CN111705348A - Processing technology of high-temperature-resistant ceramic oxide film - Google Patents
Processing technology of high-temperature-resistant ceramic oxide film Download PDFInfo
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- C—CHEMISTRY; METALLURGY
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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Abstract
The invention discloses a processing technology of a high-temperature-resistant ceramic oxide film, belonging to the technical field of inorganic materials. The method comprises the steps of modifying glucan, mixing the modified glucan and polyallylamine hydrochloride for reaction, adding metal salt to prepare modified microcapsules, adding the modified microcapsules into electrolyte mainly prepared from sodium salt and sodium hypophosphite, performing micro-arc oxidation treatment by taking a titanium alloy as an anode and a stainless steel tank as a cathode to prepare a pretreated ceramic oxide film, and performing high-temperature treatment on the pretreated ceramic oxide film to prepare the ceramic oxide film. The ceramic oxide film prepared by the invention has excellent compactness and high temperature resistance.
Description
Technical Field
The invention relates to a ceramic oxide film, belongs to the technical field of inorganic materials, and particularly relates to a processing technology of a high-temperature-resistant ceramic oxide film.
Background
The plasma electrolytic oxidation technology is an anodic oxidation technology which is established on the basis of anodic oxidation and is a relatively new metal material surface treatment technology established on the basis of anodic oxidation, wherein valve metals (called valve metals) such as aluminum, titanium, niobium, zirconium, tantalum and the like or alloys thereof are placed in an electrolyte solution, plasma arc discharge spots are generated on the surface of the material by an electrochemical method, and a ceramic film layer is generated under the combined action of thermochemistry, plasma chemistry and electrochemistry.
In the existing surface treatment technology, the anodic oxidation technology is to obtain an amorphous oxide film on the surface of aluminum, magnesium and other alloys by adopting a common alternating current or direct current power supply in an acid electrolyte. The film layer is thin (5-20 mu m), low in hardness (Hv 100-400), not resistant to high temperature, low in strength, porous in surface and required to be subjected to post-treatment.
The existing treatment technology also comprises a chemical oxidation technology, wherein chromate and additives are mainly used as electrolyte solution in the chemical oxidation technology and are subjected to chemical reaction with base metal, so that a film is formed on the surface of the base metal, the formed film is thin, the hardness of the film is low, the corrosion resistance is poor, and the environmental pollution in the preparation process is serious.
The micro-arc oxidation technology is a new surface treatment technology developed on the anodic oxidation technology, namely, a ceramic film layer mainly based on matrix metal oxide grows on the surfaces of aluminum, magnesium, titanium and alloys thereof by the combination of electrolyte and corresponding electrical parameters under the action of instantaneous high temperature and high pressure generated by micro-arc discharge.
Although the micro-arc oxidation technology can form a ceramic oxide film layer with better performance on the surface of the alloy compared with the traditional technology, the formed ceramic oxide film layer still has the defects of poor high-temperature resistance and more porosity, so that how to form the ceramic oxide film layer with better high-temperature resistance on the surface of the alloy by using the micro-arc oxidation technology still has a great deal of problems.
Disclosure of Invention
The invention provides a high-temperature-resistant ceramic oxide film and a processing technology thereof, aiming at solving the problems in the prior art that the ceramic oxide film formed on the surface of titanium alloy by the existing micro-arc oxidation technology still has poor high-temperature resistance and high porosity, so that the ceramic oxide film can be peeled off under the high-temperature condition.
In order to achieve the purpose, the invention provides the following technical scheme:
the high-temperature-resistant ceramic oxide film is characterized by mainly comprising the following raw material components in parts by weight: 32-40 parts of sodium salt, 4-5 parts of sodium hypophosphite, 1-2 parts of sodium carbonate, 2-4 parts of ammonia water and 1-3 parts of sodium fluoride, wherein the sodium salt and the sodium hypophosphite are used as electrolyte components to form a better ceramic oxide film on the surface of the alloy, the added sodium carbonate can promote the densification of the film, and the added sodium fluoride can be used as a film forming aid to promote the formation of the ceramic oxide film on the surface of the alloy.
The high-temperature-resistant ceramic oxide film is characterized by further comprising the following raw material components in parts by weight: 8-15 parts of modified microcapsules, wherein the added microcapsules can be adsorbed on the surface of the titanium alloy after being mixed with the titanium alloy, and a formed ceramic oxide film is densified in the subsequent treatment process, so that the heat resistance of the product is improved.
