CN113292350B - Normal-pressure low-temperature cured lanthanum-aluminum phosphate composite material and preparation method and application thereof - Google Patents
Normal-pressure low-temperature cured lanthanum-aluminum phosphate composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a lanthanum-aluminum phosphate composite material which comprises lanthanum phosphate and aluminum phosphate compounded with the lanthanum phosphate. The composite material has specific phase composition and microstructure, and the lanthanum phosphate and the aluminum phosphate are doped and compounded with each other and bonded through ionic bonds, so that the lanthanum-aluminum phosphate composite material which can be rapidly cured and formed at low temperature and has excellent performance at high temperature is obtained. The phosphate composite material provided by the invention can be cured and molded at normal pressure and low temperature, so that the product can be used without special high-temperature sintering by special equipment during molding, and the molding process saves complex high-temperature sintering and saves energy. The composite material has excellent high temperature resistance and good ablation resistance, the surface of a sample is complete after ablation at the ablation temperature of 2000 ℃, the melting condition is not seen, and meanwhile, the preparation process is simple and the preparation period is short.
Description
Technical Field
The invention belongs to the technical field of lanthanum-aluminum phosphate composite materials, relates to a lanthanum-aluminum phosphate composite material, and a preparation method and application thereof, and particularly relates to a normal-pressure low-temperature-cured 2000-DEG C-resistant lanthanum-aluminum phosphate composite material, and a preparation method and application thereof.
Background
With the vigorous development of science and technology, many fields (such as energy plants for aerospace, nuclear engineering and the like) involve extremely high temperature environments. As a material serving in an extreme environment, the high-temperature heat-resistant material needs to have good high-temperature resistance and other properties, so that the normal working environment of a mechanical component is ensured. In order to meet the requirements of the high-temperature application field, the preparation of high-performance and low-cost high-temperature resistant materials has important strategic significance.
At present, carbon/carbon composite materials are high-temperature resistant materials widely applied, but the carbon/carbon composite materials are easy to oxidize and lose effectiveness at high temperature. In order to improve the oxygen-rich high-temperature resistance of carbon/carbon, people try to modify carbon/carbon by a ZrC-SiC composite coating or other methods; however, these coatings either have the defects that the thermal expansion coefficients of the carbon/carbon substrate and the coating are difficult to match or the coatings are designed, so that the ablation resistance temperature is too low or the ablation loss at high temperature is too fast, and the carbon/carbon and the composite material have the fatal defects of high preparation temperature, expensive experimental raw materials, long process cycle and the like.
Researches find that the phosphate material has excellent performances of high refractoriness, good oxidation resistance and the like. According to the literature, "development of phosphate-based high-temperature-resistant adhesive, development and application of silicate inorganic adhesive, analysis and discussion of bonding mechanism of copper oxide-phosphate adhesive, and research progress of microwave wave-transmitting material", the use temperature of room-temperature phosphate curing adhesive developed in Russia, Europe and America and other countries can reach 1700 ℃. However, China is still in the development stage in the field of phosphate, and the defects of high curing temperature, poor process performance and the like generally exist. In order to solve the problem of over-high curing temperature, the applicant has made an original study that-O-Cu-O-bridged phosphate can be cured at room temperature by using metal oxide CuO as a curing agent. However, when the ablation temperature exceeds 1300 ℃, the bonded-O-Cu-O-of the material is damaged, and the material is melted.
Therefore, how to better improve the high temperature resistance of phosphate and help further develop the research of low-cost high-performance phosphate-based composite materials has become one of the focuses of great attention of many leading-edge researchers in the industry.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a lanthanum-aluminum phosphate composite material, a preparation method and an application thereof, and in particular, to a lanthanum-aluminum phosphate composite material that is cured at normal pressure and low temperature and resists 2000 ℃. The lanthanum-aluminum phosphate composite material provided by the invention can be quickly cured and molded at low temperature, has excellent high-temperature resistance and ablation resistance, is simple in preparation process, short in production period and strong in controllability, and is beneficial to subsequent large-scale production and popularization.
The invention provides a lanthanum-aluminum phosphate composite material, which comprises lanthanum phosphate and aluminum phosphate compounded with the lanthanum phosphate;
in the composite material, the molar ratio of the lanthanum phosphate to the aluminum phosphate is (1-1.78): 1;
the composite material also comprises element chromium;
the element chromium in the composite material has a chemical valence state of + 3;
the molar content of the element chromium is 0.05-0.1%.
Preferably, the compounding comprises doping;
the lanthanum phosphate and the aluminum phosphate are bonded through ionic bonds;
the composite material takes lanthanum phosphate as a main phase and is intercalated with an aluminum phosphate phase.
Preferably, the lanthanum-aluminum phosphate composite material is a high-temperature-resistant composite material;
in the composite material, the lanthanum phosphate and the aluminum phosphate are connected tightly, and the surface is smooth and compact.
Preferably, the composite material is not melted after being ablated by high-temperature flame below 2000 ℃;
the composite material is a phosphate composite material cured at normal pressure and low temperature;
the low temperature is 30-50 ℃.
The invention provides a preparation method of a lanthanum-aluminum phosphate composite material, which comprises the following steps:
1) reacting the preheated dilute phosphoric acid with aluminum hydroxide to obtain a transparent solution;
2) mixing the transparent solution obtained in the step with chromium trioxide, adding hydrogen peroxide, and carrying out heating reaction to obtain aluminum phosphate chromium-based viscose;
3) stirring and gelling the aluminum phosphate chromium-based viscose obtained in the step and lanthanum oxide, and then placing the mixture into a mold for curing to obtain the lanthanum-aluminum phosphate composite material.
