CN110877975B - Prestressed ceramic and preparation method thereof - Google Patents
Prestressed ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a prestressed ceramic and a preparation method thereof. The prestressed ceramic comprises a multilayer structure formed by a base body and a surface layer; the surface layer material constituting the surface layer has a lower expansion coefficient than that of the base material constituting the base; the elastic modulus of the surface material is not lower than that of the base material; and the surface layer coats the substrate. The prestressed ceramic has prestress, can greatly improve the strength and has good practical value.
Description
Technical Field
The invention relates to a ceramic reinforcing technology, in particular to prestressed ceramic and a preparation method thereof.
Background
The ceramic material has high insulating property, excellent corrosion resistance and high mechanical strength, and is widely applied to the fields of aviation, aerospace, ships, weapons, electronics, nuclear industry and the like.
However, the existing ceramic materials and products have two problems: firstly, the ultrahigh strength is difficult to obtain by adopting the conventional process means, and the performance index or the economic index under a specific service environment is difficult to meet; secondly, defects are introduced in the ceramic materials and ceramic products which are difficult to avoid in the preparation process, particularly in the processing process, and then the defects become weak points in the subsequent use process, so that the products are failed, and catastrophic accidents are caused. This is also a factor in the increasingly smaller structural ceramics.
The prestressed ceramics in the prior art are mainly compounded by metal and ceramics to generate prestress; the other is to apply prestress directly on the ceramic surface by a prestressing device. The prestressed interface produced by the two methods is non-uniform in distribution, more in defects and low in strength.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides prestressed ceramic with high-strength prestress and a preparation method thereof. The invention realizes the purpose of greatly improving the bending strength of two or more materials after compounding by establishing a prestressed ceramic mechanical model, designing prestress on the surface of the material and controlling key parameters such as material components, sectional area and the like. The prestressed ceramic prepared by the invention has the advantages of high strength and few defects, and the production process is simple and can meet the requirements of batch production.
According to an aspect of the present invention, there is provided a prestressed ceramic including a multi-layer structure formed of a base body and a surface layer; the surface layer material constituting the surface layer has a lower expansion coefficient than that of the base material constituting the base; the elastic modulus of the surface material is not lower than that of the base material; and the surface layer coats the substrate.
Preferably, the ratio of the cross-sectional area of the substrate to the cross-sectional area of the surface layer is 0.1 to 2500.
The skin layer may be a single component monolayer or a multi-component multilayer.
The skin material and the matrix material are different and are independently selected from the group consisting of alumina, cordierite, mullite, and magnesia alumina spinel.
Preferably, the skin material is cordierite and the matrix material is alumina.
The surface layer material completely or partially coats the base material. The partial coating is a symmetrical coating.
According to another aspect of the present invention, there is provided a method for preparing a pre-stressed ceramic, comprising the steps of:
(1) forming a base material into a predetermined shape to form a base;
(2) coating the surface of the substrate by a surface layer material in a particle accumulation mode to form a surface layer, thereby preparing a pre-stressed ceramic biscuit;
(3) sintering the pre-stressed ceramic biscuit at the high temperature of 800-1800 ℃, and then cooling to the room temperature to form the pre-stressed ceramic;
wherein the coefficient of expansion of the skin material is lower than the coefficient of expansion of the base material, and the modulus of elasticity of the skin material is not lower than the modulus of elasticity of the base material.
The prestressed ceramic according to the present invention has the following advantageous effects:
(1) the high-strength prestressed ceramic can have greatly improved bending strength which is far higher than the highest strength of the matrix and the surface layer, which is different from the situation that the strength of the conventional composite material is between the strengths of the two materials, specifically, the bending strength of the prestressed ceramic can be improved by 198 percent at most relative to the material of the surface layer and by 37 percent at most relative to the material of the matrix;
(2) the product with small size can be smaller than the similar product under the condition of ensuring the strength, so that the resource can be saved;
(3) the preparation process is simple, the composition of the matrix and the surface layer can adopt most of the existing ceramic forming process and sintering process, and the method is suitable for industrial mass production.
