CN115028471B - Antioxidant inorganic coating for carbon material product and application thereof - Google Patents
Antioxidant inorganic coating for carbon material product and application thereof Download PDFInfo
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
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Abstract
The invention relates to the technical field of low-temperature antioxidation in carbon materials; in particular to an antioxidant inorganic coating of a carbon material product and application thereof. The antioxidant inorganic coating solution comprises the following components in percentage by mole: 8 to 11 percent of phosphate radical, 1 to 3 percent of trivalent aluminum oxide, 0.05 to 0.1 percent of hydrogen phosphate radical, 0.05 to 0.1 percent of sodium silicate, 0.02 to 0.06 percent of divalent magnesium, 0.1 to 1 percent of trivalent yttrium and 0.1 to 1 percent of tetravalent zirconium; 80-90% of solvent, and the mole ratio of Al element to phosphate radical in the antioxidation inorganic coating solution is 1:2.95-3.05. The coating disclosed by the invention has the advantages of reasonable component design, simple and controllable application process, excellent performance of the obtained coating and convenience for industrialized application.
Description
Technical Field
The invention relates to the technical field of low-temperature antioxidation in carbon materials; in particular to an antioxidant inorganic coating of a carbon material product and application thereof.
Background
Carbon materials have many unique and excellent properties such as high specific strength (strength is enhanced with an increase in temperature), low Coefficient of Thermal Expansion (CTE), low density, good electrical and thermal conductivity, good chemical stability, and the like, and thus are widely used in the fields of metallurgy, machinery, chemical industry, petroleum, textile, nuclear industry, and the like. However, these excellent properties of carbon materials can be maintained only under vacuum or inert conditions. The carbon material has many pores, which can become the channel for oxygen invasion and diffusion under service conditions, so the carbon material is easily oxidized in the oxygen-containing atmosphere with the temperature of more than 400 ℃, and the oxidation rate is increased with the temperature. The oxidation corrosion of the carbon material can cause loose surface structure and even fall off phenomenon, which affects the normal use of the carbon material device, so that the improvement of the oxidation resistance of the carbon material in the oxygen-containing atmosphere is urgent.
An oxidation-resistant coating layer is prepared on the surface of a carbon material product to block oxygen contact, so that the service life of the carbon material product is prolonged, and the carbon material product is a relatively effective path and method at present. Common surface treatment methods are solid phase (embedding), atmospheric plasma spraying, chemical Vapor Deposition (CVD), sol-gel (sol-gel), hydrothermal electrophoresis deposition and dipping. The impregnation method has many advantages over other methods: (a) The common equipment has simple structure, low investment and high economic benefit; (b) the preparation process is simple and easy to operate; (c) The surface oxidation-resistant coating is not easy to fall off and generate microcracks. The impregnating solution gradually decomposes, dehydrates, polymerizes and crystallizes in the heat treatment process, fills the pores inside the carbon material and covers the surface of the carbon material, thereby isolating the contact of the oxidizing gas and the carbon material, reducing the oxidation reaction active points on the surface of the carbon material and reducing the oxidation reaction rate. Solutions currently commonly used for carbon material impregnation are borate solutions, phosphate solutions, silicate solutions, chlorine-containing solutions, mixed solutions thereof, and the like. Wherein the phosphate system can provide good antioxidation protection for carbon materials under the condition of medium and low temperature, and metal ions (Al, cr, mg, mn, zn, etc.), B and Si are introduced into the phosphate, which can further inhibit P generated by phosphoric acid decomposition in the long-term oxidation process 2 O 5 And (3) the volatilization of the coating is reduced, the damage of the coating is reduced, and the high-temperature stability of the coating is improved.
Chinese patent document CN101052253A (antioxidant for carbon material and its preparation and use method) discloses an antioxidant for carbon material, which is aqueous solution with solid content of 5-40wt%; wherein the solid component ratio: 2 to 80 weight percent of silicon, 0.5 to 10 weight percent of aluminum, 0.01 to 10 weight percent of titanium, 0.1 to 30 weight percent of phosphorus and 0.1 to 5 weight percent of boron, and the balance is oxygen or carbon in oxides and carbides containing the silicon, the aluminum, the titanium, the phosphorus and the boron.
Chinese patent document CN109534854, "process of impregnating inorganic salt for antioxidation of carbon graphite products", discloses an antioxidation liquid which is mainly prepared from the following raw materials in percentage: zinc phosphate, aluminum phosphate, 85% phosphoric acid by mass, boric acid and water. Wherein the zinc phosphate: aluminum phosphate: 85% of phosphoric acid: boric acid: the molar ratio of water is 5-4:1:35-120:0.25-0.3:4-19. The impregnation treatment is carried out by adopting a vacuum method and a pressurizing method respectively.
