CN112663056B - Phosphate-based high-temperature corrosion-resistant ceramic coating on surface of metal titanium and preparation method thereof - Google Patents
Phosphate-based high-temperature corrosion-resistant ceramic coating on surface of metal titanium and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of metal titanium surface protection, in particular to a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium and a preparation method thereof; coating materialThe paint consists of the following components: al (H) 2 PO 4 ) 3 、Al 2 O 3 And CuO, which is formed by high-temperature curing at 950-1000 ℃ after being coated on the surface of the titanium matrix by a screen printing method. After the coating prepared by the invention is subjected to an oxidation test for 1100 hours at 950 ℃, the corrosion resistance is improved by 96 percent, and the tensile strength between the substrate and the coating is 8.1MPa. The coating has simple process and lower cost, can be widely applied to the high-temperature corrosion protection of the metal titanium in the aerospace industry, the energy industry and the chemical industry, and has the advantages of simple preparation process, stable physicochemical properties at high temperature and the like.
Description
Technical Field
The invention relates to the technical field of metal titanium surface protection, in particular to a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium and a preparation method thereof.
Background
In recent years, metal titanium has become a main application material in the fields of aerospace, energy and chemical industry because it exhibits excellent physicochemical properties such as low density, high strength, high melting point and low thermal expansion coefficient in actual industrial production, compared with conventional metal materials. However, titanium metal is very easily oxidized at a high temperature of 700 ℃ or higher, and a loose oxide film is generated on the surface of a substrate, so that oxygen is easily introduced into the titanium metal to react with the substrate, thereby severely limiting the application of the titanium metal at the high temperature.
In recent years, the coating of protective coatings on the surface of metallic titanium has become an effective means for high-temperature corrosion protection. The technique adopts Al 2 O 3 CuO as main material and Al (H) 2 PO 4 ) 3 The copper oxide-phosphate adhesive is a solvent, a screen printing method is adopted to form a coating on the surface of a metal, the materials can generate polymerization reaction at high temperature, and a continuous distribution phase with covalent bonds and ionic bonds in staggered connection is formed after curing, so that the copper oxide-phosphate adhesive has higher adhesive cohesion and can better cover the surface of a metal matrix. Phosphate-based ceramics made by the above methodThe coating has low fineness and strong adhesive capacity, can obtain certain strength without high-temperature sintering, and simultaneously has the advantages of simple technical process, convenient operation, strong high-temperature corrosion resistance and the like.
In document 1, a micro-arc oxidation coating preparation process is adopted, a titanium dioxide passivation layer of about 5 μm is formed on the surface of metal titanium through local electrification treatment, so that a good high-temperature protection effect on the metal titanium can be achieved, and then a high-temperature oxidation resistance test is performed, and the test result shows that a test piece still presents good geothermal stability at 800 ℃.
Document 2 discloses a laser cladding technique for preparing Ti on a titanium substrate surface 3 The Al coating has a thickness of about 5 μm and still exhibits excellent high-temperature oxidation resistance at 800 ℃.
In document 3, the inorganic phosphate coating prepared on the surface of the titanium-based alloy still can show good high-temperature oxidation resistance at 950 ℃.
The prior art has two main disadvantages: (1) The existing technologies of laser cladding, micro-arc oxidation and the like are generally adopted for preparing the coating on the surface of the metal titanium, and the technologies need special operation equipment, have higher cost and longer consumed time, and the coating uniformity of the coating is difficult to control. (2) Although the coating sample prepared by the existing phosphate ceramic raw material can show better high-temperature oxidation resistance at 950 ℃, the oxidation resistance of the coating sample still needs to be enhanced.
Document 1: jin, F.Y., chu, paul.K., wang, K., ZHao, J., huang, A.P.and Tong, H.H., thermal stability of film prepared on titanium by micro-arc oxidation, materials Science and Engineering: A.,2008,476 (1-2), 78-82.
Document 2: guo, C, zhou, J.S., ZHao, J.R., wang, L.Q., yu, Y.J.and Chen, J.M., improvement of the Oxidation and Wear Resistance of Pure Ti by Laser-Cladding Ti 3 Al Coating at Elevated Temperature.Tribol.Lett.,2011,42(2),151-159.
Document 3: a phosphate coating for high-temp protection of Ti-base high-temp alloy and its preparing process, CN 105400240B
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium and a preparation method thereof, so as to solve the problems that the metal titanium is easy to oxidize at high temperature and the application is severely limited.
The invention adopts the following technical scheme:
on one hand, the invention provides a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium, which mainly comprises the following components in parts by mass: 45-55 parts of Al (H) 2 PO 4 ) 3 30-40 parts of Al 2 O 3 And 10 to 20 parts of CuO.
Further, the Al (H) 2 PO 4 ) 3 The solution is prepared from Al (OH) with a molar ratio of 1 3 And H 3 PO 4 Solution (H) 3 PO 4 90-95% by mass).