Drawings
FIG. 1 is a typical curve of the pre-stress-cross-sectional area ratio for a pre-stressed ceramic skin material of the present invention;
FIG. 2 is a fully-wrapped circular cross-sectional structural model of example 1 of the present invention;
FIG. 3 is a partially clad circular cross-sectional structural model of example 2 of the present invention;
FIG. 4 is a fully-wrapped rectangular cross-sectional structural model according to example 3 of the present invention;
FIG. 5 is a partially clad rectangular cross-sectional structural model according to example 4 of the present invention;
FIG. 6 is a fully-wrapped special-shaped cross-sectional structural model according to example 5 of the present invention;
fig. 7 is a partially-wrapped special-shaped cross-sectional structure model according to embodiment 6 of the present invention.
Detailed Description
The invention provides a prestressed ceramic, which comprises a multilayer structure formed by a base body and a surface layer; wherein the surface layer material constituting the surface layer has an expansion coefficient lower than that of the base material constituting the base, and the modulus of elasticity of the surface layer material is not lower than that of the base material; and the surface layer coats the substrate.
Preferably, the ratio of the cross-sectional area of the substrate to the surface layer is 0.1 to 2500, preferably 1 to 200, more preferably 3 to 150, most preferably 4 to 75, such as 6, 10, 15, 20, 25, 30.
The skin layers may be single component monolayers or multiple component multilayers.
The surface layer material and the matrix material are different and are independently selected from alumina, cordierite, mullite and magnesia alumina spinel. For example, the skin/matrix material may be any one or more of the following transition options: cordierite/alumina, mullite/alumina, cordierite/magnesia alumina spinel, cordierite/mullite.
Preferably, the skin material is cordierite and the matrix material is alumina.
The skin material may completely coat or partially coat the base material. Preferably, the partial coating is a symmetrical coating.
The invention also provides a preparation method of the prestressed ceramic, which comprises the following steps:
(1) forming a base material into a predetermined shape to form a base;
(2) coating the surface of the substrate layer with a surface layer material in a particle accumulation mode to form a surface layer, so as to prepare a pre-stressed ceramic biscuit;
(3) and (2) sintering the pre-stressed ceramic biscuit at a high temperature of 800-1800 ℃ (preferably 1300-1700 ℃, more preferably 1350-1650 ℃), and then cooling to room temperature (20 ℃) to form the pre-stressed ceramic.
In the production method according to the present invention, the skin material and the base material have bondability. Wherein the coefficient of expansion of the skin material is lower than the coefficient of expansion of the base material, and the modulus of elasticity of the skin material is not lower than the modulus of elasticity of the base material.
The step 1 of forming the substrate material into a substrate with a predetermined shape, such as a regular shape like a cylinder, a square cylinder, etc., or other irregular shapes, can be performed by a conventional method in the art. The base material may be a material only or may be a member. The porosity of the matrix material is generally controlled to be less than 90%, preferably 60-80%.
According to a specific embodiment, in step 2, when preparing the pre-stressed ceramic biscuit, a pre-stress value is firstly set for the surface layer material, and then the cross-sectional area ratio of the surface layer and the substrate is calculated by the following formula, so as to calculate the thickness of the surface layer:
wherein A isSAnd ACThe cross sectional areas of the substrate and the surface layer are respectively; sigmapreIs prestressed; alpha is alphasAnd alphacThe thermal expansion coefficients of the base material and the surface layer material are respectively; eSAnd ECThe elastic modulus of the base material and the elastic modulus of the surface material are respectively; delta TCIs the equivalent temperature difference when the sintering temperature of the prestressed ceramic is reduced to room temperature (20 ℃);
the surface layer material is then applied to the substrate surface by conventional means, such as spraying.
The setting of the prestress value needs to meet the following conditions:
1. the pressure stress is formed on the surface layer;
2. the pressure resistance value of the surface layer can not be exceeded;
3. the tensile stress developed in response cannot exceed the strength of the matrix.
After the prestress value meeting the above conditions is set, the corresponding cross-sectional area ratio can be calculated according to the above formula, and thus the coating thickness of the surface layer material can be determined. The prestress value is preferably within the range of 1000-1500 MPa, and preferably 1100-1350 MPa.
Specifically, fig. 1 shows a typical graph of the prestress-cross-sectional area ratio when the skin material is cordierite and the base material is alumina.
Application of the skin material may be carried out using techniques conventional in the art, such as spraying.
The prestressed ceramic has the bending strength of 400-650 MPa, which can be improved by 198% at most relative to a surface material and 37% at most relative to a base material.
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings.
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the specific product, and the conditions used in the experiments are not generally indicated.
Materials, reagents and the like used in the following examples are commercially available.