Preferably, the sodium salt is sodium silicate or any one of sodium silicates, and ceramic oxide films with different components can be formed on the surface of the alloy by adding different aluminum salts.
The modified microcapsule contains modified glucose, polyallylamine hydrochloride and acid radical ions as optimization, wherein the modified glucose is aldehyde glucose.
As optimization, the high-temperature resistant ceramic oxide film comprises the following raw material components in parts by weight: 40 parts of sodium silicate, 5 parts of sodium hypophosphite, 2 parts of sodium carbonate, 3 parts of ammonia water, 1 part of sodium fluoride and 12 parts of modified microcapsules.
As optimization, the processing technology of the high-temperature resistant ceramic oxide film mainly comprises the following steps:
(1) modifying glucan;
(2) mixing the modified glucan and polyallylamine hydrochloride solution in an inert gas atmosphere for reaction, then adding a reducing agent for reduction reaction, filtering, and freeze-drying;
(3) mixing the substance obtained in the step (2) with a metal salt solution under an acidic condition, filtering and drying;
(4) mixing sodium salt and sodium hypophosphite, adding sodium carbonate, sodium fluoride, ammonia water, water and the substance obtained in the step (3), and stirring and mixing;
(5) performing micro-arc oxidation treatment by taking the substance obtained in the step (4) as an electrolyte, taking a titanium alloy as an anode and a stainless steel tank as a cathode to obtain a pretreated ceramic oxide film, and performing high-temperature treatment on the pretreated ceramic oxide film;
(6) and (4) performing index analysis on the product obtained in the step (4).
As optimization, the processing technology of the high-temperature resistant ceramic oxide film mainly comprises the following steps:
(1) mixing glucan and water according to a mass ratio of 1: 200-1: 220, adding potassium periodate accounting for 0.1-0.2 times of the mass of the glucan, stirring and reacting to obtain a modified glucan mixed solution, and mixing the modified glucan mixed solution with a barium chloride solution according to a mass ratio of 1: 2, mixing, stirring for reaction, filtering to obtain a pretreated glucan solution, and mixing the pretreated glucan solution with a sodium sulfate solution according to a mass ratio of 1: 2, mixing, stirring for reaction, and filtering;
(2) mixing the substance obtained in the step (1) and a polyallylamine hydrochloride solution according to a mass ratio of 2: 1, mixing, stirring and reacting in an alkaline environment under the nitrogen atmosphere to obtain a pretreated microcapsule dispersion liquid, and mixing the pretreated microcapsule dispersion liquid with sodium borohydride according to a mass ratio of 100: 1, mixing, stirring for reaction, filtering, and freeze-drying;
(3) mixing the substance obtained in the step (2) with water according to the mass ratio of 1: 18-1: 20, adjusting the pH value to 5-6, adding metal salt with the mass 0.3-0.5 time that of the substance obtained in the step (2), stirring for reaction, filtering and drying;
(4) sodium salt and sodium hypophosphite are mixed according to the mass ratio of 8: 1, adding sodium carbonate which is 0.4-0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.6-0.7 time of the mass of sodium hypophosphite, sodium fluoride which is 0.2-0.3 time of the mass of sodium hypophosphite, a substance obtained in the step (3) which is 2-3 times of the mass of sodium hypophosphite and water which is 20-40 times of the mass of sodium hypophosphite, and stirring and mixing;
(5) taking the substance obtained in the step (4) as an electrolyte, taking a titanium alloy as an anode and a stainless steel electrolytic cell as a cathode, carrying out an electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at the temperature of 300-400 ℃ in a nitrogen atmosphere for 1-2 h, and calcining for 1-2 h at the temperature of 200-400 ℃ and under the oxygen concentration of 120-200 mg/L;
(6) and (5) performing index analysis on the product obtained in the step (5), namely testing the high temperature resistance and the density of the product.
In the titanium alloy obtained in the step (5), the mass fraction of titanium element is 92%, the mass fraction of aluminum element is 5.0-6.5%, and the mass fraction of vanadium element is 3.5-4.5%.
Preferably, the metal salt in the step (3) is prepared by mixing potassium metaaluminate and potassium tetrachloropalladate according to a mass ratio of 2: 1-3: 1, mixing to obtain the metal salt.
In the step (5), the electrolysis parameters are that the current density is 4-8A/dm 2, the frequency is 150-450 Hz, the duty ratio is 10-35%, and the voltage is 200-700V.