Preferably, the preheating temperature is 80-85 ℃;
the molar ratio of the aluminum hydroxide to the phosphoric acid is (0.2-0.4): (0.8 to 1);
the reaction temperature is 80-85 ℃;
the reaction time is 1-1.5 h.
Preferably, the molar ratio of the aluminum hydroxide to the chromium trioxide is (0.2-0.4): (0.1 to 0.2);
the molar ratio of the hydrogen peroxide to the chromium trioxide is (0.1-0.2): (0.1 to 0.2);
the heating reaction mode is water bath heating;
the temperature of the heating reaction is 80-85 ℃;
the heating reaction time is 20-30 min.
Preferably, the mass ratio of the lanthanum oxide to the aluminum hydroxide is (2-3.7): 1;
the temperature for stirring and gelling is 80-85 ℃;
the stirring gelling time is 1-1.5 h;
the viscosity after stirring and gelling is 8-15 pa.s.
Preferably, the curing temperature is 30-50 ℃;
the curing time is 1-2 h;
the step of low-temperature heat treatment is also included after the solidification;
the temperature of the low-temperature heat treatment is 300-450 ℃.
The invention also provides the application of the lanthanum-aluminum phosphate composite material prepared by the preparation method in any one of the technical schemes or the lanthanum-aluminum phosphate composite material prepared by the preparation method in any one of the technical schemes in the field of high-temperature resistant materials.
The invention provides a lanthanum-aluminum phosphate composite material, which comprises lanthanum phosphate and aluminum phosphate compounded with the lanthanum phosphate; in the composite material, the molar ratio of the lanthanum phosphate to the aluminum phosphate is (1-1.78): 1; the composite material also comprises element chromium; the element chromium in the composite material has a chemical valence state of + 3; the molar content of the element chromium is 0.05-0.1%. Compared with the prior art, the invention aims at the defects of poor temperature resistance, high curing temperature, poor process performance and the like in the preparation of the existing phosphate material. The invention adds high melting point metal oxygenCompound La2O3The ablation resistance of the phosphate is improved, and the phosphate can be rapidly cured at low temperature and normal pressure, so that the phosphate composite material which can meet the technical idea of low cost and short time is obtained.
The lanthanum-aluminum phosphate composite material provided by the invention has specific phase composition and microstructure, and lanthanum phosphate and aluminum phosphate are doped and compounded with each other and bonded through ionic bonds, so that the lanthanum-aluminum phosphate composite material which can be rapidly cured and formed at low temperature and has excellent performance at high temperature is obtained. The phosphate composite material provided by the invention can be cured and molded at normal pressure and low temperature, so that the product can be used without special high-temperature sintering by special equipment during molding, and the molding process saves complex high-temperature sintering and saves energy. And the preparation process is simple and the preparation period is short. The raw material and reagent used for preparation are easy to obtain, the preparation process is simple, and the cost is low. The whole experimental preparation has no complex processes such as temperature adjustment and the like, the total time is less than 1.5h, and the preparation temperature is not high (70-85 ℃). And the composite material has excellent high temperature resistance, and the prepared phosphate sample is sintered and oxidized at the highest temperature (1700 ℃), and the La-Al series phosphate sample has excellent performance and does not have large deformation and defects, thereby showing the excellent high temperature resistance of the low-temperature cured phosphate. Meanwhile, the ablation resistance is good, and the surface of the ablated sample is relatively complete at the ablation temperature of 2000 ℃, and no melting condition is found.
The phosphate composite material provided by the invention can resist the high temperature of 2000 ℃, has lower density, and compensates the defect of high density of a high-temperature metal-based material; the material cost is low, and the defect of high cost of a heat shield and the like is compensated; meanwhile, the material has short preparation period and low treatment temperature, and compensates the defects of complicated preparation and high treatment temperature of the ceramic matrix.
Experimental results show that the La-Al series phosphate prepared by the invention forms compact LaPO in the ablation center4And AlPO4The high-temperature phase is used for resisting ablation at 2000 ℃, and no melting condition is seen, so that the high-temperature resistance of the low-temperature cured phosphate is excellent, and the ablation resistance is good.
Drawings
FIG. 1 is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 1 of the present invention after a 1700 ℃ high temperature resistance experiment;
FIG. 2 is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 1 of the present invention and subjected to high temperature resistance experiments at 300 deg.C, 500 deg.C, 700 deg.C, 1000 deg.C, 1500 deg.C, 1700 deg.C;
FIG. 3 is an XRD spectrum of the La-Al phosphate composite material prepared in example 1 of the present invention and the La-Al phosphate composite material after high temperature experiment;
FIG. 4 is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 2 of the present invention after a 1700 ℃ high temperature resistance experiment;
FIG. 5 is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 2 of the present invention and subjected to high temperature resistance experiments at 300 deg.C, 500 deg.C, 700 deg.C, 1000 deg.C, 1500 deg.C, 1700 deg.C;
fig. 6 is an XRD spectrum of the lanthanum aluminum phosphate composite material prepared in example 2 of the present invention and the lanthanum aluminum phosphate composite material after high temperature experiment;
FIG. 7 is an appearance diagram of a lanthanum-aluminum phosphate composite material ablated after a high-temperature experiment in example 2 of the present invention;
FIG. 8 is a BSEM back scattering scanning electron microscope image of lanthanum aluminum phosphate composite ablated after a high temperature experiment in example 2 of the present invention;
FIG. 9 is an external view of an ablated lanthanum aluminum phosphate composite material prepared in example 2 of the present invention;
FIG. 10 is a BSEM back-scattering scanning electron microscope image of the lanthanum aluminum phosphate composite material prepared in example 2 of the present invention after ablation.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs a purity which is conventional in the field of analytical purification or phosphate composite materials.