Example 1
The surface layer material of the prestressed ceramic is cordierite, the elastic modulus is 145GPa, and the expansion coefficient is 2.1 multiplied by 10-6/° c; the matrix material is alumina, the elastic modulus is 390GPa, and the expansion coefficient is 7.8 multiplied by 10-6V. C. The substrate is a cylinder with the diameter of 5mm and the length of 50mm, and the cross-sectional area ratio is calculated by a circular cross section.
Firstly, presetting an internal stress value (namely a prestress value) of 1134.63MPa for a surface layer material, and calculating a corresponding sectional area ratio by the following formula, wherein the numerical value corresponding relation of the two is shown in a table 1:
wherein A isSAnd ACThe cross sectional areas of the substrate and the surface layer are respectively; sigmapreIs prestressed; alpha is alphasAnd alphacThe thermal expansion coefficients of the base material and the surface layer material are respectively; eSAnd ECThe elastic modulus of the base material and the elastic modulus of the surface material are respectively; delta TCIs the equivalent temperature difference when the sintering temperature of the prestressed ceramic is reduced to room temperature (20 ℃).
The preparation method of the prestressed ceramic comprises the following steps:
(1) the alumina is made into a non-compact cylinder with the diameter of 5mm and the length of 50mm and the porosity of 80 percent;
(2) preparing a prestressed ceramic biscuit: firstly, setting a prestress numerical value, and then calculating the sectional area ratio of the surface layer material and the base material through a sectional area ratio calculation formula (a prestress-sectional area ratio curve is shown in figure 1), so as to calculate the thickness of the surface layer material; then, the cordierite material is used for uniformly and completely coating the surface of the alumina cylinder by a spraying method (the coating schematic diagram is shown in figure 2, wherein the cross-sectional area ratio of the two is calculated by a top view);
(3) and (3) high-temperature sintering: and (3) sintering the pre-stressed ceramic biscuit at 1500 ℃ for 3h, and then cooling to room temperature to form the pre-stressed ceramic.
The parameters are shown in table 1, example 1;
the curves of the prestress and the sectional area ratio of the prestressed ceramic prepared in this example are shown in FIG. 1. As can be seen from fig. 1, the prestress value increases with the increase of the ratio of the cross-sectional areas of the substrate and the surface layer within a certain range, and the prestress value does not increase any more beyond the certain range.
The flexural strength of the prestressed ceramic, the matrix and the surface material prepared in this example were tested to be 494.43MPa, 435.0MPa and 200.0MPa, respectively, by a three-point bending test method under the same dimensions. Therefore, the bending strength of the prestressed ceramic prepared by the embodiment is improved by 147.21% compared with that of a surface layer material, and is improved by 13.88% compared with that of a base body.
Example 2
In this example, parameters were set in accordance with example 2 in table 1, in which a cordierite material was partially symmetrically coated on the surface of an alumina cylinder by a spray coating method (see fig. 3 for a schematic coating diagram in which the ratio of the cross-sectional areas was calculated in a plan view), and the rest of the conditions were the same as in example 1.
The flexural strengths of the pre-stressed ceramic, the base and the skin material prepared in this example were tested to be 510.20MPa, 435.0MPa and 200.0MPa, respectively, in the same size by the three-point bending test method. The bending strength of the prestressed ceramic prepared by the method is improved by 155.10% compared with that of a surface layer material, and is improved by 17.29% relative to a base body.
Example 3
In this example, the parameters were set according to example 3 in table 1, wherein the base material in this example was alumina cubic cylinders with width, thickness of 5mm and length of 50mm, and the cordierite material was uniformly and completely coated on the surfaces of the alumina cubic cylinders by a spray coating method (see fig. 4 for a schematic coating diagram, wherein the cross-sectional area ratio of the two is calculated in a plan view), and the rest conditions were the same as in example 1.
The flexural strengths of the pre-stressed ceramics, matrix and skin materials prepared in this example were tested by the three-point bending test method at the same dimensions of 544.78MPa, 435.0MPa and 200.0 MPa. The bending strength of the prestressed ceramic prepared by the method is improved by 172.39% compared with that of a surface layer material, and is improved by 25.48% relative to a base body.