Compared with the prior art, the invention has the beneficial effects that: the invention adds the modified microcapsule when preparing the high temperature resistant ceramic oxide film, firstly, the modified microcapsule is prepared by mixing the aldehydic glucan and the polyallylamine hydrochloride, because the microcapsule has pH stimulation responsiveness, the microcapsule can expand under the acidic condition, the added palladate ions and the meta-aluminate ions can be absorbed in the microcapsule, and in the subsequent heat treatment process, because the glucan and the polyallylamine hydrochloride can be carbonized under the high temperature condition, carbonaceous materials with reducibility can be formed inside the ceramic oxide film, further the palladate ions and the meta-aluminate ions can be reduced to form metal simple substances, the metal simple substances can fill the ceramic oxide film, the density of the ceramic oxide film is improved, and because the filling of the material, the heat conductivity of the ceramic oxide film can be improved together with the metal materials, thereby the heat resistance of the product is improved, and moreover, because the microcapsules contain polyallylamine hydrochloride, the polyallylamine hydrochloride has excellent affinity to inorganic metal materials and can be adsorbed on the surface of the titanium alloy after being mixed with the titanium alloy, so that the polyallylamine hydrochloride is uniformly distributed in the ceramic oxide film, and the heat resistance of the product is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method of the present invention, the following examples are given, and the method of testing each index of the high temperature resistant ceramic oxide film produced in the following examples is as follows:
high temperature resistance: carrying out heat preservation treatment on the high-temperature-resistant ceramic oxide film obtained in each example and a comparative product at the temperature of 700 ℃ for 5 hours, and observing the shape of the ceramic oxide film on the surface of the titanium alloy;
density: and (3) placing the high-temperature-resistant ceramic oxide film obtained in each example and a comparative product in a sodium chloride solution with the concentration of 10%, standing at constant temperature for 96h, and measuring the weight loss rate, wherein the smaller the weight loss rate is, the better the density is.
Example 1:
a high-temperature-resistant ceramic oxide film mainly comprises the following raw materials in parts by weight: 40 parts of sodium silicate, 5 parts of sodium hypophosphite, 2 parts of sodium carbonate, 3 parts of ammonia water, 1 part of sodium fluoride and 12 parts of modified microcapsules;
a high-temperature resistant ceramic oxide film processing technology mainly comprises the following steps:
(1) mixing glucan and water according to a mass ratio of 1: 220, adding potassium periodate with the mass 0.2 time that of the glucan, stirring and reacting for 2 hours at the temperature of 60 ℃ and the rotating speed of 300r/min to obtain modified glucan mixed liquor, mixing the modified glucan mixed liquor with a barium chloride solution with the mass fraction of 12% according to the mass ratio of 1: 2, mixing, stirring for reacting for 80min, filtering to obtain a pretreated glucan solution, mixing the pretreated glucan solution with a sodium sulfate solution with the mass fraction of 15% according to a mass ratio of 1: 2, mixing, stirring and reacting for 60min, and filtering;
(2) mixing the substance obtained in the step (1) with a polyallylamine hydrochloride solution with the mass fraction of 0.4% according to the mass ratio of 2: 1, mixing the materials in the reaction kettle, introducing nitrogen into the reaction kettle at a speed of 50mL/min, adjusting the pH of the materials in the reaction kettle to 10.0, stirring and reacting for 2 hours under the conditions that the temperature is 30 ℃ and the rotating speed is 280r/min to obtain a pretreated microcapsule dispersion liquid, and mixing the pretreated microcapsule dispersion liquid and sodium borohydride according to a mass ratio of 100: 1, mixing, stirring and reacting for 10 hours at the temperature of 35 ℃ and the rotating speed of 320r/min, filtering, and freeze-drying;
(3) mixing the substance obtained in the step (2) with water according to the mass ratio of 1: 20, mixing, adjusting the pH value to 6, adding metal salt with the mass 0.5 time that of the substance obtained in the step (2), stirring and reacting for 2 hours at the temperature of 45 ℃ and the rotating speed of 250r/min, filtering and drying;
(4) sodium silicate and sodium hypophosphite are mixed according to the mass ratio of 8: 1, mixing the mixture in a beaker, adding sodium carbonate which is 0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.7 time of the mass of the sodium hypophosphite and has the mass fraction of 10%, sodium fluoride which is 0.3 time of the mass of the sodium hypophosphite, a substance which is 3 times of the mass of the sodium hypophosphite and is obtained in the step (3) and water which is 40 times of the mass of the sodium hypophosphite into the beaker, and stirring and mixing the mixture for 80min at the temperature of 40 ℃ and the rotating speed of 300 r/min;
(5) taking the substance obtained in the step (4) as electrolyte, taking titanium alloy as an anode and a stainless steel electrolytic tank as a cathode, carrying out electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at 400 ℃ in a nitrogen atmosphere for 2h, and calcining for 2h under the conditions that the temperature is 300 ℃ and the oxygen concentration is 180 mg/L;
(6) and (5) performing index analysis on the product obtained in the step (5).