The invention provides a lanthanum-aluminum phosphate composite material, which comprises lanthanum phosphate and aluminum phosphate compounded with the lanthanum phosphate;
in the composite material, the molar ratio of the lanthanum phosphate to the aluminum phosphate is (1-1.78): 1;
the composite material also comprises element chromium;
the element chromium in the composite material has a chemical valence state of + 3;
the molar content of the element chromium is 0.05-0.1%.
In the present invention, the composite material includes elemental chromium. Specifically, the composite material preferably includes chromium ions.
In the present invention, the elemental chromium in the composite material has a chemical valence of + 3.
In the invention, the molar content of the element chromium is 0.05-0.1%, preferably 0.06-0.09%, and more preferably 0.07-0.08%.
In the present invention, the recombination preferably includes doping.
In the composite material, the molar ratio of the lanthanum phosphate to the aluminum phosphate is preferably (1-1.78): 1, more preferably (1.1 to 1.7): 1, more preferably (1.3 to 1.6): 1, more preferably (1.4 to 1.5): 1.
in the present invention, the lanthanum phosphate and the aluminum phosphate are preferably bonded by an ionic bond.
In the invention, the composite material preferably takes lanthanum phosphate as a main phase and is intercalated with an aluminum phosphate phase.
In the composite material, the phases of lanthanum phosphate and aluminum phosphate are preferably tightly connected, and the surface is smooth and compact.
In the present invention, the lanthanum aluminate phosphate composite is preferably a high temperature resistant composite.
In the present invention, the composite material is preferably not melted after flame ablation at a high temperature of 2000 ℃ or lower, more preferably not melted at 1900 ℃ or lower, and still more preferably not melted at 1800 ℃ or lower. Specifically, the temperature can be 1700-2000 ℃, or 1800-1900 ℃. The composite material prepared by the invention still has a compact phase structure at the high temperature of 2000 ℃ and is not melted.
In the present invention, the composite material is preferably a phosphate composite material cured at normal pressure and low temperature.
In the invention, the low-temperature curing temperature is preferably 30-50 ℃, more preferably 34-46 ℃, and more preferably 38-42 ℃.
In view of the drawbacks of thermal protective materials in terms of production and high temperature performance. The invention discovers that in the process of researching phosphate: the metal oxide and the aluminum chromium phosphate can be cured and formed at normal pressure and low temperature, and have good high-temperature resistance. Therefore, the invention provides the material which has simple preparation process and can resist the high temperature of 2000 ℃, namely, the material takes the aluminum chromium phosphate as the matrix and the La as the material2O3The aluminum-chromium phosphate composite material is a curing agent, can be cured and molded at normal pressure and low temperature, namely 50 ℃, and has excellent high-temperature resistance and oxidation resistance. The high-temperature-resistant phosphate obtained by the invention is LaPO4(melting point is more than or equal to 2100 ℃) as a main phase and is mixed with AlPO4(the melting point is more than or equal to 1500 ℃) phase. The microstructure can show that the two high-temperature phases are connected closely, the surface is smooth and compact, and the two LaPOs are4：AlPO4The amount ratio of the substances (A) to (B) is about (1-1.78): about 1. The invention provides high temperature resistant LaPO4The composite material can resist oxyacetylene flame ablation treatment at 2000 ℃, is the highest temperature which can be reached by the research of curing phosphate at normal pressure and low temperature in China at present, so that the development of phosphate series in temperature resistance enters a new stage, and is the first oxyacetylene flame ablation test for phosphate materials in China.
The invention provides a preparation method of a lanthanum-aluminum phosphate composite material, which comprises the following steps:
1) reacting the preheated dilute phosphoric acid with aluminum hydroxide to obtain a transparent solution;
2) mixing the transparent solution obtained in the step with chromium trioxide, adding hydrogen peroxide, and carrying out heating reaction to obtain aluminum phosphate chromium-based viscose;
3) stirring and gelling the aluminum phosphate chromium-based viscose obtained in the step and lanthanum oxide, and then placing the mixture into a mold for curing to obtain the lanthanum-aluminum phosphate composite material.
The method comprises the steps of firstly reacting preheated dilute phosphoric acid with aluminum hydroxide to obtain a transparent solution.
In the invention, the preheating temperature is preferably 80-85 ℃, more preferably 81-84 ℃, and more preferably 82-83 ℃.
In the present invention, the molar ratio of the aluminum hydroxide to the phosphoric acid is preferably (0.2 to 0.4): (0.8-1), more preferably (0.24-0.36): (0.8 to 1), more preferably (0.28 to 0.32): (0.8-1), more preferably (0.2-0.4): (0.84-0.96), more preferably (0.2-0.4): (0.88-0.92).
In the invention, the reaction temperature is preferably 80-85 ℃, more preferably 81-84 ℃, and more preferably 82-83 ℃.
The reaction time is preferably 1 to 1.5 hours, more preferably 1.1 to 1.4 hours, and still more preferably 1.2 to 1.3 hours.
The transparent solution obtained in the step is mixed with chromium trioxide, hydrogen peroxide is added, and heating reaction is carried out to obtain the aluminum phosphate chromium-based viscose.
