阅读说明：本技术 一种用于超高温环境下陶瓷钉及制备方法 (Ceramic nail used in ultra-high temperature environment and preparation method thereof ) 是由 于文齐 熊进勇 于 2021-01-25 设计创作，主要内容包括：本发明涉及陶瓷钉生产技术领域,尤其涉及一种用于超高温环境下陶瓷钉及制备方法,该陶瓷钉按质量份计包括以下原料：氧化铝粉80～90份、二氧化钛粉2～6份、氧化镁粉2～8份、纳米陶瓷粉体0.5～1.5份、纳米二氧化硅1.5～3.5份、甲基丙烯酸甲酯12～18份和抗腐蚀添加剂25～45份,且其制备方法包括以下步骤：S1、按量称取原料,备用；S2、将原料中的固体研磨成粉并与其余粉体相混合,得到生料粉末,再将生料粉末倒入抗腐蚀添加剂中搅拌混匀,得生料；S3、将生料装入模具,经脉冲电流烧结后得到氧化铝陶瓷。本发明不仅能够改善陶瓷钉的可降解能力,而且还能改善其抗腐蚀能力。(The invention relates to the technical field of ceramic nail production, in particular to a ceramic nail used in an ultrahigh temperature environment and a preparation method thereof, wherein the ceramic nail comprises the following raw materials in parts by mass: 80-90 parts of alumina powder, 2-6 parts of titanium dioxide powder, 2-8 parts of magnesia powder, 0.5-1.5 parts of nano ceramic powder, 1.5-3.5 parts of nano silicon dioxide, 12-18 parts of methyl methacrylate and 25-45 parts of anti-corrosion additive, and the preparation method comprises the following steps: s1, weighing the raw materials according to the weight for later use; s2, grinding the solid in the raw material into powder and mixing the powder with the rest powder to obtain raw material powder, pouring the raw material powder into the anti-corrosion additive, and stirring and mixing uniformly to obtain raw material; and S3, filling the raw material into a die, and sintering by pulse current to obtain the alumina ceramic. The invention can not only improve the degradability of the ceramic nail, but also improve the corrosion resistance of the ceramic nail.)

1. The ceramic nail for the ultrahigh-temperature environment is characterized by comprising the following raw materials in parts by mass: 80-90 parts of alumina powder, 2-6 parts of titanium dioxide powder, 2-8 parts of magnesium oxide powder, 0.5-1.5 parts of nano ceramic powder, 1.5-3.5 parts of nano silicon dioxide, 12-18 parts of methyl methacrylate and 25-45 parts of an anti-corrosion additive;

wherein the nano ceramic powder is a mixed powder of silicon nitride powder and zirconia powder.

2. The ceramic nail for the ultra-high temperature environment according to claim 1, wherein the mass ratio of the alumina powder to the anti-corrosion additive is (2-3): 1.

3. the ceramic nail for the ultra-high temperature environment according to claim 1, wherein the anti-corrosion additive is made of nickel-based alloy, inorganic zinc silicate and inorganic antibacterial powder, wherein the nickel-based alloy is Ni-Mo alloy, the inorganic antibacterial powder is JDGKP-010E, and the anti-corrosion additive is prepared by the following steps: the nickel-based alloy and the inorganic zinc silicate are crushed and then mixed with the inorganic antibacterial powder, and the mixture is granulated in a granulator after being uniformly mixed to obtain the granular anti-corrosion additive.

4. The ceramic nail for the ultra-high temperature environment according to claim 3, wherein the extracting solution is concentrated by a reverse dialysis concentration method.

5. The ceramic nail for the ultra-high temperature environment according to claim 3, wherein the density of the concentrated solution of the extracting solution is 1.12-1.15.

6. A preparation method of a ceramic nail used in an ultrahigh temperature environment is characterized by comprising the following steps:

s1, weighing the raw materials according to the weight for later use;

s2, grinding the solid in the raw material into powder and mixing the powder with the rest powder to obtain raw material powder, pouring the raw material powder into the anti-corrosion additive, and stirring and mixing uniformly to obtain raw material;

s3, loading the raw material into a die, and sintering by pulse current to obtain alumina ceramic;

s4, taking polyoxosilane as a precursor, and carrying out vacuum impregnation and inert atmosphere cracking on the alumina ceramic to obtain a primary blank;

s5, processing the primary blank into a semi-finished product according to the requirements of the screw;

and S6, performing vacuum impregnation and inert atmosphere cracking treatment on the semi-finished product for 8-12 times, and finally obtaining the finished ceramic nail.