In the titanium alloy obtained in the step (5), the mass fraction of the titanium element is 92%, the mass fraction of the aluminum element is 4.5%, and the mass fraction of the vanadium element is 3.5%.
Preferably, the metal salt in the step (3) is prepared by mixing potassium metaaluminate and potassium tetrachloropalladate according to a mass ratio of 3: 1, mixing to obtain the metal salt.
As optimization, the electrolysis parameters in the step (5) are that the current density is 6A/dm2, the frequency is 220Hz, the duty ratio is 10 percent, and the voltage is 400V.
Example 2:
a high-temperature-resistant ceramic oxide film mainly comprises the following raw materials in parts by weight: 40 parts of sodium silicate, 5 parts of sodium hypophosphite, 2 parts of sodium carbonate, 3 parts of ammonia water, 1 part of sodium fluoride and 12 parts of modified microcapsules;
a high-temperature resistant ceramic oxide film processing technology mainly comprises the following steps:
(1) mixing glucan and water according to a mass ratio of 1: 220, adding potassium periodate with the mass 0.2 time that of the glucan, stirring and reacting for 2 hours at the temperature of 60 ℃ and the rotating speed of 300r/min to obtain modified glucan mixed liquor, mixing the modified glucan mixed liquor with a barium chloride solution with the mass fraction of 12% according to the mass ratio of 1: 2, mixing, stirring for reacting for 80min, filtering to obtain a pretreated glucan solution, mixing the pretreated glucan solution with a sodium sulfate solution with the mass fraction of 15% according to a mass ratio of 1: 2, mixing, stirring and reacting for 60min, and filtering;
(2) mixing the substance obtained in the step (1) with a polyallylamine hydrochloride solution with the mass fraction of 0.4% according to the mass ratio of 2: 1, mixing the materials in the reaction kettle, introducing nitrogen into the reaction kettle at a speed of 50mL/min, adjusting the pH of the materials in the reaction kettle to 10.0, stirring and reacting for 2 hours under the conditions that the temperature is 30 ℃ and the rotating speed is 280r/min to obtain a pretreated microcapsule dispersion liquid, and mixing the pretreated microcapsule dispersion liquid and sodium borohydride according to a mass ratio of 100: 1, mixing, stirring and reacting for 10 hours at the temperature of 35 ℃ and the rotating speed of 320r/min, filtering, and freeze-drying;
(3) sodium silicate and sodium hypophosphite are mixed according to the mass ratio of 8: 1, mixing the mixture in a beaker, adding sodium carbonate which is 0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.7 time of the mass of the sodium hypophosphite and has the mass fraction of 10%, sodium fluoride which is 0.3 time of the mass of the sodium hypophosphite, a substance which is 3 times of the mass of the sodium hypophosphite and is obtained in the step (2) and water which is 40 times of the mass of the sodium hypophosphite into the beaker, and stirring and mixing the mixture for 80min at the temperature of 40 ℃ and the rotating speed of 300 r/min;
(4) taking the substance obtained in the step (3) as electrolyte, taking titanium alloy as an anode and a stainless steel electrolytic tank as a cathode, carrying out electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at 400 ℃ in a nitrogen atmosphere for 2h, and calcining for 2h under the conditions that the temperature is 300 ℃ and the oxygen concentration is 180 mg/L;
(5) and (4) performing index analysis on the product obtained in the step (4).
In the titanium alloy obtained in the step (4), the mass fraction of the titanium element is 92%, the mass fraction of the aluminum element is 4.5%, and the mass fraction of the vanadium element is 3.5%.
As optimization, the electrolysis parameters in the step (4) are that the current density is 6A/dm2, the frequency is 220Hz, the duty ratio is 10 percent, and the voltage is 400V.