In another aspect, the present invention provides a method for preparing a phosphate-based high-temperature corrosion-resistant ceramic coating on a metallic titanium surface, comprising the following steps:
1) After the metal titanium matrix is ultrasonically cleaned, the SiC sand paper is used for polishing the surface of the metal, and then the metal is ultrasonically cleaned again;
2) Mixing Al (H) 2 PO 4 ) 3 Solution, al 2 O 3 And CuO are fully ball-milled and stirred to form a coating;
3) Coating the coating on a substrate to form a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of the metallic titanium, heating for high-temperature curing, and cooling along with a furnace after heat preservation to finish the preparation.
Further, in the step 1), the ultrasonic cleaning time is 50-65 minutes.
Further, in the step 1), the surface stains are removed by using an alcohol solution 20-30 minutes before the ultrasonic cleaning, and the surface alcohol residues are removed by using distilled water 30-35 minutes later.
Further, the SiC sand paper is 1000-1500 meshes of SiC sand paper.
Further, in step 3), the process of coating the paint is as follows: and coating the coating on the substrate by adopting a screen printing mode.
Further, the high-temperature curing temperature is 900-1000 ℃, and the temperature is kept for 1.5-2 hours. Further, the high-temperature curing temperature is 950-1000 ℃.
Further, the high-temperature curing is carried out in a muffle furnace and is prepared in an argon atmosphere, wherein the heating rate is 2.8-3 ℃/min at 0-500 ℃, 1.7-2 ℃/min at 500-800 ℃ and 0.8-1 ℃/min at 800-1000 ℃.
Furthermore, the ball milling adopts a planetary ball mill, and the ball milling time is 6-8 hours.
Further, a mechanical stirrer is adopted for stirring, and the stirring time is 1.5-2 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the coating of the invention consists of Al (H) 2 PO 4 ) 3 、Al 2 O 3 And CuO, and the coating film is formed by polymerization and solidification at high temperature of 900-1000 ℃ after being coated on the surface of the titanium matrix by adopting a screen printing method; after curing, a continuous distribution phase with cross-linked covalent bonds and ionic bonds is formed, so that the copper oxide-phosphate adhesive has higher adhesive cohesion and can better cover the surface of a metal matrix. The coating prepared by the method has low fineness and strong adhesive capacity, and can obtain higher strength without high-temperature firing. After the coating is prepared, 1100 hours of oxidation test is carried out at 950 ℃, and a tensile strength characterization test between the coating and a substrate is carried out after the test is finished; therefore, the protective effect, the thermal stability and the physical and chemical properties of the phosphate-based ceramic coating at high temperature are researched. After the coating prepared by the invention is subjected to 1100-hour oxidation test at 950 ℃, the corrosion resistance is improved by 96 percent, and the tensile strength between the substrate and the coating is 8.1MPa.
2. Compared with the traditional spraying process, the coating method adopting the silk-screen printing does not need to be diluted by adding water, the condition of damaging the uniformity of the coating is avoided, and the condition of local cracking of the coating due to the difference of thermal expansion coefficients in the heat treatment process can be avoided; when the silk screen is adopted for brushing, the probability of crack defects is relatively low because the coating is thin and does not need to be diluted by adding water; the method is simple to operate, the obtained coating is thin, the surface is relatively flat, the coating efficiency is high, and the coating has excellent thermal stability and chemical stability at high temperature.
3. Compared with the domestic patent CN 105400240B, the corrosion resistance of the coating sample is improved by about 50% under the same conditions (after 1100 hours oxidation test at 950 ℃), and a better high temperature resistant protection effect is presented.
4. The coating of the invention adopts Al 2 O 3 CuO as main material and Al (H) 2 PO 4 ) 3 As a solvent, several polymerization reactions can take place at high temperatures (see fig. 2):
(1) polyphosphoric acid molecules form-O-Cu-O-side chains by themselves;
(2) polyphosphoric acid molecules are transversely bonded through an-O-Cu-O-bond bridge;
(3) polyphosphoric acid molecules are transversely bonded and can be longitudinally bonded through-O-Cu-O-bond bridges to form a high molecular polymer with a net structure.
Because of the generation of the inorganic high molecular polymers, a continuously distributed phase with cross-linked covalent bonds and ionic bonds is formed after curing, so that the copper oxide-phosphate adhesive has higher adhesive cohesion and can better cover the surface of the metal heating element.
5. The phosphate-based ceramic coating prepared by the method has low fineness and strong adhesive capacity, can obtain certain strength without high-temperature sintering, and has the advantages of simple technical process, convenient operation, strong high-temperature corrosion resistance, high film forming efficiency, uniform coating and the like.
6. The coating material of the invention is a coating material which can ensure that the metallic titanium substrate still has better high-temperature thermal stability after being subjected to long-time hot corrosion.