Example 4
In this example, the parameters were set according to example 4 in table 1, wherein the alumina matrix material in this example was a cubic cylinder with a width, a thickness of 5mm, a length of 50mm, and a porosity of 60%, and the cordierite material was coated on the surface of the alumina cubic cylinder by a spray coating method in a partially symmetrical manner (see fig. 5 for a schematic coating diagram, wherein the ratio of the two cross-sectional areas is calculated in a top view), and the rest conditions were the same as in example 1.
The flexural strengths of the pre-stressed ceramics, matrix and skin materials prepared in this example were tested by the three-point bending test method at the same dimensions of 548.24MPa, 435.0MPa and 200.0 MPa. The bending strength of the prestressed ceramic prepared by the method is improved by 174.12% compared with that of a surface layer material, and is improved by 26.28% relative to a substrate.
Example 5
In this example, parameters were set according to example 5 in table 1, wherein the alumina matrix material of this example is a special-shaped structure, the cordierite material was uniformly and completely coated on the surface of the alumina special-shaped structure by spraying (see fig. 6 for a schematic coating diagram, and the ratio of the cross-sectional areas of the two is calculated from the cross-sectional diagram in the figure), and the rest conditions were the same as those in example 1.
The flexural strengths of the pre-stressed ceramics, matrix and skin materials prepared in this example were tested by the three-point bending test method at the same dimensions of 571.99MPa, 435.0MPa and 200.0 MPa. The bending strength of the prestressed ceramic prepared by the method is improved by 185.99% compared with that of a surface layer material, and is improved by 31.49% compared with that of a base body.
Example 6
In this example, parameters were set according to example 6 in table 1, wherein the alumina matrix material in this example is a special-shaped structure, and the cordierite material was coated on the surface of the alumina special-shaped structure by spraying, partially and symmetrically (see fig. 7 for a schematic coating diagram, and the cross-sectional area ratio is calculated by the cross-sectional view in the figure), and the rest conditions were the same as those in example 1.
The flexural strengths of the pre-stressed ceramics, matrix and skin materials prepared in this example were tested by the three-point bending test method at the same dimensions of 571.99MPa, 435.0MPa and 200.0 MPa. The bending strength of the prestressed ceramic prepared by the method is improved by 185.99% compared with that of a surface layer material, and is improved by 31.49% compared with that of a base body.
Example 7
This example sets the parameters according to example 7 in table 1, and the rest of the conditions are the same as example 2.
The flexural strengths of the pre-stressed ceramics, matrix and skin materials prepared in this example were tested by the three-point bending test method at the same dimensions of 592.80MPa, 435.0MPa and 200.0 MPa. The bending strength of the prestressed ceramic prepared by the method is improved by 196.4% compared with that of a surface layer material, and is improved by 36.27% relative to a base body.
Example 8
This example sets the parameters according to example 8 in table 1, and the rest of the conditions are the same as example 2.
The flexural strengths of the pre-stressed ceramics, matrix and skin materials prepared by the three-point bending test method of this example were 594.36MPa, 435.0MPa and 200.0MPa for the same dimensions. The bending strength of the prestressed ceramic prepared by the method is improved by 197.18% compared with that of a surface layer material, and is improved by 36.63% compared with that of a base body.
TABLE 1
In summary, the present invention forms a base material and a surface material from two or more bondable materials, respectively, and forms a prestressed ceramic by high-temperature sintering. The base material should have sufficient strength and a high expansion coefficient, the surface layer material should have a low expansion coefficient and a high elastic modulus, balance between surface layer compressive stress and base tensile stress is formed after high-temperature sintering, and the bending strength of the prestressed ceramic can be greatly improved by the surface layer compressive stress. The magnitude of the compressive stress can be adjusted by optimizing the section ratio of two materials of the cross section, for the given two materials, the surface prestress is designed to be higher than the strength value of the surface layer material, the section ratio is determined by deduction and calculation of a prestress calculation formula, the prestress ceramic with the prestress is obtained after sintering, and the strength of the prestress ceramic can be greatly improved. Therefore, the invention solves the problem that the strength of the existing structural ceramic is difficult to improve, and has good practical value.
The bending strength of the prestressed ceramic prepared according to the invention is greatly improved, specifically, the bending strength can be improved by 198% at most relative to a surface material, and can be improved by 37% at most relative to a base material. The preparation method has simple process, and the composition of the matrix and the surface layer can adopt most of the existing ceramic forming process and sintering process, thereby being suitable for industrial mass production.