Example 3:
a high-temperature-resistant ceramic oxide film mainly comprises the following raw materials in parts by weight: 40 parts of sodium silicate, 5 parts of sodium hypophosphite, 2 parts of sodium carbonate, 3 parts of ammonia water, 1 part of sodium fluoride and 12 parts of modified microcapsules;
a high-temperature resistant ceramic oxide film processing technology mainly comprises the following steps:
(1) adding 0.4% by mass of polyallylamine hydrochloride solution into a reaction kettle, adjusting the pH of the material in the reaction kettle to 6, stirring and reacting for 2 hours at 45 ℃ and at a rotating speed of 250r/min for metal salt with the mass fraction of 0.4% by mass of the polyallylamine hydrochloride solution, carrying out rotary evaporation and concentration at 80 ℃, 120r/min and 600kPa until the water content is 0.1%, and drying;
(2) sodium silicate and sodium hypophosphite are mixed according to the mass ratio of 8: 1, mixing the mixture in a beaker, adding sodium carbonate which is 0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.7 time of the mass of the sodium hypophosphite and has the mass fraction of 10%, sodium fluoride which is 0.3 time of the mass of the sodium hypophosphite, a substance which is 3 times of the mass of the sodium hypophosphite and is obtained in the step (1) and water which is 40 times of the mass of the sodium hypophosphite into the beaker, and stirring and mixing the substances and the water for 80min at the temperature of 40 ℃ and the rotating speed of 300 r/min;
(3) taking the substance obtained in the step (2) as electrolyte, taking titanium alloy as an anode and a stainless steel electrolytic tank as a cathode, carrying out electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at 400 ℃ in a nitrogen atmosphere, and calcining for 2 hours at 300 ℃ and under the condition of oxygen concentration of 180mg/L after carbonizing for 2 hours;
(4) and (4) performing index analysis on the product obtained in the step (3).
In the titanium alloy obtained in the step (3), the mass fraction of the titanium element is 92%, the mass fraction of the aluminum element is 4.5%, and the mass fraction of the vanadium element is 3.5%.
Preferably, the metal salt in the step (1) is prepared by mixing potassium metaaluminate and potassium tetrachloropalladate according to a mass ratio of 3: 1, mixing to obtain the metal salt.
As optimization, the electrolysis parameters in the step (3) are that the current density is 6A/dm2, the frequency is 220Hz, the duty ratio is 10 percent, and the voltage is 400V.
Example 4:
a high-temperature-resistant ceramic oxide film mainly comprises the following raw materials in parts by weight: 40 parts of sodium silicate, 5 parts of sodium hypophosphite, 2 parts of sodium carbonate, 3 parts of ammonia water, 1 part of sodium fluoride and 12 parts of modified microcapsules;
a high-temperature resistant ceramic oxide film processing technology mainly comprises the following steps:
(1) mixing glucan and water according to a mass ratio of 1: 220, adding potassium periodate with the mass 0.2 time that of the glucan, stirring and reacting for 2 hours at the temperature of 60 ℃ and the rotating speed of 300r/min to obtain modified glucan mixed liquor, mixing the modified glucan mixed liquor with a barium chloride solution with the mass fraction of 12% according to the mass ratio of 1: 2, mixing, stirring for reacting for 80min, filtering to obtain a pretreated glucan solution, mixing the pretreated glucan solution with a sodium sulfate solution with the mass fraction of 15% according to a mass ratio of 1: 2, mixing, stirring and reacting for 60min, and filtering;
(2) mixing the substance obtained in the step (1) with a polyallylamine hydrochloride solution with the mass fraction of 0.4% according to the mass ratio of 2: 1, mixing the materials in the reaction kettle, introducing nitrogen into the reaction kettle at a speed of 50mL/min, adjusting the pH of the materials in the reaction kettle to 10.0, stirring and reacting for 2 hours under the conditions that the temperature is 30 ℃ and the rotating speed is 280r/min to obtain a pretreated microcapsule dispersion liquid, and mixing the pretreated microcapsule dispersion liquid and sodium borohydride according to a mass ratio of 100: 1, mixing, stirring and reacting for 10 hours at the temperature of 35 ℃ and the rotating speed of 320r/min, filtering, and freeze-drying;
(3) mixing the substance obtained in the step (2) with water according to the mass ratio of 1: 20, mixing, adjusting the pH value to 6, adding metal salt with the mass 0.5 time that of the substance obtained in the step (2), stirring and reacting for 2 hours at the temperature of 45 ℃ and the rotating speed of 250r/min, filtering and drying;
(4) sodium silicate and sodium hypophosphite are mixed according to the mass ratio of 8: 1, mixing the mixture in a beaker, adding sodium carbonate which is 0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.7 time of the mass of the sodium hypophosphite and has the mass fraction of 10%, sodium fluoride which is 0.3 time of the mass of the sodium hypophosphite, a substance which is 3 times of the mass of the sodium hypophosphite and is obtained in the step (3) and water which is 40 times of the mass of the sodium hypophosphite into the beaker, and stirring and mixing the mixture for 80min at the temperature of 40 ℃ and the rotating speed of 300 r/min;
(5) taking the substance obtained in the step (4) as electrolyte, taking titanium alloy as an anode and a stainless steel electrolytic tank as a cathode, carrying out electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at 400 ℃ in a nitrogen atmosphere for 2h, and calcining for 2h under the conditions that the temperature is 300 ℃ and the oxygen concentration is 180 mg/L;
(6) and (5) performing index analysis on the product obtained in the step (5).