In Chinese patent document CN102775991, an immersed antioxidant liquid for improving the high-temperature oxidation resistance of a graphite product and an application method thereof, a high-temperature oxidation resistance method of the graphite product is disclosed. Wherein the first impregnating solution is: 50-80% of ammonium hexametaphosphate, 20-50% of aluminum potassium sulfate and a mass ratio of solute to water of 1:0.1-0.125; the second impregnating solution is: 30-70% of sodium silicate, 30-70% of sodium tetraborate and the mass ratio of solute to water is 1:3.3-5.0. And the graphite is subjected to two-step impregnation treatment under normal pressure or pressure of 0.1-0.6 MPa.
Chinese patent document CN102910909, a graphite carbon sleeve and an antioxidation impregnation treatment method thereof, discloses an antioxidation impregnation liquid which is prepared from the following raw materials in percentage: 10-15% of trisodium phosphate, 10-15% of zinc phosphate, 15-25% of aluminum dihydrogen phosphate and the balance of water. The dipping treatment is carried out by adopting two modes of vacuum and pressurization.
The search found that the introduction of Y in the acid aluminum phosphate impregnating solution is not adopted to solve the problems of less adhesion of the coating on the graphite surface, poor interface bonding strength between the prepared coating and the matrix, low oxidation resistance temperature and the like 3+ 、Zr 4 + Scheme of plasma metal ion.
Disclosure of Invention
The invention firstly tries to simultaneously introduce Y into the acid aluminum phosphate impregnating solution 3+ 、Zr 4+ The metal ions solve the problems of less adhesion on the graphite surface, poor interface bonding strength between the prepared coating and the matrix, low oxidation resistance temperature and the like. After heat treatment, the impregnated graphite exhibits excellent oxidation resistance in the temperature range of 400-1200 ℃.
In order to achieve the expected aim, the technical scheme provided by the invention specifically comprises the following steps:
an antioxidant inorganic coating for carbon material products, wherein the antioxidant inorganic coating solution comprises the following components in percentage by mole: 8 to 11 percent of phosphate radical, 1 to 3 percent of trivalent aluminum oxide, 0.05 to 0.1 percent of hydrogen phosphate radical, 0.05 to 0.2 percent of sodium silicate, 0.02 to 0.06 percent of divalent magnesium, 0.1 to 1 percent of trivalent yttrium, 0.1 to 1 percent of tetravalent zirconium and 80 to 90 percent of solvent, and the mole ratio of Al element to phosphate radical in the antioxidation inorganic coating solution is 1:2.95 to 3.05, preferably 1:3 to 3.05. In the present invention, when the molar ratio of the Al element to the phosphate is out of the range defined in the present invention, the properties of the product rapidly decay.
Preferably, the carbon material product antioxidation inorganic paint comprises the following components in percentage by mole: phosphoric acid (H) 3 PO 4 ) 8 to 11 percent of alumina (Al) 2 O 3 ) 1 to 3 percent of disodium hydrogen phosphate dodecahydrate (Na) 2 HPO 4 ·12H 2 O) 0.05-0.1%, water glass (Na) 2 SiO 3 ·12H 2 O) 0.05-0.2%, magnesium oxide (MgO) 0.02-0.06%, yttrium oxide (Y) 2 O 3 ) 0.05 to 0.5 percent of zirconium hydroxide (Zr (OH) 4 ) 0.1-1%, solvent 80-90%, all of which are analytical grade (AR). The inventor finds that when the series of preferred embodiments are adopted, some products only have excellent low-temperature oxidation resistance (such as in an atmosphere at 1000 ℃); there are a few proposals with excellent high temperature oxidation resistance. Thus, further preference is given to the following solutions:
as a further preferred, an oxidation-resistant inorganic coating for carbon material products, the oxidation-resistant inorganic coating solution comprises the following components in mole percent: phosphoric acid (H) 3 PO 4 ) 8.8 to 9.2 percent of alumina (Al) 2 O 3 ) 1.25 to 1.75 percent of water glass (Na) 2 SiO 3 ·12H 2 O) 0.05-0.2%, magnesium oxide (MgO) 0.05-0.06%, yttrium oxide (Y) 2 O 3 ) 0.075-0.25% zirconium hydroxide (Zr (OH) 4 ) 0.25-0.35%, solvent 80-90%, wherein the raw materials are all analytical grade (AR).
As a further preferable mode, the content of yttrium oxide in the components in the oxidation-resistant inorganic coating solution is 0.12-0.18% in terms of mole percent.
As still further preferred, an oxidation resistant inorganic coating for a carbon material article, the oxidation resistant inorganic coating solution comprising, in mole percent, the following components: 9%H 3 PO 4 ，1.5％Al 2 O 3 ，0.1％Na 2 HPO 4 ·12H 2 O，0.2％Na 2 SiO 3 ·12H 2 O，0.05％MgO，0.15％Y 2 O 3 ，0.3％Zr(OH) 4 ，88.7％H 2 O. The product obtained by the scheme is oxidized for 5 hours at 1000 ℃ in air atmosphere, which is recorded as 1000 ℃/5 hours, and the weight loss per unit area is 5.94mg/cm 2 The oxidation rate was 7.9%. After 1200 ℃/5h, the weight loss per unit area is 8.97mg/cm 2 The oxidation rate was 9.8%. The effect of this scheme is far superior to that of other schemes.