Drawings
FIG. 1 is a schematic diagram of a phosphate-based high temperature corrosion resistant ceramic coating on the surface of a titanium substrate prepared in example 3; in the figure, A is a coating; b is a matrix;
FIG. 2 shows Al 2 O 3 And adding Al (H) to CuO 2 PO 4 ) 3 Mechanistic diagram of the relevant reactions taking place in solution: (FIG. 2-1 is a schematic diagram of-O-Cu-O-side chain formation of polyphosphoric acid molecules per se; FIG. 2-2 is a schematic diagram of transverse bonding through-O-Cu-O-bond bridges between polyphosphoric acid molecules; and FIG. 2-3 is a schematic diagram of a high molecular polymer in which polyphosphoric acid molecules simultaneously generate transverse bonding and longitudinal bonding through-O-Cu-O-bond bridges to form a network structure).
FIG. 3 is a surface SEM image of a phosphate-based high temperature corrosion-resistant ceramic coating prepared in example 3 (FIG. 3-1 is a surface SEM image of a coating sample prepared completely; FIG. 3-2 is a surface SEM image of the coating sample after an oxidation test (1100 hours at 950 ℃ C.)).
FIG. 4 is a graph of the oxidation profile of the phosphate-based high temperature corrosion-resistant ceramic coating prepared in example 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
Respectively measuring 45 parts of Al (H) 2 PO 4 ) 3 30 parts of Al 2 O 3 And 10 parts of CuO are placed in a ball milling tank, ball milling is carried out for 6 hours by a planetary ball mill, and stirring is carried out for 1.5 hours by a mechanical stirrer, so that slurry required by the phosphate-based ceramic coating can be obtained.
The preparation process of the coating comprises the following steps: the obtained slurry was brush-coated on a titanium plate through a 180-mesh polyester screen using a screen printer, and after the substrate was left to stand at room temperature for 8 minutes, it was dried in a forced air dryer for 50 minutes at a drying temperature of 65 ℃. And (3) putting the mixture into a muffle furnace in an argon atmosphere, heating to 500 ℃ at the speed of 2.8-3 ℃/min, heating to 800 ℃ from 500 ℃ at the speed of 1.7-2 ℃/min, heating to 900 ℃ at the speed of 0.8-1 ℃/min, keeping the temperature for 1.5 hours, and then cooling along with the furnace to finish the preparation of the coating.
Example 2
55 parts of Al (H) are measured out respectively 2 PO 4 ) 3 40 parts of Al 2 O 3 And 20 parts of CuO are placed in a ball milling tank, ball milling is carried out for 8 hours through a planetary ball mill, and stirring is carried out for 2 hours through a mechanical stirrer, so that slurry required by the phosphate-based ceramic coating can be obtained.
The preparation process of the coating comprises the following steps: the obtained slurry was brush-coated on a titanium plate through a 200-mesh polyester screen by a screen printer, and after the substrate was left at room temperature for 12 minutes, it was dried in a forced air dryer for 60 minutes at a drying temperature of 70 ℃. And (3) putting the mixture into a muffle furnace in an argon atmosphere, heating to 500 ℃ at the speed of 2.8-3 ℃/min, heating to 800 ℃ from 500 ℃ at the speed of 1.7-2 ℃/min, heating to 1000 ℃ from 800 ℃ at the speed of 0.8-1 ℃/min, preserving the temperature for 1.5-2 hours, cooling along with the furnace, and finishing the preparation of the coating.
Example 3
50 parts of Al (H) were measured out separately 2 PO 4 ) 3 35 parts of Al 2 O 3 And 15 parts of CuO are placed in a ball milling tank, ball milling is carried out for 7 hours by a planetary ball mill, and stirring is carried out for 2 hours by a mechanical stirrer, so that slurry required by the phosphate-based ceramic coating can be obtained.
The preparation process of the coating comprises the following steps: the resulting slurry was brush-coated on a titanium plate through a 200-mesh polyester screen using a screen printer, and after the substrate was left to stand at room temperature for 10 minutes, it was dried in a forced air dryer for 55 minutes at a drying temperature of 65 ℃. And (3) putting the mixture into a muffle furnace in an argon atmosphere, heating to 500 ℃ at the speed of 2.8-3 ℃/min, heating to 800 ℃ from 500 ℃ at the speed of 1.7-2 ℃/min, heating to 1000 ℃ from 800 ℃ at the speed of 0.8-1 ℃/min, preserving the temperature for 1.5-2 hours, cooling along with the furnace, and finishing the preparation of the coating.
Example 4
The coating samples prepared in examples 1 to 3 were subjected to a high-temperature corrosion resistance test, which specifically includes the following procedures:
the sample coated with the coating and the sample of the bare titanium plate not coated with the coating were respectively placed in an oxygen atmosphere furnace, and the corrosion test temperature was 950 ℃ and the test time was 1100 hours (see fig. 3 for a surface view of the sample coated with the coating after the oxidation test).