In the titanium alloy obtained in the step (5), the mass fraction of the titanium element is 92%, the mass fraction of the aluminum element is 4.5%, and the mass fraction of the vanadium element is 3.5%.
Preferably, the metal salt in the step (3) is prepared by mixing potassium metaaluminate and potassium tetrachloropalladate according to a mass ratio of 3: 1, mixing to obtain the metal salt.
As optimization, the electrolysis parameters in the step (5) are that the current density is 6A/dm2, the frequency is 220Hz, the duty ratio is 10 percent, and the voltage is 400V.
Example 5:
a high-temperature-resistant ceramic oxide film mainly comprises the following raw materials in parts by weight: 40 parts of sodium silicate, 5 parts of sodium hypophosphite, 2 parts of sodium carbonate, 3 parts of ammonia water, 1 part of sodium fluoride and 12 parts of modified microcapsules;
a high-temperature resistant ceramic oxide film processing technology mainly comprises the following steps:
(1) mixing glucan and water according to a mass ratio of 1: 220, adding potassium periodate with the mass 0.2 time that of the glucan, stirring and reacting for 2 hours at the temperature of 60 ℃ and the rotating speed of 300r/min to obtain modified glucan mixed liquor, mixing the modified glucan mixed liquor with a barium chloride solution with the mass fraction of 12% according to the mass ratio of 1: 2, mixing, stirring for reacting for 80min, filtering to obtain a pretreated glucan solution, mixing the pretreated glucan solution with a sodium sulfate solution with the mass fraction of 15% according to a mass ratio of 1: 2, mixing, stirring and reacting for 60min, and filtering;
(2) mixing the substance obtained in the step (1) with a polyallylamine hydrochloride solution with the mass fraction of 0.4% according to the mass ratio of 2: 1, mixing the materials in the reaction kettle, introducing nitrogen into the reaction kettle at a speed of 50mL/min, adjusting the pH of the materials in the reaction kettle to 10.0, stirring and reacting for 2 hours under the conditions that the temperature is 30 ℃ and the rotating speed is 280r/min to obtain a pretreated microcapsule dispersion liquid, and mixing the pretreated microcapsule dispersion liquid and sodium borohydride according to a mass ratio of 100: 1, mixing, stirring and reacting for 10 hours at the temperature of 35 ℃ and the rotating speed of 320r/min, filtering, and freeze-drying;
(3) sodium silicate and sodium hypophosphite are mixed according to the mass ratio of 8: 1, mixing the mixture in a beaker, adding sodium carbonate which is 0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.7 time of the mass of the sodium hypophosphite and has the mass fraction of 10%, sodium fluoride which is 0.3 time of the mass of the sodium hypophosphite, a substance which is 3 times of the mass of the sodium hypophosphite and is obtained in the step (2) and water which is 40 times of the mass of the sodium hypophosphite into the beaker, and stirring and mixing the mixture for 80min at the temperature of 40 ℃ and the rotating speed of 300 r/min;
(4) taking the substance obtained in the step (3) as electrolyte, taking titanium alloy as an anode and a stainless steel electrolytic tank as a cathode, carrying out electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at 400 ℃ in a nitrogen atmosphere for 2h, and calcining for 2h under the conditions that the temperature is 300 ℃ and the oxygen concentration is 180 mg/L;
(5) and (4) performing index analysis on the product obtained in the step (4).
In the titanium alloy obtained in the step (4), the mass fraction of the titanium element is 92%, the mass fraction of the aluminum element is 4.5%, and the mass fraction of the vanadium element is 3.5%.
As optimization, the electrolysis parameters in the step (4) are that the current density is 6A/dm2, the frequency is 220Hz, the duty ratio is 10 percent, and the voltage is 400V.