In industrial application, the mass fraction of phosphoric acid is 85% of concentrated phosphoric acid.
The solvent is preferably deionized water (H) 2 O)。
Preferably, al is represented by a molar ratio of Y to Zr=10:1:1.
The invention relates to application of an antioxidant inorganic coating for a carbon material product, which comprises the following steps:
(a) Polishing: polishing a graphite sample, ultrasonically cleaning the graphite sample by alcohol, and drying the graphite sample in an oven at 150 ℃ for later use; the graphite is fine particle graphite block with porosity of 15-20%, preferably 18-19%;
(b) Preparing an impregnating solution: the raw materials are weighed according to the proportion. The acid solution of phosphoric acid and water is used to dissolve Y completely 2 O 3 Or Zr (OH) 4 Adding other raw materials into the solution, and regulating the pH value of the solution to 2-5 by using hydrochloric acid (HCl);
(c) Stirring: adding the impregnating solution obtained in the step (b), stirring in a water bath kettle, and fully reacting;
(d) Impregnating under normal pressure: placing the graphite obtained in the step (a) in impregnating solution, and impregnating for 20-30 min at room temperature;
(e) Vacuum impregnation: placing the graphite obtained in the step (d) into phosphate impregnation liquid, and vacuumizing and impregnating for 20-30 min.
(f) And (3) drying: placing the sample obtained in the step (e) into an oven, and drying for 20-30 min;
(g) And (3) final drying: placing the impregnated sample into a drying oven, drying the water, and preferably, drying for 4-6 hours;
(h) And (3) heat treatment: and (3) placing the sample obtained in the step (g) into a tube furnace for heat treatment to obtain a graphite sample with the surface coated with the phosphate coating.
Further, in the step (a), the SiC sand paper with 800 meshes and the SiC sand paper with 1000 meshes are used for polishing so that the graphite surface has a certain roughness, and the adhesion of the coating is facilitated.
Further, in the step (b), Y is used 2 O 3 The particle size of the powder is 0.1-0.5 μm, zr (OH) is used 4 The particle size of the powder is 0.3-0.8 mu m.
Further, in the step (c), the water bath temperature is 80-90 ℃ and the stirring time is 2-4 h.
Further, in the step (e), the vacuum degree is-0.09 to-0.1 MPa (reading on a vacuum gauge).
Furthermore, on the basis of normal pressure impregnation, the vacuum impregnation is further adopted, so that the gas in the pores inside the graphite material can be further exhausted, and the impregnation liquid can be easily diffused into the graphite material.
Further, the steps (d) and (e) are repeated for three times, and after each impregnation is completed, the process is carried out for 20 to 30 minutes at the temperature of 90 ℃ in an electrothermal blowing drying oven, and then the next impregnation is carried out; multiple impregnations are adopted, and in the process of each impregnation, the direction of impregnation is changed, so that the phenomenon of uneven coating application caused by the action of gravity is overcome.
Further, the repeated step (f) after each impregnation is completed is beneficial to the adhesion of the impregnation solution on the surface of the graphite substrate, and besides, the temperature difference at the interface is beneficial to the diffusion of the impregnation solution to the inside and the adhesion of the impregnation solution on the surface in the next impregnation process.
Further, in the step (h), the specific heat treatment process is that the temperature is raised to 500-600 ℃ at the heating rate of 2-4 ℃/min, the heat is preserved for 1.5-2 h, then the temperature is raised to 800-900 ℃ at the heating rate of 2-4 ℃/min, the heat is preserved for 1.5-2 h, and then the temperature is cooled to the room temperature along with the furnace. The water and low-melting point components in the impregnated graphite can be fully volatilized by adopting a heat treatment mode of sectional heat preservation, and the prepared coating is more compact;
further, in the step (h), argon (Ar) is introduced as a shielding gas during the whole heat treatment process.
Further, the thickness of the surface coating of the phosphate impregnated graphite prepared by the invention is about 5.5-50 mu m. The ion types used for modifying the impregnating solution are different, and the prepared coating protection mechanism is different.
As an optimization scheme, the product obtained by the invention is sintered for 5 hours at 1000 ℃ in the atmosphere, the coating has no obvious cracking and falling phenomena, and the weight loss per unit area is less than 6mg/cm after the product is sintered for 5 hours at 1000 DEG C 2 The oxidation rate is less than 8%; sintering at 1200 deg.c for 5 hr to obtain a weight loss of less than 9mg/cm 2 The oxidation rate is less than 10%.