7. The method for preparing the ceramic nail used in the ultra-high temperature environment according to claim 6, wherein the particle size of the powder in S2 is less than or equal to 1 μm.

8. The method for preparing the ceramic nail used in the ultra-high temperature environment according to claim 6, wherein the vacuum impregnation time in S6 is 2-8 h, and the temperature of the inert atmosphere cracking is 800-1000 ℃.

9. The method for manufacturing the ceramic nail used in the ultrahigh-temperature environment according to claim 6, wherein the vacuum impregnation is performed by taking a polyoxosilane solution as an impregnation solution, the mass fraction of the polyoxosilane is 50%, and ethanol is used as a solvent.

Technical Field

The invention relates to the technical field of ceramic nail production, in particular to a ceramic nail used in an ultrahigh temperature environment and a preparation method thereof.

Background

With the development of the technology in the high temperature field, people put higher performance requirements on materials for preparing high temperature devices. The ceramic matrix composite has excellent performances of high temperature resistance, high specific strength and the like, and is widely applied in the field of high temperature. Although the traditional metal screw is easy to machine and form, compared with the screw which is low in strength and not high-temperature resistant, the screw prepared from graphite and C/C composite materials is easy to oxidize at high temperature and is not high in strength, so that the screw is not suitable for connecting high-temperature devices, and the ceramic screw is more suitable for the high-temperature field due to excellent performance.

When the existing ceramic nail is used in a strong corrosive environment, large-area corrosion is easily caused, the connection effect of the ceramic nail is influenced, and the waste ceramic nail does not have the degradability. Therefore, we propose a ceramic nail for use in ultra-high temperature environment and a preparation method thereof to solve the above problems.

Disclosure of Invention

The invention aims to solve the defects in the prior art, and provides a ceramic nail used in an ultrahigh-temperature environment and a preparation method thereof.

A ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 80-90 parts of alumina powder, 2-6 parts of titanium dioxide powder, 2-8 parts of magnesium oxide powder, 0.5-1.5 parts of nano ceramic powder, 1.5-3.5 parts of nano silicon dioxide, 12-18 parts of methyl methacrylate and 25-45 parts of an anti-corrosion additive;

wherein the nano ceramic powder is a mixed powder of silicon nitride powder and zirconia powder.

Preferably, the mass ratio of the alumina powder to the anti-corrosion additive is (2-3): 1.

preferably, the anti-corrosion additive is prepared from a nickel-based alloy, inorganic zinc silicate and inorganic antibacterial powder, wherein the nickel-based alloy is a Ni-Mo alloy, the model of the inorganic antibacterial powder is JDGKP-010E, and the preparation method of the anti-corrosion additive comprises the following steps: the nickel-based alloy and the inorganic zinc silicate are crushed and then mixed with the inorganic antibacterial powder, and the mixture is granulated in a granulator after being uniformly mixed to obtain the granular anti-corrosion additive.

Preferably, the process for concentrating the extracting solution adopts a reverse dialysis concentration method.

Preferably, the density of the concentrated solution of the extracting solution is 1.12-1.15.

A preparation method of a ceramic nail used in an ultrahigh temperature environment comprises the following steps:

s1, weighing the raw materials according to the weight for later use;

s2, grinding the solid in the raw material into powder and mixing the powder with the rest powder to obtain raw material powder, pouring the raw material powder into the anti-corrosion additive, and stirring and mixing uniformly to obtain raw material;

s3, loading the raw material into a die, and sintering by pulse current to obtain alumina ceramic;

s4, taking polyoxosilane as a precursor, and carrying out vacuum impregnation and inert atmosphere cracking on the alumina ceramic to obtain a primary blank;

s5, processing the primary blank into a semi-finished product according to the requirements of the screw;

and S6, performing vacuum impregnation and inert atmosphere cracking treatment on the semi-finished product for 8-12 times, and finally obtaining the finished ceramic nail.

Preferably, the particle size of the powder in S2 is less than or equal to 1 μm.

Preferably, the vacuum impregnation time in the S6 is 2-8 h, and the temperature of the inert atmosphere cracking is 800-1000 ℃.