Example 6:
a high-temperature-resistant ceramic oxide film mainly comprises the following raw materials in parts by weight: 40 parts of sodium silicate, 5 parts of sodium hypophosphite, 2 parts of sodium carbonate, 3 parts of ammonia water, 1 part of sodium fluoride and 12 parts of modified microcapsules;
a high-temperature resistant ceramic oxide film processing technology mainly comprises the following steps:
(1) adding 0.4% by mass of polyallylamine hydrochloride solution into a reaction kettle, adjusting the pH of the material in the reaction kettle to 6, stirring and reacting for 2 hours at 45 ℃ and at a rotating speed of 250r/min for metal salt with the mass fraction of 0.4% by mass of the polyallylamine hydrochloride solution, carrying out rotary evaporation and concentration at 80 ℃, 120r/min and 600kPa until the water content is 0.1%, and drying;
(2) sodium silicate and sodium hypophosphite are mixed according to the mass ratio of 8: 1, mixing the mixture in a beaker, adding sodium carbonate which is 0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.7 time of the mass of the sodium hypophosphite and has the mass fraction of 10%, sodium fluoride which is 0.3 time of the mass of the sodium hypophosphite, a substance which is 3 times of the mass of the sodium hypophosphite and is obtained in the step (1) and water which is 40 times of the mass of the sodium hypophosphite into the beaker, and stirring and mixing the substances and the water for 80min at the temperature of 40 ℃ and the rotating speed of 300 r/min;
(3) taking the substance obtained in the step (2) as electrolyte, taking titanium alloy as an anode and a stainless steel electrolytic tank as a cathode, carrying out electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at 400 ℃ in a nitrogen atmosphere, and calcining for 2 hours at 300 ℃ and under the condition of oxygen concentration of 180mg/L after carbonizing for 2 hours;
(4) and (4) performing index analysis on the product obtained in the step (3).
In the titanium alloy obtained in the step (3), the mass fraction of the titanium element is 92%, the mass fraction of the aluminum element is 4.5%, and the mass fraction of the vanadium element is 3.5%.
Preferably, the metal salt in the step (1) is prepared by mixing potassium metaaluminate and potassium tetrachloropalladate according to a mass ratio of 3: 1, mixing to obtain the metal salt.
As optimization, the electrolysis parameters in the step (3) are that the current density is 6A/dm2, the frequency is 220Hz, the duty ratio is 10 percent, and the voltage is 400V.
Comparative example:
a high-temperature-resistant ceramic oxide film mainly comprises the following raw materials in parts by weight: 40 parts of sodium silicate, 5 parts of sodium hypophosphite, 2 parts of sodium carbonate, 3 parts of ammonia water and 1 part of sodium fluoride;
a high-temperature resistant ceramic oxide film processing technology mainly comprises the following steps:
(1) sodium silicate and sodium hypophosphite are mixed according to the mass ratio of 8: 1, mixing the mixture in a beaker, adding sodium carbonate which is 0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.7 time of the mass of the sodium hypophosphite and has the mass fraction of 10%, sodium fluoride which is 0.3 time of the mass of the sodium hypophosphite and water which is 40 times of the mass of the sodium hypophosphite into the beaker, and stirring and mixing the mixture for 80min under the conditions that the temperature is 40 ℃ and the rotating speed is 300 r/min;
(2) taking the substance obtained in the step (1) as electrolyte, taking titanium alloy as an anode and a stainless steel electrolytic tank as a cathode, carrying out electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at 400 ℃ in a nitrogen atmosphere for 2h, and calcining for 2h under the conditions that the temperature is 300 ℃ and the oxygen concentration is 180 mg/L;
(3) and (3) performing index analysis on the product obtained in the step (2).
In the titanium alloy obtained in the step (2), the mass fraction of titanium element is 92%, the mass fraction of aluminum element is 4.5%, and the mass fraction of vanadium element is 3.5%.
As optimization, the electrolysis parameters in the step (2) are that the current density is 6A/dm2, the frequency is 220Hz, the duty ratio is 10 percent, and the voltage is 400V.
Example of effects:
table 1 below shows the index analysis results of the high temperature resistant ceramic oxide films and the processes thereof using examples 1 to 6 of the present invention and comparative examples.