Beneficial results
The invention is doped with a proper amount of rare earth ion Y on the basis of aluminum phosphate impregnating solution 3+ And tetravalent ion Zr 4+ The problems of less adhesion of antioxidant substances on the graphite surface, poor interface bonding strength of the coating and a matrix, low antioxidant temperature and the like can be remarkably improved by matching with proper Al, Y and Zr proportions, and a necessary condition is provided for obtaining a phosphate coating with excellent antioxidant properties at low temperature and high temperature.
Y 3+ And Al 3+ Having the same valence state, Y 3+ The addition of the phosphate impregnation liquid reduces the viscosity of the impregnation liquid, improves the wettability of the phosphate impregnation liquid on the surface of graphite, and reduces the wetting angle. The liquid spreads more easily on the surface of the graphite and diffuses into the interior of the graphite, reducing the oxidative active sites of the graphite. Zr is introduced into the phosphate impregnation liquid 4+ It is connected withThe phosphate ion reaction generates ZrP 2 O 7 。ZrP 2 O 7 Is AM 2 O 7 One member of the group (a=sn, ti, zr etc.; m=p, V, as) has a low or even negative Coefficient of Thermal Expansion (CTE), which can lower the CTE of the phosphate coating, resulting in a CTE of the whole coating system (3-4 x 10 -6 Low CTE (3 to 5X 10) with graphite -6 /K) are more matched. After heat treatment, the main phase of the graphite surface coating is Al (PO 3 ) 3 Introduced Y 3+ And Zr (Zr) 4+ Y (PO) formed after the heat treatment 3 ) 3 And ZrP 2 O 7 The complexity of the coating network is increased, and the oxidation resistance is improved. According to the invention, during impregnation, vacuum impregnation is added on the basis of normal pressure impregnation, so that the gas amount adsorbed in graphite pores is discharged, the impregnation solution is easier to contact with a graphite substrate, and the impregnation efficiency is improved. The temperature is increased and decreased at a slower rate in the heat treatment process, so that volatile low-melting-point substances in the coating can be fully diffused, the porosity of the sintered coating is reduced, and the compactness of the coating is improved.
The modified phosphate coating is prepared on the surface of graphite, the surface of the coating is uniform and compact, the interface combination with a matrix is firm, and the coating does not have obvious cracking and falling in an oxygen-containing atmosphere at 400-1200 ℃ and has good oxidation resistance.
According to the optimization scheme, the obtained product has excellent oxidation resistance in the atmospheric atmosphere at 1000 ℃ and 1200 ℃.
Drawings
FIG. 1 is an oxidation-weight loss curve of example 1 and comparative example 3
FIG. 2 shows the surface topography before and after oxidation of the samples in example 1 and comparative example 3
FIG. 3 shows the cross-sectional morphology of the samples of example 1 and comparative example 3 before and after oxidation.
As can be seen from fig. 1, Y 3+ And Zr (Zr) 4+ The doping of the phosphate coating sample can reduce the oxidation weight loss of the phosphate coating sample, and further improve the oxidation resistance of the phosphate coating.
In FIG. 2, (a) is a surface topography of the sample obtained in example 1 before oxidation, and (b) is a surface topography of the sample obtained in example 1 after oxidation; (c) A surface topography of the sample obtained in comparative example 3 before oxidation, and (d) a surface topography of the sample obtained in comparative example 3 after oxidation;
in FIG. 3, (a) is a cross-sectional view of the sample obtained in example 1 before oxidation, and (b) is a cross-sectional view of the sample obtained in example 1 after oxidation; (c) A cross-sectional profile of the sample obtained in comparative example 3 before oxidation, and (d) a cross-sectional profile of the sample obtained in comparative example 3 after oxidation;
as can be seen from fig. 2 and 3, there are some differences in the surface and cross-sectional morphology of the different phosphate coating samples, the coating thickness of example 1 increased and the coating density increased after oxidation, indicating Y 3+ And Zr (Zr) 4+ The doping of the aluminum phosphate coating improves the thermal stability of the aluminum phosphate coating.
Detailed Description
The invention provides a high-temperature oxidation-resistant inorganic coating for graphite products, which is characterized in that after impregnation treatment, the oxidation resistance of graphite is obviously improved, and the mechanical properties of the graphite are basically maintained.