In the present invention, the molar ratio of the aluminum hydroxide to the chromium trioxide is preferably (0.2 to 0.4): (0.1-0.2), more preferably (0.24-0.36): (0.1 to 0.2), more preferably (0.28 to 0.32): (0.1 to 0.2), more preferably (0.2 to 0.4): (0.12-0.18), more preferably (0.2-0.4): (0.14-0.16).
In the present invention, the molar ratio of the hydrogen peroxide to the chromium trioxide is preferably (0.1 to 0.2): (0.1 to 0.2), more preferably (0.12 to 0.18): (0.1 to 0.2), more preferably (0.14 to 0.16): (0.1-0.2), more preferably (0.1-0.2): (0.12-0.18), more preferably (0.1-0.2): (0.14-0.16).
In the present invention, the heating reaction is preferably carried out by water bath heating.
In the invention, the heating reaction temperature is preferably 80-85 ℃, more preferably 81-84 ℃, and more preferably 82-83 ℃.
In the invention, the heating reaction time is preferably 20-30min, more preferably 22-28 min, and more preferably 24-26 min.
The invention utilizes Cr3+Can form a complex (aluminum chromium phosphate) with aluminum phosphate, stabilize the solution, and simultaneously form the complex, the bonding energy of crystal water in phosphate is reduced, and the phosphate is dehydrated more quickly with the increase of temperature. Due to Cr2O3The invention does not directly introduce trivalent chromium into the water-insoluble solution, so hexavalent chromium is introduced and then rapidly reduced into trivalent chromium. And the chromium in the composite material forms Cr (OH)3And (3) waiting for the low-temperature-point compound, wherein the chromium element volatilizes along with the compound along with the increase of the temperature.
Finally, stirring and gelling the aluminum phosphate chromium-based viscose obtained in the step and lanthanum oxide, and then placing the mixture into a mold for curing to obtain the lanthanum-aluminum phosphate composite material.
In the invention, the mass ratio of the lanthanum oxide to the aluminum hydroxide is preferably (2-3.7): 1, more preferably (2.4 to 3.3): 1, more preferably (2.8 to 2.9): 1.
in the invention, the temperature of stirring and gelling is preferably 80-85 ℃, more preferably 81-84 ℃, and more preferably 82-83 ℃.
In the invention, the stirring and gelling time is preferably 1-1.5 h, more preferably 1.1-1.4 h, and more preferably 1.2-1.3 h.
In the invention, the viscosity after stirring and gelling is preferably 8-15 pa.s, more preferably 9-14 pa.s, more preferably 10-13 pa.s, and more preferably 11-12 pa.s.
In the invention, the curing temperature is preferably 30-50 ℃, more preferably 34-46 ℃, and more preferably 38-42 ℃.
In the invention, the curing time is preferably 1-2h, more preferably 1.2-1.8 h, and more preferably 1.4-1.6 h.
In the present invention, it is preferable that the curing further comprises a low-temperature heat treatment step;
in the invention, the temperature of the low-temperature heat treatment is preferably 300-450 ℃, more preferably 325-425 ℃, and more preferably 350-400 ℃.
According to the invention, modification treatment of aluminum chromium phosphate is not required, only the aluminum chromium phosphate is prepared to have the properties of viscosity and the like suitable for the lanthanum oxide added raw material, hydrogen peroxide is added immediately after the chromium oxide is added, the chromium oxide and the hydrogen peroxide are added almost synchronously, and the proportion is preferably 1: 1, rapid reaction of Cr6+Reduction to Cr3+So that the solution becomes weakly acidic and the stability of the solution is improved; on the other hand, Cr6+The phenomena of volatilization and the like occur in a high-temperature environment (water bath temperature) for a long time with higher toxicity, and the Cr is reduced6+And the damage to experimenters and the environment is reduced due to the fact that the temperature is excessively high and the environment is exposed for a long time. In addition, the temperature of the water bath kettle can be constant without being adjusted in the whole process, and the complicated preparation processes such as repeated temperature adjustment and the like are reduced, so that the time benefit is brought; the preparation of the aluminum chromium phosphate is finished without cooling treatment, lanthanum oxide can be directly added, the mixture is manually stirred to be gelatinized to proper viscosity, and meanwhile, the lanthanum oxide reacts with the aluminum chromium phosphate, so that the curing time is greatly shortened.
The invention obtains LaPO4And AlPO4As main phase or with LaPO4Bulk material with a main phase and the ratio of the two phases in terms of mass (LaPO)4：AlPO4) About 1 to 1.78. The invention selects the lanthanum oxide with high melting point from the aspects of reducing the curing temperature of phosphate and improving the temperature resistance of phosphate, thereby preparing the LaPO4The phosphate composite material has excellent heat resistance and ablation resistance, and can withstand oxyacetylene flame thermal ablation at 2000 ℃.
The invention is a complete and refined integral preparation process, better ensures the microscopic appearance and structure of the lanthanum-aluminum phosphate composite material, better ensures the rapid curing and molding at low temperature, and improves the high temperature resistance and the ablation resistance of the lanthanum-aluminum phosphate composite material, and the preparation method of the normal-pressure low-temperature curing high-temperature-resistant lanthanum-aluminum phosphate composite material can specifically comprise the following steps:
the preparation process comprises the following materials: phosphoric acid, aluminum hydroxide, La2O3、CrO3Hydrogen peroxide and deionized water.
