way as in example 2, 68.1 percent of resin, 11.1 percent of curing agent, 10 percent of self-made titanium-molybdenum alloy nano powder and 10 percent of self-made modified wear-resistant anti-friction filler.
Example 5:
in the same way as in example 1, 64.7 percent of resin, 9.5 percent of curing agent, 15 percent of self-made titanium-molybdenum alloy nano powder and 10 percent of self-made modified wear-resistant anti-friction filler.
Example 6:
like example 2, 64.7% of resin, 9.5% of curing agent, 10% of self-made titanium-molybdenum alloy nano powder and 15% of self-made modified wear-resistant anti-friction filler; the curing agent adopts Lewis acid-amine complex.
Comparative example 1:
like example 1, 0% of self-made titanium molybdenum alloy nano powder and 0% of self-made modified wear-resistant anti-friction filler; 26.2 percent of general filler.
The detection method of the coating performance comprises the following steps:
and (3) after the test piece is manufactured according to the requirements of the standard SY/T6717-2016, performing performance detection:
1 coating adhesion test: SY/T6717-2016 appendix B;
2 coating abrasion resistance test: SY/T6717-2016 appendix D;
3 chemical resistance assay, performing standard SY/T6717-2016.
The coatings of the respective examples were tested according to the above test method, and the results are shown in the following table.
Table one coating performance test results
According to the detection results in the table I, the abrasion resistance (sand falling method) of the examples 1 to 6 can reach more than 4.9mg compared with the comparative example, the comprehensive performance is greatly improved, and good beneficial effects are obtained. Further, the coatings of examples 1-2 have better wear resistance and more excellent overall properties.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the disclosure of the present invention are covered by the scope of the claims of the present invention.
Claims (7)
1. An anti-eccentric anti-corrosion powder coating, characterized in that the coating comprises the following components: 54.5-68.1% of resin, 9.5-14.8% of curing agent, 10-15% of self-made titanium-molybdenum alloy nano powder, 10-15% of self-made modified wear-resistant anti-friction filler and 0.8% of auxiliary agent; the percentage is mass percentage;
the self-made titanium molybdenum alloy nano powder comprises: 50-55% of titanium-containing coarse powder, 37-42% of molybdenum-containing coarse powder, 3% of a dispersing agent and 5% of a bonding agent; the percentage is mass percentage; the self-made titanium molybdenum alloy nano powder is prepared by a mechanochemical method, and the steps are as follows:
1) premixing: adding the raw material coarse powder into a ball mill according to the formula amount for mixing;
2) primary grinding: filling inert gas into the ball milling tank, and performing dry milling to fully ball mill the materials, keeping the inert gas environment, and performing primary refining;
3) high-energy ball milling: under the inert gas environment, the rotating speed is increased to further refine the materials, so that the materials react with the added bonding agent; performing high-energy ball milling to obtain slurry;
4) milling: the powder process comprises two steps: a. separating the dispersant and the solid powder in the slurry by using a high-speed centrifuge; b. drying the solid powder under the protection of inert gas or under a certain vacuum degree; the obtained dried substance is the titanium molybdenum alloy nano powder;
the inert gas is nitrogen;
the self-made modified wear-resistant anti-friction filler adopts metal oxide as wear-resistant aggregate, wear-resistant ceramic powder as filler, directional and non-directional reinforced ceramic fiber powder as internal force reinforcement, and spherical graphite powder and molybdenum powder as surface smoothing agents; the metal oxide comprises 15-20% of magnesium oxide, 20-25% of aluminum oxide, 30-35% of silicon oxide and 25-30% of zirconium oxide; premixing the raw materials; the percentage is mass percentage;
the resin is selected from phenolic resin modified epoxy resin; the mass ratio of the epoxy resin to the phenolic resin is 1: 0.1-0.2; the molecular weight range of the epoxy resin is 2000-2500.
2. The anti-eccentric anti-corrosion powder coating according to claim 1, wherein the curing agent is a latent curing agent.
3. The anti-eccentric anti-corrosion powder coating as claimed in claim 1, wherein the self-made titanium molybdenum alloy nanopowder is in a spherical net connection state, and the average particle size is 18 ± 2 nm.
4. The method for preparing the anti-eccentric anti-corrosion powder coating according to any one of claims 1 to 3, wherein the coating is formed by coating and curing an anti-eccentric anti-corrosion powder coating; the preparation method of the anti-eccentric wear anticorrosive powder coating comprises the following steps: weighing raw materials, premixing the raw materials, melting, extruding, cooling, grinding and sieving.
5. The method for constructing an anti-eccentric anti-corrosion powder coating as claimed in claim 4, wherein the coating is coated on the inner wall of the oil pipe; the construction steps of the coating are as follows: processing a raw pipe, preheating the raw pipe, coating paint and curing the paint;
the original pipe treatment comprises original pipe thread protection cleaning, original pipe pretreatment, high-temperature cleaning, sand blasting and rust removing, demagnetization treatment, primary purging, thread protection anchoring and secondary purging;
the primary tube is preheated by intermediate frequency heating;
the coating adopts spray coating;
the coating curing is a rotational curing.
6. The method for constructing the anti-eccentric anti-corrosion powder coating according to claim 5, wherein the coating comprises preheating a pipe body of a primary pipe and spraying the coating; the preheating temperature of the tube body is 220-260 ℃; the preheating time of the pipe body is less than or equal to 3 hours; the film thickness of the coating is uniform, and the dry film thickness of the coating is more than or equal to 600 microns; the curing temperature of the coating is 190-230 ℃; the curing time of the coating is more than or equal to 1 h.
7. A coating formed by the construction method of the anti-eccentric anti-corrosion powder coating according to claim 5 or 6, wherein the wear resistance of the coating is tested according to the method of standard SY/T6717-2016 appendix D and reaches 4.9L/μm.
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| CN113102197A (en) * | 2021-03-01 | 2021-07-13 | 胜利油田金岛实业有限责任公司 | Polyfluorinated ceramic anticorrosive oil pipe and production process thereof |
| CN113603948B (en) * | 2021-08-27 | 2023-03-31 | 温州市巨创鞋材有限公司 | Wear-resistant elastic sole and preparation process thereof |
| CN114836068A (en) * | 2022-04-27 | 2022-08-02 | 株洲飞鹿高新材料技术股份有限公司 | Nano slurry, preparation method thereof and nano modified anticorrosive paint |
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| CN101081434B (en) * | 2006-05-29 | 2010-08-04 | 长沙科星纳米工程技术有限公司 | Method for preparing titanium alloy nanometer powder |
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