Preferably, the vacuum impregnation is performed by taking a polyoxosilane solution as an impregnation liquid, the mass fraction of the polyoxosilane is 50%, and ethanol is taken as a solvent.

The invention has the beneficial effects that:

1. add methyl methacrylate in the raw materials composition, make ceramic nail through processes such as crocus, mixture, flooding and schizolysis, make the methyl methacrylate who adds decompose under high temperature to make the inside a plurality of spaces that form of ceramic nail, and then improve the degradability of this ceramic nail.

2. The anti-corrosion additive is added into the raw material composition, so that the anti-corrosion capability of the ceramic nail can be improved, and the ceramic nail is favorable for use in severe environment.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples.

A ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 80-90 parts of alumina powder, 2-6 parts of titanium dioxide powder, 2-8 parts of magnesium oxide powder, 0.5-1.5 parts of nano ceramic powder, 1.5-3.5 parts of nano silicon dioxide, 12-18 parts of methyl methacrylate and 25-45 parts of an anti-corrosion additive;

the nano ceramic powder is a mixed powder of silicon nitride powder and zirconia powder, and the mass ratio of the alumina powder to the anti-corrosion additive is (2-3): 1.

the anti-corrosion additive is prepared from a nickel-based alloy, inorganic zinc silicate and inorganic antibacterial powder, wherein the nickel-based alloy is a Ni-Mo alloy, the model of the inorganic antibacterial powder is JDGKP-010E, and the preparation method of the anti-corrosion additive comprises the following steps: the nickel-based alloy and the inorganic zinc silicate are crushed and then mixed with the inorganic antibacterial powder, and the mixture is granulated in a granulator after being uniformly mixed to obtain the granular anti-corrosion additive.

A preparation method of a ceramic nail used in an ultrahigh temperature environment comprises the following steps:

s1, weighing the raw materials according to the weight for later use;

s2, grinding the solid in the raw material into powder with the granularity less than or equal to 1 mu m, mixing the powder with the rest powder to obtain raw material powder, pouring the raw material powder into the anti-corrosion additive, and uniformly stirring to obtain raw material;

s3, loading the raw material into a die, and sintering by pulse current to obtain alumina ceramic;

s4, taking polyoxosilane as a precursor, and carrying out vacuum impregnation and inert atmosphere cracking on the alumina ceramic to obtain a primary blank;

s5, processing the primary blank into a semi-finished product according to the requirements of the screw;

and S6, performing vacuum impregnation and inert atmosphere cracking treatment on the semi-finished product for 8 times to finally obtain the finished ceramic nail.

Wherein the vacuum impregnation in S6 is carried out for 3h, the cracking temperature in inert atmosphere is 800 ℃, the vacuum impregnation takes polyoxosilane solution as impregnation liquid, the mass fraction of polyoxosilane is 50%, and ethanol is used as solvent.

The first embodiment is as follows:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 80 parts of alumina powder, 2 parts of titanium dioxide powder, 2 parts of magnesium oxide powder, 0.5 part of nano ceramic powder, 1.5 parts of nano silicon dioxide, 12 parts of methyl methacrylate and 40 parts of anti-corrosion additive.

Example two:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 85 parts of alumina powder, 4 parts of titanium dioxide powder, 5 parts of magnesium oxide powder, 1 part of nano ceramic powder, 2.5 parts of nano silicon dioxide, 15 parts of methyl methacrylate and 42.5 parts of anti-corrosion additive.

Example three:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 90 parts of alumina powder, 6 parts of titanium dioxide powder, 8 parts of magnesium oxide powder, 1.5 parts of nano ceramic powder, 3.5 parts of nano silicon dioxide, 18 parts of methyl methacrylate and 45 parts of anti-corrosion additive.

In the first to third embodiments, the mass ratio of the alumina powder to the anti-corrosion additive is 2:1, and the method for preparing the ceramic nail from the raw materials in the above embodiments comprises the following steps:

s1, weighing the raw materials according to the weight for later use;

s2, grinding the solid in the raw material into powder with the granularity less than or equal to 1 mu m, mixing the powder with the rest powder to obtain raw material powder, pouring the raw material powder into the anti-corrosion additive, and uniformly stirring to obtain raw material;

s3, loading the raw material into a die, and sintering by pulse current to obtain alumina ceramic;

s4, taking polyoxosilane as a precursor, and carrying out vacuum impregnation and inert atmosphere cracking on the alumina ceramic to obtain a primary blank;

s5, processing the primary blank into a semi-finished product according to the requirements of the screw;

and S6, performing vacuum impregnation and inert atmosphere cracking treatment on the semi-finished product for 8 times to finally obtain the finished ceramic nail.