TABLE 1
From the experimental data in table 1, it can be seen that the density and high temperature resistance of the ceramic oxide film on the surface of the alloy of the present invention are significantly better than those of the comparative product, as can be seen from the comparison between example 1 and the comparative product, the density and high temperature resistance of the ceramic oxide film can be effectively improved by adding the modified microcapsule in the preparation process of the product, as can be seen from the comparison between example 1 and example 2, when no metal salt is added in the microcapsule, the metal oxide is contained in the ceramic oxide film layer on the surface of the alloy, thereby affecting the density and high temperature resistance of the ceramic oxide film, as can be seen from the comparison between example 1 and example 3, when the modified dextran is not added, the microcapsule can not be formed, thereby forming the polyallylamine hydrochloride on the surface of the alloy, although the density of the product can be improved, because the existence of the polyallylamine hydrochloride affects the binding force between the ceramic oxide film and the alloy, thereby affecting the high temperature, comparing example 1 with example 4, example 2 with example 5, and example 3 with example 6, when different sodium salts are used as the components of the electrolyte, the density and the high temperature resistance of the ceramic oxide film can be improved by adding the modified microcapsule.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference thereto is therefore intended to be embraced therein.
Claims (1)
1. A processing technology of a high-temperature resistant ceramic oxide film is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) mixing glucan and water according to a mass ratio of 1: 220, adding potassium periodate with the mass 0.2 time that of the glucan, stirring and reacting for 2 hours at the temperature of 60 ℃ and the rotating speed of 300r/min to obtain modified glucan mixed liquor, mixing the modified glucan mixed liquor with a barium chloride solution with the mass fraction of 12% according to the mass ratio of 1: 2, mixing, stirring for reacting for 80min, filtering to obtain a pretreated glucan solution, mixing the pretreated glucan solution with a sodium sulfate solution with the mass fraction of 15% according to a mass ratio of 1: 2, mixing, stirring and reacting for 60min, and filtering;
(2) mixing the substance obtained in the step (1) with a polyallylamine hydrochloride solution with the mass fraction of 0.4% according to the mass ratio of 2: 1, mixing the materials in the reaction kettle, introducing nitrogen into the reaction kettle at a speed of 50mL/min, adjusting the pH of the materials in the reaction kettle to 10.0, stirring and reacting for 2 hours under the conditions that the temperature is 30 ℃ and the rotating speed is 280r/min to obtain a pretreated microcapsule dispersion liquid, and mixing the pretreated microcapsule dispersion liquid and sodium borohydride according to a mass ratio of 100: 1, mixing, stirring and reacting for 10 hours at the temperature of 35 ℃ and the rotating speed of 320r/min, filtering, and freeze-drying;
(3) mixing the substance obtained in the step (2) with water according to the mass ratio of 1: 20, mixing, adjusting the pH value to 6, adding metal salt with the mass 0.5 time that of the substance obtained in the step (2), stirring and reacting for 2 hours at the temperature of 45 ℃ and the rotating speed of 250r/min, filtering and drying;
(4) sodium silicate and sodium hypophosphite are mixed according to the mass ratio of 8: 1, mixing the mixture in a beaker, adding sodium carbonate which is 0.5 time of the mass of sodium hypophosphite, ammonia water which is 0.7 time of the mass of the sodium hypophosphite and has the mass fraction of 10%, sodium fluoride which is 0.3 time of the mass of the sodium hypophosphite, a substance which is 3 times of the mass of the sodium hypophosphite and is obtained in the step (3) and water which is 40 times of the mass of the sodium hypophosphite into the beaker, and stirring and mixing the mixture for 80min at the temperature of 40 ℃ and the rotating speed of 300 r/min;
(5) taking the substance obtained in the step (4) as electrolyte, taking titanium alloy as an anode and a stainless steel electrolytic tank as a cathode, carrying out electrolytic reaction to obtain a pretreated ceramic oxide film, carbonizing the pretreated ceramic oxide film at 400 ℃ in a nitrogen atmosphere for 2h, and calcining for 2h under the conditions that the temperature is 300 ℃ and the oxygen concentration is 180 mg/L;
(6) performing index analysis on the product obtained in the step (5);
the metal salt in the step (3) is prepared by mixing potassium metaaluminate and potassium tetrachloropalladate according to a mass ratio of 3: 1, mixing to obtain metal salt;
in the step (5), the mass fraction of titanium element in the titanium alloy is 92%, the mass fraction of aluminum element is 4.5%, and the mass fraction of vanadium element is 3.5%;
and (5) the electrolysis parameters are that the current density is 6A/dm2, the frequency is 220Hz, the duty ratio is 10 percent, and the voltage is 400V.
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