Comparative example 1:
the phosphate antioxidant impregnating solution of the embodiment comprises the following components in mole percent:
9％H 3 PO 4 ，1.5％Al 2 O 3 ，0.1％Na 2 HPO 4 ·12H 2 O，0.2％Na 2 SiO 3 ·12H 2 O，0.05％MgO，0.15％Y 2 O 3 ，89％H 2 O。
the phosphate impregnated graphite article of this example was prepared by the following steps:
(a) Polishing: polishing graphite samples with 800-mesh and 1000-mesh SiC sand paper respectively, ultrasonically cleaning with alcohol, and drying in an oven at 150 ℃ for later use; the density of the graphite sample was 1.83g/cm 3 The open porosity is 18.62%;
(b) Preparing an impregnating solution: weighing the raw materials according to a certain proportion. FirstComplete dissolution of Y with an acidic solution of phosphoric acid and water 2 O 3 Then adding other raw materials into the impregnating solution, and adjusting the pH value of the solution to 3 by using hydrochloric acid (HCl);
(c) Stirring: placing the impregnating solution in a water bath kettle, stirring, and fully and uniformly mixing at 70 ℃/5 hours;
(d) Impregnating under normal pressure: placing graphite treated at 150 ℃ in the impregnating solution for 20min;
(e) Vacuum impregnation: placing graphite into phosphate impregnation liquid, and vacuumizing and impregnating for 20min, wherein the vacuum degree is-0.09 MPa (gauge pressure);
(f) And (3) drying: placing the impregnated sample into a drying oven, and drying the sample at 120 ℃/5 hours to obtain water;
(g) And (3) heat treatment: and (3) placing the impregnated graphite sample obtained in the step (f) into a tube furnace for heat treatment. The temperature is kept for 2 hours at the temperature rising rate of 2 ℃/min and at the temperature of 500 ℃ and 800 ℃, ar is always used as a protective gas in the whole heat treatment process, and the flow rate of the Ar is about 0.05L/min.
Oxidation experiment: the obtained sample is subjected to an oxidation experiment (air atmosphere) at 400-1200 ℃ in a vacuum tube furnace, the coating has no obvious cracking and falling phenomenon in the whole oxidation process, the coating is oxidized for 5 hours at 1000 ℃ in the air atmosphere, 1000 ℃/5 hours is recorded, and the weight loss per unit area is 9.15mg/cm 2 The oxidation rate was 12.1%. After 1200 ℃/5h, the weight loss per unit area is 16.32mg/cm 2 Oxidation ratio of 20.1% comparative example 2:
the phosphate antioxidant impregnating solution of the embodiment comprises the following components in mole percent:
9％H 3 PO 4 ，1.5％Al 2 O 3 ，0.1％Na 2 HPO 4 ·12H 2 O，0.2％Na 2 SiO 3 ·12H 2 O，0.05％MgO，0.3％Zr(OH) 4 ，88.85％H 2 O。
the phosphate impregnated graphite article of this example was prepared by the following steps:
(a) Polishing: graphite samples were polished sequentially with 800 mesh and 1000 mesh SiC sandpaper, respectively, with ethanolAfter ultrasonic cleaning, drying in an oven at 150 ℃ for standby; the density of the graphite sample was 1.83g/cm 3 The open porosity is 18.62%;
(b) Preparing an impregnating solution: weighing the raw materials according to a certain proportion. Firstly, using acid solution of phosphoric acid and water to completely dissolve Zr (OH) 4 Then adding other raw materials into the impregnating solution, and adjusting the pH value of the solution to 3 by using hydrochloric acid (HCl);
(c) Stirring: placing the impregnating solution in a water bath kettle, stirring, and fully and uniformly mixing at 70 ℃/5 hours;
(d) Impregnating under normal pressure: placing graphite treated at 150 ℃ in the impregnating solution for 20min;
(e) Vacuum impregnation: placing graphite into phosphate impregnation liquid, and vacuumizing and impregnating for 20min, wherein the vacuum degree is-0.09 MPa (gauge pressure);
(f) And (3) drying: placing the impregnated sample into a drying oven, and drying the sample at 120 ℃/5 hours to obtain water;
(g) And (3) heat treatment: and (3) placing the impregnated graphite sample obtained in the step (f) into a tube furnace for heat treatment. The temperature is kept for 2 hours at the temperature rising rate of 2 ℃/min and at the temperature of 500 ℃ and 800 ℃, ar is always used as a protective gas in the whole heat treatment process, and the flow rate of the Ar is about 0.05L/min.
Oxidation experiment: the obtained sample is subjected to an oxidation experiment at 400-1200 ℃ in a vacuum tube furnace, the coating has no obvious cracking and falling phenomenon in the whole oxidation process, the coating is oxidized for 5 hours at 1000 ℃ in an air atmosphere, 1000 ℃/5 hours is recorded, and the weight loss per unit area is 7.12mg/cm 2 The oxidation rate was 10.3%. After 1200 ℃/5h, the weight loss per unit area is 9.15mg/cm 2 The oxidation rate was 12.7%.