Wherein, the Al (OH)3The particle size is-200 meshes for analytically pure powder; said H3PO4For analysis of the pure solution, H3PO4The content is more than or equal to 75 percent; the La2O3、CrO3And the hydrogen peroxide is analytically pure.
The method specifically comprises the following steps:
(1) 0.8 to 1mol of H3PO4Mixing (analytically pure) and 60ml of distilled water to prepare a dilute phosphoric acid solution, and putting the diluted phosphoric acid into a water bath kettle at the temperature of 80-85 ℃ for heating and stirring to obtain preheated dilute phosphoric acid;
(2) adding 0.2-0.4mol of Al (OH) into preheated dilute phosphoric acid3Stirring and heating to 80-85 ℃, and reacting to obtain a transparent solution with a certain viscosity;
(3) at this time, 0.1 to 0.2mol of CrO is added3Adding the above solution until CrO is formed3Completely dissolving, and immediately adding 0.1-0.2mol of H2O2. And then stirring and heating the mixed solution in a water bath kettle at the temperature of 80-85 ℃, and reacting for 20-30min to obtain the aluminum phosphate chromium-based adhesive with certain viscosity.
(4) Finally weighing 30-40 parts of La2O3Mixing with aluminum chromium phosphate, stirring in 80-85 deg.C water bath, gelatinizing to appropriate viscosity, pouring into appropriate mold, vibrating, exhausting, drying in oven, and curing for 1-2 hr to obtain high temperature resistant LaPO4A material.
More specifically, the curing temperature can be 50 ℃, and the curing time is 1-2 h.
The invention can be cured at normal pressure and low temperature, and a proper amount of La is directly added into the aluminum chromium phosphate adhesive2O3Phosphate composites are at temperatures of around 50 deg.CAnd (5) curing and forming in an oven. Therefore, the product can be used without special high-temperature sintering by special equipment during the molding process, the complex high-temperature sintering is omitted in the molding process, and the energy is saved. And the preparation process is simple and the preparation period is short. The raw material and reagent used for preparation are easy to obtain, the preparation process is simple, and the cost is low. The whole experimental preparation has no complex processes such as temperature adjustment and the like, the total time is less than 1.5h, and the preparation temperature is not high (70-85 ℃). Meanwhile, the high temperature resistance is excellent. The La-Al series phosphate samples exhibited excellent performance with respect to the prepared phosphate samples sintered and oxidized at the highest temperature (1700 ℃) reached by the muffle furnace of the experimental equipment, and no large deformation and defects occurred. It is sufficient to demonstrate the superiority of the high temperature resistance of the low temperature (50 ℃ C.) cured phosphate. The invention has good ablation resistance. In the experiment, oxyacetylene flame ablation is carried out on the 40% La-Al series phosphate subjected to heat treatment at 1000 ℃ and 427 ℃, the ablation temperature and the ablation time are 2000 ℃ and 30 seconds respectively, and the surface of the ablated sample is relatively complete.
The invention provides the high-temperature resistant lanthanum-aluminum phosphate composite material which is simple in preparation process, short in experimental period, capable of being rapidly cured and formed at low temperature and excellent in performance at high temperature. The invention directly adds the single metal oxide La into the prepared aluminum chromium phosphate2O3Stirring to proper viscosity, pouring into proper mould, solidifying and shaping. The obtained phosphate meets the requirement of low material density, and compensates the defect of high density of the high-temperature metal-based material; the material has low cost, and compensates the defects of high cost of a heat shield and the like; the material has short preparation period and low treatment temperature, and compensates the defects of complicated preparation and high treatment temperature of the ceramic matrix. The material has the performance characteristic of resisting high temperature of 2000 ℃. The invention utilizes the inherent stickiness of the phosphate to perform crosslinking reaction with the single metal oxide until the phosphate is solidified at low temperature, and the aluminum chromium phosphate and the selected high-melting-point metal oxide ensure that the prepared single metal oxide has good high-temperature performance. Compared with the prior art for preparing the high-temperature-resistant material, the invention has the advantages that the low-temperature curing molding is only used, the high-temperature stability is realized, and the preparation process has the advantages of short period, simple process, low cost and energy consumption and the like.
The invention provides an application of the lanthanum-aluminum phosphate composite material or the lanthanum-aluminum phosphate composite material prepared by the preparation method in any one of the technical schemes in the field of high-temperature resistant materials.
The invention provides a normal-pressure low-temperature-cured 2000 ℃ resistant lanthanum-aluminum phosphate composite material, and a preparation method and application thereof. The invention adds the high-melting-point metal oxide La2O3The ablation resistance of the phosphate is improved, and the phosphate can be rapidly cured at low temperature and normal pressure, so that the phosphate composite material which can meet the technical idea of low cost and short time is obtained.
The lanthanum-aluminum phosphate composite material provided by the invention has specific phase composition and microstructure, and lanthanum phosphate and aluminum phosphate are doped and compounded with each other and bonded through ionic bonds, so that the lanthanum-aluminum phosphate composite material which can be rapidly cured and formed at low temperature and has excellent performance at high temperature is obtained. The phosphate composite material provided by the invention can be cured and molded at normal pressure and low temperature, so that the product can be used without special high-temperature sintering by special equipment during molding, and the molding process saves complex high-temperature sintering and saves energy. And the preparation process is simple and the preparation period is short. The raw material and reagent used for preparation are easy to obtain, the preparation process is simple, and the cost is low. The whole experimental preparation has no complex processes such as temperature adjustment and the like, the total time is less than 1.5h, and the preparation temperature is not high (70-85 ℃). And the composite material has excellent high temperature resistance, and the La-Al series phosphate sample has excellent performance and does not have large deformation and defects when the prepared phosphate sample is sintered and oxidized at the highest temperature (1700 ℃), which shows that the low-temperature cured phosphate has excellent high temperature resistance. Meanwhile, the ablation resistance is good, and the surface of the ablated sample is relatively complete at the ablation temperature of 2000 ℃, and no melting condition is found.