And (3) corrosion rate characterization by adopting a weight gain method, and characterizing the corrosion condition of the sample by adopting a corrosion weight gain rate, wherein the corrosion rate is defined as:
sample corrosion weight gain rate = (mass after corrosion-mass before corrosion)/(coating surface area of test piece)
The high temperature corrosion behavior (oxidation curve) of the two sample materials is shown in FIG. 4.
The corrosion resistance improvement rate of the metal titanium is characterized by adopting a ratio method, the corrosion resistance of the coating is characterized by adopting the mass change ratio of the sample coating and the uncoated coating, and the ratio is defined as:
metallic titanium corrosion resistance improvement rate = (weight increase after bare titanium plate test of uncoated coating-weight increase after sample test of coated coating)/(weight increase after bare titanium plate test of uncoated coating)
The corrosion resistance improvement rates of the metal titanium are respectively 96%, 97% and 96.5%.
Example 5
The tensile strength test was carried out on the samples subjected to the oxidation test in examples 1 to 3, and the specific test procedures were as follows:
the test specimens were placed in a universal testing machine for tensile testing.
And (3) representing the tensile strength of an interface between the matrix and the coating by adopting a bonding and stretching method, bonding the coating sample and the chuck by adopting high-strength structural adhesive under pressure, and preserving heat for 2 hours at the temperature of 80 ℃ for curing for later use.
The strength of the coating when it leaves the substrate is the tensile strength, defined as:
tensile strength of coating to substrate = stretching force/surface area involved in stretching when coating peels off from substrate or coating breaks
The tensile strength of the sample material after 1100 hours of oxidation test at 950 ℃ is 8.10MPa, 8.15MPa and 8.2MPa respectively.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of the metal titanium is characterized in that the phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of the metal titanium consists of the following components in parts by mass: 45-55 parts of Al (H) 2 PO 4 ) 3 Solution, 30-40 parts of Al 2 O 3 And 10 to 20 parts of CuO;
the Al (H) 2 PO 4 ) 3 The solution is prepared from Al (OH) with a molar ratio of 1 3 And H 3 PO 4 Preparing a solution; wherein said H 3 PO 4 The mass fraction of the solution is 90-95%;
the preparation method comprises the following preparation steps:
1) After the metal titanium substrate is ultrasonically cleaned, polishing the metal surface by using SiC sand paper, and then ultrasonically cleaning again;
2) Mixing Al (H) 2 PO 4 ) 3 Solution, al 2 O 3 And CuO are fully ball-milled and stirred to form a coating;
3) Coating the paint on the substrate to form a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of the metallic titanium, and heating to high temperature
Curing, keeping the temperature, and then cooling along with the furnace to finish the preparation; the coating process comprises the following steps: and coating the coating on the substrate by adopting a screen printing mode.
2. The method for preparing a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metallic titanium according to claim 1, wherein the ultrasonic cleaning time in step 1) is 50-65 minutes.
3. The method for preparing a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium according to claim 1, wherein in the step 1), the alcohol solution is used for removing surface stains 20-30 minutes before ultrasonic cleaning, and the distilled water is used for removing surface alcohol residues 30-35 minutes later;
the SiC sand paper is 1000-1500 meshes.
4. The method for preparing a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium according to claim 1, wherein the high-temperature curing temperature is 900-1000 ℃, and the temperature is kept for 1.5-2 hours.
5. The method for preparing a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium according to claim 4, wherein the high-temperature curing is performed in a muffle furnace and is performed in an argon atmosphere, and the heating rate is 2.8-3 ℃/min at 0-500 ℃, 1.7-2 ℃/min at 500-800 ℃, and 0.8-1 ℃/min at 800-1000 ℃.
6. The method for preparing a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium according to claim 1, wherein the ball milling is carried out by using a planetary ball mill for 6-8 hours.
7. The method for preparing a phosphate-based high-temperature corrosion-resistant ceramic coating on the surface of metal titanium according to claim 1, wherein the stirring is performed by a mechanical stirrer for 1.5-2 hours.
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| CN105400240B (en) * | 2014-09-09 | 2018-03-20 | 中国科学院金属研究所 | A kind of phosphate coating for the protection of titanium group high temperature alloy high-temp and preparation method thereof |
| CN107747083B (en) * | 2017-09-05 | 2019-11-22 | 航天特种材料及工艺技术研究所 | A kind of metal matrix ceramic composite coating and preparation method thereof |
| CN111910105A (en) * | 2019-05-09 | 2020-11-10 | 中国科学院金属研究所 | High-temperature oxidation resistant coating for titanium 65 alloy phosphate and preparation method thereof |
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