Example 1:
the phosphate antioxidant impregnating solution of the embodiment comprises the following components in mole percent:
9％H 3 PO 4 ，1.5％Al 2 O 3 ，0.1％Na 2 HPO 4 ·12H 2 O，0.2％Na 2 SiO 3 ·12H 2 O，0.05％MgO，0.15％Y 2 O 3 ，0.3％Zr(OH) 4 ，88.7％H 2 O。
the phosphate impregnated graphite article of this example was prepared by the following steps:
(a) Polishing: polishing graphite samples with 800-mesh and 1000-mesh SiC sand paper respectively, ultrasonically cleaning with alcohol, and drying in an oven at 150 ℃ for later use; the density of the graphite sample was 1.83g/cm 3 The open porosity is 18.62%; (and comparative example 1 was the same batch of raw materials)
(b) Preparing an impregnating solution: weighing the raw materials according to a certain proportion. The acid solution of phosphoric acid and water is used to dissolve Y completely 2 O 3 And Zr (OH) 4 Then adding other raw materials into the impregnating solution, and adjusting the pH value of the solution to 3 by using hydrochloric acid (HCl);
(c) Stirring: placing the impregnating solution in a water bath kettle, stirring, and fully and uniformly mixing at 70 ℃/5 hours;
(d) Impregnating under normal pressure: placing graphite treated at 150 ℃ in the impregnating solution for 30min;
(e) Vacuum impregnation: placing graphite into phosphate impregnation liquid, and vacuumizing and impregnating for 30min, wherein the vacuum degree is-0.09 to-0.1 MPa;
(f) And (3) drying: placing the impregnated sample into a drying oven, and drying the sample at 150 ℃/5h to obtain water;
(g) And (3) heat treatment: and (3) placing the impregnated graphite sample obtained in the step (f) into a tube furnace for heat treatment. The temperature is kept for 2 hours at 600 ℃ and 900 ℃ at a heating rate of 2 ℃/min, ar is always used as a protective gas in the whole heat treatment process, and the flow rate of the Ar is about 0.05L/min.
Oxidation experiment: the obtained sample is subjected to an oxidation experiment at 400-1200 ℃ in a vacuum tube furnace, the coating has no obvious cracking and falling phenomenon in the whole oxidation process, the coating is oxidized for 5 hours at 1000 ℃ in an air atmosphere, 1000 ℃/5 hours is recorded, and the weight loss per unit area is 5.94mg/cm 2 The oxidation rate was 7.9%. After 1200 ℃/5h, the weight loss per unit area is 8.97mg/cm 2 The oxidation rate was 9.8%.
Example 2:
the phosphate antioxidant impregnating solution of the embodiment comprises the following components in mole percent:
9％H 3 PO 4 ，1.5％Al 2 O 3 ，0.1％Na 2 HPO 4 ·12H 2 O，0.2％Na 2 SiO 3 ·9H 2 O，0.05％MgO，0.2％Y 2 O 3 ,0.2％Zr(OH) 4 ，88.75％H 2 o. The phosphate impregnated graphite article of this example was prepared by the following steps:
(a) Polishing: polishing graphite samples with 800-mesh and 1000-mesh SiC sand paper respectively, ultrasonically cleaning with alcohol, and drying in an oven at 150 ℃ for later use; the density of the graphite sample was 1.83g/cm 3 The open porosity is 18.62%; (and comparative example 1 was the same batch of raw materials)
(b) Preparing an impregnating solution: weighing the raw materials according to a certain proportion. The acid solution of phosphoric acid and water is used to dissolve Y completely 2 O 3 And Zr (OH) 4 Then adding other raw materials into the impregnating solution, and adjusting the pH value of the solution to 3 by using hydrochloric acid (HCl);
(c) Stirring: placing the impregnating solution in a water bath kettle, stirring, and fully and uniformly mixing at 80 ℃/5 hours;
(d) Impregnating under normal pressure: placing graphite treated at 150 ℃ in the impregnating solution for 20min;
(e) Vacuum impregnation: placing graphite into phosphate impregnation liquid, vacuumizing and impregnating for 20min, wherein the vacuum degree is-0.09 to-0.1 MPa (gauge pressure);
(f) And (3) drying: placing the impregnated sample into a drying oven, and drying the sample at 120 ℃/5 hours to obtain water;
(g) And (3) heat treatment: and (3) placing the impregnated graphite sample obtained in the step (f) into a tube furnace for heat treatment. The temperature is kept for 2 hours at 600 ℃ and 800 ℃ at a heating rate of 3 ℃/min, ar is always used as a protective gas in the whole heat treatment process, and the flow rate of the Ar is about 0.05L/min;
oxidation experiment: the obtained sample is subjected to an oxidation experiment at 400-1200 ℃ in a vacuum tube furnace, the coating has no obvious cracking and falling phenomenon in the whole oxidation process, and the oxidation is carried out for 5 hours at 1000 ℃ in an air atmosphere, which is recorded as 1000 DEG CPer 5h, the weight loss per unit area is 8.59mg/cm 2 The oxidation rate was 11.6%. After 1200 ℃/5h, the weight loss per unit area is 11.25mg/cm 2 The oxidation rate was 13.3%.