The phosphate composite material provided by the invention can resist the high temperature of 2000 ℃, has lower density, and compensates the defect of high density of a high-temperature metal-based material; the material cost is low, and the defect of high cost of a heat shield and the like is compensated; meanwhile, the material has short preparation period and low treatment temperature, and compensates the defects of complicated preparation and high treatment temperature of the ceramic matrix.
Experimental results show that the La-Al series phosphate prepared by the invention forms compact LaPO in the ablation center4And AlPO4The high-temperature phase is used for resisting ablation at 2000 ℃, and no melting condition is seen, so that the high-temperature resistance of the low-temperature cured phosphate is excellent, and the ablation resistance is good.
In order to further illustrate the present invention, the lanthanum aluminate phosphate composite material, the preparation method and the application thereof are described in detail with reference to the following examples, but it should be understood that the examples are implemented on the premise of the technical scheme of the present invention, and the detailed embodiments and the specific operation procedures are given, which are only for further illustrating the features and advantages of the present invention, but not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
Adding 0.8-1mol of H into 60-80ml of distilled water3PO4(analytically pure), and putting the diluted phosphoric acid into a water bath kettle at the temperature of 80-85 ℃ for heating and stirring; then 0.2-0.4mol of Al (OH)3Adding into preheated dilute phosphoric acid, and stirring until the solution has a certain viscosity. In this case, 0.1 to 0.2mol of CrO3Adding the above solution until CrO is formed3Dissolving and immediately adding 0.1-0.2mol of H2O2. And then stirring the mixed solution for 20-30min to obtain the aluminum phosphate chromium-based adhesive. Finally weighing 30 parts of La2O3Adding into aluminum chromium phosphate, continuously stirring in a water bath kettle at 80-85 ℃ until the viscosity is proper, pouring into a proper mould, putting into a 50 ℃ oven, drying and curing for 1-2h to obtain the 30% La-Al series phosphate high-temperature resistant material.
The lanthanum-aluminum phosphate composite material prepared in the embodiment 1 of the invention is subjected to high temperature resistance detection.
The high-temperature-resistant heat treatment detection is carried out on the La-Al series phosphate solidified at the normal temperature by 30 percent, and the technological parameters are as follows:
1) temperature: 1000 ℃;
time: 2 h;
atmosphere: an environment;
a cooling mode: and (5) cooling along with the furnace.
2) Temperature: 1500 ℃;
time: 2 h;
atmosphere: an environment;
a cooling mode: and (5) cooling along with the furnace.
3) Temperature: 1700 ℃;
time: 2 h;
atmosphere: an environment;
a cooling mode: and (5) cooling along with the furnace.
Referring to fig. 1, fig. 1 is a BSEM back scattering scanning electron microscope image of the lanthanum aluminum phosphate composite material prepared in example 1 of the present invention after a 1700 ℃ high temperature resistance experiment.
As can be seen from FIG. 1, after the lanthanum-aluminum phosphate composite material prepared in example 1 of the present invention is subjected to high temperature treatment at 1700 ℃, the sample surface is relatively compact and has no cracks, which indicates that the normal temperature cured phosphate of the present invention can resist the high temperature of 1700 ℃.
Referring to fig. 2, fig. 2 is a BSEM back-scattering scanning electron microscope image of the lanthanum-aluminum phosphate composite material prepared in example 1 of the present invention and subjected to high temperature resistance experiments at 300 ℃, 500 ℃, 700 ℃, 1000 ℃, 1500 ℃, 1700 ℃. Wherein, the figure a is a BSEM back scattering scanning electron microscope image of the lanthanum aluminum phosphate composite material prepared in the embodiment 1 of the invention; fig. b is a BSEM back scattering scanning electron microscope image of the lanthanum-aluminum phosphate composite material prepared in example 1 of the present invention after a high temperature resistance test at 300 ℃; fig. c is a BSEM back scattering scanning electron microscope image of the lanthanum aluminum phosphate composite material prepared in example 1 of the present invention after a 500 ℃ high temperature resistance experiment; fig. d is a BSEM back scattering scanning electron microscope image of the lanthanum-aluminum phosphate composite material prepared in example 1 of the present invention after a high temperature resistance test at 700 ℃; fig. e is a BSEM back scattering scanning electron microscope image of the lanthanum-aluminum phosphate composite material prepared in example 1 of the present invention after a high temperature resistance test at 1000 ℃; fig. f is a BSEM back scattering scanning electron microscope image of the lanthanum-aluminum phosphate composite material prepared in example 1 of the present invention after 1500 ℃ high temperature resistance experiment; fig. g is a BSEM back scattering scanning electron microscope image of the lanthanum-aluminum phosphate composite material prepared in example 1 of the present invention after a 1700 ℃ high temperature resistance experiment.
As can be seen from FIG. 2, with the increase of the detection temperature, the densification tendency of the sample surface is increased and stable LaPO is formed4And AlPO4The high temperature phase substance can be used for detection tests resisting higher temperature.