The embodiments are merely preferred examples of the present invention, and are not intended to limit the scope of the present invention. It should be noted that modifications and adaptations may occur to those skilled in the art without departing from the principles of the present invention and should be considered within the scope of the present invention.
Claims (4)
1. A pre-stressed ceramic, characterized in that it comprises a multilayer structure formed by a matrix and a surface layer; the surface layer material constituting the surface layer has a lower expansion coefficient than that of the base material constituting the base; the elastic modulus of the surface material is not lower than that of the base material; and the surface layer coats the substrate;
the prestressed ceramic is prepared by the following steps:
(1) forming a base material into a predetermined shape to form a base;
(2) coating the surface of the substrate by a surface layer material in a particle accumulation mode to form a surface layer, thereby preparing a pre-stressed ceramic biscuit;
when the prestressed ceramic biscuit is prepared, firstly, a prestress value is set for a surface layer material, and then the sectional area ratio of the surface layer and a matrix is calculated through the following formula, so that the thickness of the surface layer is calculated:
wherein A isSAnd ACThe cross sectional areas of the substrate and the surface layer are respectively; sigmapreIs prestressed; alpha is alphasAnd alphacThe thermal expansion coefficients of the base material and the surface layer material are respectively; eSAnd ECThe elastic modulus of the base material and the elastic modulus of the surface material are respectively; delta TCThe equivalent temperature difference of the prestressed ceramic when the sintering temperature is reduced to the room temperature;
(3) sintering the pre-stressed ceramic biscuit at a high temperature of 800-1800 ℃, then cooling to room temperature to form the pre-stressed ceramic,
the ratio of the cross sections of the substrate and the surface layer is 0.1-2500;
the surface layer material is cordierite, and the matrix material is alumina.
2. The pre-stressed ceramic of claim 1, wherein the skin material completely or partially coats the matrix material.
3. The pre-stressed ceramic of claim 2, wherein the partial cladding is a symmetric cladding.
4. The preparation method of the prestressed ceramic is characterized by comprising the following steps of:
(1) forming a base material into a predetermined shape to form a base;
(2) coating the surface of the substrate by a surface layer material in a particle accumulation mode to form a surface layer, thereby preparing a pre-stressed ceramic biscuit;
when the prestressed ceramic biscuit is prepared, firstly, a prestress value is set for a surface layer material, and then the sectional area ratio of the surface layer and a matrix is calculated through the following formula, so that the thickness of the surface layer is calculated:
wherein A isSAnd ACThe cross sectional areas of the substrate and the surface layer are respectively; sigmapreIs prestressed; alpha is alphasAnd alphacThe thermal expansion coefficients of the base material and the surface layer material are respectively; eSAnd ECThe elastic modulus of the base material and the elastic modulus of the surface material are respectively; delta TCThe equivalent temperature difference of the prestressed ceramic when the sintering temperature is reduced to the room temperature;
(3) sintering the pre-stressed ceramic biscuit at a high temperature of 800-1800 ℃, then cooling to room temperature to form the pre-stressed ceramic,
the ratio of the cross sections of the substrate and the surface layer is 0.1-2500;
the surface layer material is cordierite, and the matrix material is alumina;
wherein the coefficient of expansion of the skin material is lower than the coefficient of expansion of the base material, and the modulus of elasticity of the skin material is not lower than the modulus of elasticity of the base material.
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| CN112645696A (en) * | 2020-12-30 | 2021-04-13 | 深圳天一山科技有限公司 | Alumina-reinforced ZTA ceramic substrate and preparation method thereof |
| CN114956868B (en) * | 2021-02-27 | 2024-04-02 | Oppo广东移动通信有限公司 | Ceramic shell, preparation method and electronic equipment |
| CN113264783B (en) * | 2021-07-20 | 2021-11-02 | 佛山市东鹏陶瓷发展有限公司 | Prestressed ceramic and preparation method thereof |
| CN114409383A (en) * | 2022-01-26 | 2022-04-29 | 苏州鼎安科技有限公司 | Surface-enhanced ceramic artificial joint convex-spherical friction part and preparation method thereof |
| CN115043648A (en) * | 2022-07-15 | 2022-09-13 | 中国国检测试控股集团股份有限公司 | Prestressed alumina ceramic composite material and preparation method thereof |
| CN115043672A (en) * | 2022-07-15 | 2022-09-13 | 中国国检测试控股集团股份有限公司 | Method for realizing re-strengthening of alumina ceramic |
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