Example 3:
the phosphate antioxidant impregnating solution of the embodiment comprises the following components in mole percent: 9%H 3 PO 4 ，1.5％Al 2 O 3 ，0.1％Na 2 HPO 4 ·12H 2 O，0.2％Na 2 SiO 3 ·9H 2 O，0.05％MgO，0.075％Y 2 O 3 ,0.15％Zr(OH) 4 ，88.93％H 2 O。
The phosphate impregnated graphite article of this example was prepared by the following steps:
(a) Polishing: polishing graphite samples with 800-mesh and 1000-mesh SiC sand paper respectively, ultrasonically cleaning with alcohol, and drying in an oven at 150 ℃ for later use; the density of the graphite sample was 1.83g/cm 3 The open porosity is 18.62%; (and comparative example 1 was the same batch of raw materials)
(b) Preparing an impregnating solution: weighing the raw materials according to a certain proportion. The acid solution of phosphoric acid and water is used to dissolve Y completely 2 O 3 And Zr (OH) 4 Then adding other raw materials into the impregnating solution, and adjusting the pH value of the solution to 3 by using hydrochloric acid (HCl);
(c) Stirring: placing the impregnating solution in a water bath kettle, stirring, and fully and uniformly mixing at 80 ℃/5 hours;
(d) Impregnating under normal pressure: placing graphite treated at 150 ℃ in the impregnating solution for 20min;
(e) Vacuum impregnation: placing graphite into phosphate impregnation liquid, vacuumizing and impregnating for 20min, wherein the vacuum degree is-0.09 to-0.1 MPa (gauge pressure);
(f) And (3) drying: placing the impregnated sample into a drying oven, and drying the sample at 120 ℃/5 hours to obtain water;
(g) And (3) heat treatment: and (3) placing the impregnated graphite sample obtained in the step (f) into a tube furnace for heat treatment. The temperature is kept for 2 hours at 600 ℃ and 800 ℃ at a heating rate of 3 ℃/min, ar is always used as protective gas in the whole heat treatment process, and the flow of the Ar is
Oxidation experiment: the obtained sample is subjected to an oxidation experiment at 500-1200 ℃ in a vacuum tube furnace, the coating has no obvious cracking and falling phenomenon in the whole oxidation process, the coating is oxidized for 5 hours at 1000 ℃ in an air atmosphere, and the weight loss per unit area is 6.34mg/cm after 1000 ℃/5 hours 2 The oxidation rate is 8.1%; after 1200 ℃/5h, the weight loss per unit area is 14.64mg/cm 2 The oxidation rate was 16.1%. The product obtained by the scheme used in this example has excellent low-temperature oxidation resistance, but high-temperature oxidation resistance is not particularly desirable.
Example 4:
the phosphate antioxidant impregnating solution of the embodiment comprises the following components in mole percent: 9%H 3 PO 4 ，1.5％Al 2 O 3 ，0.1％Na 2 HPO 4 ·12H 2 O，0.2％Na 2 SiO 3 ·9H 2 O，0.05％MgO，0.1％Y 2 O 3 ,0.1％Zr(OH) 4 ，88.95％H 2 O。
The phosphate impregnated graphite article of this example was prepared by the following steps:
(a) Polishing: polishing graphite samples with 800-mesh and 1000-mesh SiC sand paper respectively, ultrasonically cleaning with alcohol, and drying in an oven at 150 ℃ for later use; the density of the graphite sample was 1.83g/cm 3 The open porosity is 18.62%;
(b) Preparing an impregnating solution: weighing the raw materials according to a certain proportion. The acid solution of phosphoric acid and water is used to dissolve Y completely 2 O 3 And Zr (OH) 4 Then adding other raw materials into the impregnating solution, and adjusting the PH of the solution to 3 by hydrochloric acid (HCl);
(c) Stirring: placing the impregnating solution in a water bath kettle, stirring, and fully and uniformly mixing at 80 ℃/5 hours;
(d) Impregnating under normal pressure: placing graphite treated at 150 ℃ in the impregnating solution for 20min;
(e) Vacuum impregnation: placing graphite into phosphate impregnation liquid, and vacuumizing and impregnating for 30min, wherein the vacuum degree is-0.09 to-0.1 MPa;
(f) And (3) drying: placing the impregnated sample into a drying oven, and drying the sample at 120 ℃/5 hours to obtain water;
(g) And (3) heat treatment: and (3) placing the impregnated graphite sample obtained in the step (f) into a tube furnace for heat treatment. The temperature is kept for 2 hours at 600 ℃ and 800 ℃ at a heating rate of 3 ℃/min, ar is always used as protective gas in the whole heat treatment process, and the flow of the Ar is
Oxidation experiment: the obtained sample is subjected to an oxidation experiment at 400-1200 ℃ in a vacuum tube furnace, the coating has no obvious cracking and falling phenomenon in the whole oxidation process, the oxidation is carried out for 5 hours at 1000 ℃ in an air atmosphere, the oxidation is recorded as 1000 ℃/5 hours, and the weight loss per unit area is 5.89mg/cm 2 The oxidation rate was 7.74%. After 1200 ℃/5h, the weight loss per unit area is 13.55mg/cm 2 The oxidation rate was 14.9%. The low temperature oxidation resistance of the product obtained by the scheme used in this example is extremely superior, but the high temperature oxidation resistance is not particularly desirable.