The lanthanum-aluminum phosphate composite material prepared in example 1 of the present invention and the lanthanum-aluminum phosphate composite material subjected to a high temperature test were characterized.
Referring to fig. 3, fig. 3 is an XRD spectrum of the lanthanum aluminate phosphate composite material prepared in example 1 of the present invention and the lanthanum aluminate phosphate composite material after high temperature experiment.
Example 2
Adding 0.8-1mol of H into 60-80ml of distilled water3PO4(analytically pure), and putting the diluted phosphoric acid into a water bath kettle at the temperature of 80-85 ℃ for heating and stirring; then 0.2-0.4mol of Al (OH)3Adding into preheated dilute phosphoric acid, and stirring until the solution has a certain viscosity. In this case, 0.1 to 0.2mol of CrO3Adding the above solution until CrO is formed3Dissolving and immediately adding 0.1-0.2mol of H2O2. And then stirring the mixed solution for 20-30min to obtain the aluminum phosphate chromium-based adhesive. Finally weighing 30 parts of La2O3Adding into aluminum chromium phosphate, continuously stirring in a water bath kettle at 80-85 ℃ until the viscosity is proper, pouring into a proper mould, putting into a 50 ℃ oven, drying and curing for 1-2h to obtain the 40% La-Al series phosphate high-temperature resistant material.
The lanthanum-aluminum phosphate composite material prepared in the embodiment 2 of the invention is subjected to high temperature resistance detection.
The high-temperature-resistant heat treatment detection is carried out on the La-Al series phosphate solidified at normal temperature by 40 percent, and the technological parameters are as follows:
1) temperature: 1000 ℃;
time: 2 h;
atmosphere: an environment;
a cooling mode: and (5) cooling along with the furnace.
2) Temperature: 1500 ℃;
time: 2 h;
atmosphere: an environment;
a cooling mode: and (5) cooling along with the furnace.
3) Temperature: 1700 ℃;
time: 2 h;
atmosphere: an environment;
a cooling mode: and (5) cooling along with the furnace.
Referring to fig. 4, fig. 4 is a BSEM back scattering scanning electron microscope image of the lanthanum aluminum phosphate composite material prepared in example 2 of the present invention after a 1700 ℃ high temperature resistance experiment.
As can be seen from FIG. 4, after the lanthanum-aluminum phosphate composite material prepared in example 2 of the present invention is subjected to high temperature treatment at 1700 ℃, the sample surface is relatively dense and has no cracks, which indicates that the normal temperature cured phosphate of the present invention can resist the high temperature of 1700 ℃.
Referring to fig. 5, fig. 5 is a BSEM back-scattering scanning electron microscope image of the lanthanum-aluminum phosphate composite material prepared in example 2 of the present invention and subjected to high temperature resistance experiments at 300 ℃, 500 ℃, 700 ℃, 1000 ℃, 1500 ℃, 1700 ℃. Wherein, fig. a is a BSEM back scattering scanning electron microscope image of the lanthanum aluminum phosphate composite material prepared in example 2 of the present invention; FIG. B is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 2 of the present invention after a high temperature resistance test at 300 ℃; FIG. C is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 2 of the present invention after a 500 ℃ high temperature resistance experiment; FIG. D is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 2 of the present invention after a 700 ℃ high temperature resistance experiment; FIG. E is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 2 of the present invention after a high temperature resistance test at 1000 ℃; FIG. F is a BSEM back scattering scanning electron microscope image of the La-Al phosphate composite material prepared in example 2 of the present invention after 1500 ℃ high temperature resistance experiment; fig. G is a BSEM back-scattering scanning electron microscope image of the lanthanum-aluminum phosphate composite material prepared in example 2 of the present invention after a 1700 ℃ high temperature resistance experiment.
As can be seen from FIG. 5, with the increase of the detection temperature, the densification tendency of the sample surface is increased and stable LaPO is formed4And AlPO4The high-temperature phase substance of (2),can be used for detection tests resisting higher temperatures.
The lanthanum-aluminum phosphate composite material prepared in example 2 of the present invention and the lanthanum-aluminum phosphate composite material subjected to a high temperature test were characterized.
Referring to fig. 6, fig. 6 is an XRD spectrum of the lanthanum aluminate phosphate composite material prepared in example 2 of the present invention and the lanthanum aluminate phosphate composite material after high temperature experiment.
The lanthanum-aluminum phosphate composite material subjected to the high-temperature test at 1000 ℃ in the embodiment 2 of the invention is subjected to an oxyacetylene flame ablation test.
Referring to fig. 7, fig. 7 is a physical appearance diagram of the lanthanum aluminum phosphate composite material ablated after the high temperature experiment in example 2 of the present invention.
Referring to fig. 8, fig. 8 is a BSEM back scattering scanning electron microscope image of the lanthanum aluminum phosphate composite material ablated after the high temperature experiment in example 2 of the present invention.
An oxyacetylene flame ablation experiment was performed on the lanthanum-aluminum phosphate composite material prepared in example 2 of the present invention.
In practical production application, the energy consumption is saved, the sample is solidified at low temperature and normal pressure, and heat treatment at a certain temperature is needed, so that the performance of the sample reaches a certain degree, and the sample is prevented from being damaged by sudden high temperature in practical application. Therefore, after the heat treatment at 427 ℃ is carried out (1.5-2 h), the oxyacetylene ablation at 2000 ℃ for 30s is carried out, and the result shows that the lanthanum-aluminum phosphate composite material prepared by the invention has excellent performance under the high-temperature ablation at 2000 ℃.
Referring to fig. 9, fig. 9 is an appearance diagram of an ablated lanthanum aluminum phosphate composite material prepared in example 2 of the present invention.
Referring to fig. 10, fig. 10 is a BSEM back-scattering scanning electron microscope image of the lanthanum aluminum phosphate composite material prepared in example 2 of the present invention after ablation.
As can be seen from the graphs of 7-10, after the sample is thermally shocked and ablated by oxyacetylene flame at 2000 ℃, the sample is not melted, the surface is relatively complete, and the ablation center can be seen to form a compact microscopic profile graphLaPO4And AlPO4A high temperature phase for resisting ablation at 2000 ℃. The physical map can also show that the appearance of the whole sample is relatively complete, and the edges of the sample fall off, which may include two reasons: firstly, the sample is tested at a high temperature of 1000 ℃ to have defects, secondly, the central ablation flame has larger attacking force, stress accumulation is generated, and in addition, the edge area of the sample is not reinforced in the later period, and the like, so that the edge of the sample is peeled off. Therefore, the low-temperature and normal-pressure fast curing phosphate provided by the invention has excellent heat resistance and ablation resistance.
The above detailed description of the invention provides a 2000 ℃ resistant lanthanum aluminate phosphate composite material cured at low temperature under normal pressure, its preparation method and application, and the present invention is described in the principle and embodiments thereof with specific examples, which are provided only to help understand the method and its core idea, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any device or system and implementing any combination of methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The lanthanum-aluminum phosphate composite material solidified at normal pressure and low temperature is characterized by comprising lanthanum phosphate and aluminum phosphate compounded with the lanthanum phosphate;
in the composite material, the molar ratio of the lanthanum phosphate to the aluminum phosphate is (1-1.78): 1;
the composite material also comprises element chromium;
the element chromium in the composite material has a chemical valence state of + 3;
the molar content of the element chromium is 0.05% -0.1%;
the preparation method of the lanthanum-aluminum phosphate composite material comprises the following steps:
1) reacting the preheated dilute phosphoric acid with aluminum hydroxide to obtain a transparent solution;
2) mixing the transparent solution obtained in the step with chromium trioxide, adding hydrogen peroxide, and carrying out heating reaction to obtain aluminum phosphate chromium-based viscose;
3) stirring and gelling the aluminum phosphate chromium-based viscose obtained in the step and lanthanum oxide, and then placing the mixture into a mold for curing to obtain the lanthanum-aluminum phosphate composite material.
2. The composite material of claim 1, wherein the compounding comprises doping;
the lanthanum phosphate and the aluminum phosphate are bonded through ionic bonds;
the composite material takes lanthanum phosphate as a main phase and is intercalated with an aluminum phosphate phase.
3. The composite material of claim 1, wherein the lanthanum aluminophosphate composite is a high temperature resistant composite;
in the composite material, the lanthanum phosphate and the aluminum phosphate are connected tightly, and the surface is smooth and compact.
4. The composite material of claim 1, wherein the composite material does not melt after flame ablation at a high temperature of 2000 ℃ or less;
the composite material is a phosphate composite material cured at normal pressure and low temperature;
the low temperature is 30-50 ℃.
5. A preparation method of the lanthanum aluminum phosphate composite material solidified at normal pressure and low temperature as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
1) reacting the preheated dilute phosphoric acid with aluminum hydroxide to obtain a transparent solution;
2) mixing the transparent solution obtained in the step with chromium trioxide, adding hydrogen peroxide, and carrying out heating reaction to obtain aluminum phosphate chromium-based viscose;
3) stirring and gelling the aluminum phosphate chromium-based viscose obtained in the step and lanthanum oxide, and then placing the mixture into a mold for curing to obtain the lanthanum-aluminum phosphate composite material.
6. The preparation method according to claim 5, wherein the preheating temperature is 80-85 ℃;
the molar ratio of the aluminum hydroxide to the phosphoric acid is (0.2-0.4): (0.8 to 1);
the reaction temperature is 80-85 ℃;
the reaction time is 1-1.5 h.
7. The production method according to claim 5, wherein the molar ratio of the aluminum hydroxide to the chromium trioxide is (0.2 to 0.4): (0.1 to 0.2);
the molar ratio of the hydrogen peroxide to the chromium trioxide is (0.1-0.2): (0.1 to 0.2);
the heating reaction mode is water bath heating;
the temperature of the heating reaction is 80-85 ℃;
the heating reaction time is 20-30 min.
8. The preparation method according to claim 5, wherein the mass ratio of the lanthanum oxide to the aluminum hydroxide is (2-3.7): 1;
the temperature for stirring and gelling is 80-85 ℃;
the stirring gelling time is 1-1.5 h;
the viscosity after stirring and gelling is 8-15 pa.s.
9. The preparation method according to claim 5, wherein the curing temperature is 30-50 ℃;
the curing time is 1-2 h;
the step of low-temperature heat treatment is also included after the solidification;
the temperature of the low-temperature heat treatment is 300-450 ℃.
10. Use of the lanthanum aluminium phosphate composite material according to any one of claims 1 to 4 or the lanthanum aluminium phosphate composite material prepared by the preparation method according to any one of claims 5 to 9 in the field of high temperature resistant materials.
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| CN114716228B (en) * | 2022-04-07 | 2022-11-08 | 中南大学 | Ultrahigh temperature resistant low-heat-conductivity magnesium-aluminum-chromium multi-phosphate composite material and preparation method thereof |
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