Comparative example 3:
the phosphate antioxidant impregnating solution of the embodiment comprises the following components in mole percent: 9%H 3 PO 4 ，1.5％Al 2 O 3 ，0.1％Na 2 HPO 4 ·12H 2 O，0.2％Na 2 SiO 3 ·9H 2 O，0.05％MgO，89.15％H 2 O。
The phosphate impregnated graphite article of this example was prepared by the following steps:
(a) Polishing: polishing graphite samples with 800-mesh and 1000-mesh SiC sand paper respectively, ultrasonically cleaning with alcohol, and drying in an oven at 150 ℃ for later use; the density of the graphite sample was 1.83g/cm 3 The open porosity was 18.62%.
(b) Preparing an impregnating solution: weighing the raw materials according to a certain proportion. Completely dissolving the rest raw material components by using an acidic solution of phosphoric acid and water, and then adjusting the pH of the solution to 3 by using hydrochloric acid (HCl);
(c) Stirring: placing the impregnating solution in a water bath kettle, stirring, and fully and uniformly mixing at 70 ℃/5 hours;
(d) Impregnating under normal pressure: placing graphite treated at 150 ℃ in the impregnating solution for 20min;
(e) Vacuum impregnation: placing graphite into phosphate impregnation liquid, vacuumizing and impregnating for 20min, wherein the vacuum degree is-0.09 to-0.1 MPa (gauge pressure);
(f) And (3) drying: placing the impregnated sample into a drying oven, and drying the sample at 120 ℃/5 hours to obtain water;
(g) And (3) heat treatment: and (3) placing the impregnated graphite sample obtained in the step (f) into a tube furnace for heat treatment. The temperature is kept for 2 hours at 500 ℃ and 800 ℃ at a heating rate of 2 ℃/min, ar is always used as a protective gas in the whole heat treatment process, and the flow of the Ar is the same.
(h) Oxidation experiment: the obtained sample is subjected to an oxidation experiment (atmosphere) at 400-1200 ℃ in a vacuum tube furnace, the coating has no obvious cracking and falling phenomenon in the whole oxidation process, the oxidation is carried out for 5 hours at 1000 ℃ in the air atmosphere, the oxidation is recorded as 1000 ℃/5 hours, and the weight loss per unit area is 11.59mg/cm after 1000 ℃/5 hours 2 The oxidation rate was 16%.
Claims (1)
1. An application of an antioxidant impregnating solution for a carbon material product is characterized in that: the antioxidant impregnating solution comprises the following components in percentage by mole:
9% H 3 PO 4 ，1.5% Al 2 O 3 ，0.1% Na 2 HPO 4 ·12H 2 O，0.2% Na 2 SiO 3 ·12H 2 O，0.05% MgO，0.15% Y 2 O 3 ，0.3% Zr(OH) 4 ，88.7% H 2 O；
the application of the carbon material product oxidation-resistant impregnating solution comprises the following steps:
(a) Polishing: polishing graphite samples with 800-mesh and 1000-mesh SiC sand paper respectively, ultrasonically cleaning with alcohol, and drying in an oven at 150 ℃ for later use; the density of the graphite sample was 1.83g/cm 3 The open porosity is 18.62%;
(b) Preparing an impregnating solution: weighing the raw materials in proportion; the acid solution of phosphoric acid and water is used to dissolve Y completely 2 O 3 And Zr (OH) 4 Then other raw materials are added into the solution, and the pH value of the solution is adjusted to 3 by hydrochloric acid;
(c) Stirring: placing the impregnating solution in a water bath kettle, stirring, and fully and uniformly mixing at 70 ℃/5 hours;
(d) Impregnating under normal pressure: placing graphite treated at 150 ℃ in the impregnating solution for 30min;
(e) Vacuum impregnation: placing graphite into the impregnating solution, and vacuumizing and impregnating for 30min, wherein the vacuum degree is-0.09 to-0.1 MPa;
(f) And (3) drying: placing the impregnated sample into a drying oven, and drying the sample at 150 ℃/5h to obtain water;
(g) And (3) heat treatment: placing the impregnated graphite sample obtained in the step (f) into a tube furnace for heat treatment; the temperature is kept for 2 hours at the temperature rising rate of 2 ℃/min and at the temperature of 600 ℃ and 900 ℃, ar is always used as a protective gas in the whole heat treatment process, and the flow rate of the Ar is 0.05L/min;
oxidation experiment: the obtained sample is subjected to an oxidation experiment at 400-1200 ℃ in a vacuum tube furnace, in the whole oxidation process, the coating has no obvious cracking and falling phenomenon, the coating is oxidized for 5 hours at 1000 ℃ in an air atmosphere, 1000 ℃/5 hours is recorded, and the weight loss per unit area is 5.94mg/cm 2 The oxidation rate is 7.9%; after 1200 ℃/5h, the weight loss per unit area is 8.97mg/cm 2 The oxidation rate was 9.8%.
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