Test one: determination of degradability of the ceramic nail

Comparative example one:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 80 parts of alumina powder, 2 parts of titanium dioxide powder, 2 parts of magnesia powder, 0.5 part of nano ceramic powder, 1.5 parts of nano silicon dioxide and 40 parts of anti-corrosion additive.

Comparative example two:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 85 parts of alumina powder, 4 parts of titanium dioxide powder, 5 parts of magnesia powder, 1 part of nano ceramic powder, 2.5 parts of nano silicon dioxide and 42.5 parts of anti-corrosion additive.

Comparative example three:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 90 parts of alumina powder, 6 parts of titanium dioxide powder, 8 parts of magnesia powder, 1.5 parts of nano ceramic powder, 3.5 parts of nano silicon dioxide and 45 parts of anti-corrosion additive.

The above comparative examples can each be prepared by the following procedure:

s1, weighing the raw materials according to the weight for later use;

s2, grinding the solid in the raw material into powder and mixing the powder with the rest powder to obtain raw material powder, pouring the raw material powder into the anti-corrosion additive, and stirring and mixing uniformly to obtain raw material;

s3, loading the raw material into a die, and sintering by pulse current to obtain alumina ceramic;

s4, taking polyoxosilane as a precursor, and carrying out vacuum impregnation and inert atmosphere cracking on the alumina ceramic to obtain a primary blank;

s5, processing the primary blank into a semi-finished product according to the requirements of the screw;

and S6, performing vacuum impregnation and inert atmosphere cracking treatment on the semi-finished product for 8 times to finally obtain the finished ceramic nail.

Preparation of organic dye solution: respectively weighing 0.0050g of organic dye (eosin, methyl orange, acid fuchsin and methyl red) in a small beaker, transferring 10ml of distilled water by using a transfer pipette to dissolve, transferring 5ml of solution by using the transfer pipette to a volumetric flask of 250ml, and then fixing the volume and shaking up to prepare an organic dye solution;

photocatalytic degradation: adding one ceramic nail in the embodiment and the comparative example into the organic dye solution respectively, stirring for 2 hours under dark conditions, then placing the mixture under natural light for degradation reaction, taking supernatant liquid every 5min, centrifuging the supernatant liquid by using a centrifuge, taking the supernatant liquid, and detecting the degradation rate of the organic dye solution by using an ultraviolet-visible spectrophotometer, wherein specific results are shown in the table below.

Percent of degradation/%)	Dawn (dawn of dawn colour)	Methyl orange	Acid fuchsin	Methyl Red
					Example one	97.3	99.2	89.5	94.6
Example two	97.2	98.7	89.1	93.9
					EXAMPLE III	97.0	98.8	90.2	95.3
Comparative example 1	37.8	38.5	40.3	45.6
					Comparative example No. two	38.1	38.5	41.6	45.0
Comparative example No. three	36.8	37.2	46.1	44.3

As can be seen from the data in the above table, the degradation rate in the examples was higher than that in the comparative examples, that is, the ceramic nail prepared by the formulation of the examples and the process steps thereof was superior in degradability.

And (2) test II: measurement of the Corrosion resistance of the ceramic nail

Comparative example four:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 80 parts of alumina powder, 2 parts of titanium dioxide powder, 2 parts of magnesium oxide powder, 0.5 part of nano ceramic powder, 1.5 parts of nano silicon dioxide and 12 parts of methyl methacrylate.

Comparative example five:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 85 parts of alumina powder, 4 parts of titanium dioxide powder, 5 parts of magnesium oxide powder, 1 part of nano ceramic powder, 2.5 parts of nano silicon dioxide and 15 parts of methyl methacrylate.

Comparative example six:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 90 parts of alumina powder, 6 parts of titanium dioxide powder, 8 parts of magnesium oxide powder, 1.5 parts of nano ceramic powder, 3.5 parts of nano silicon dioxide and 18 parts of methyl methacrylate.

The above comparative examples can each be prepared by the following procedure:

s1, weighing the raw materials according to the weight for later use;

s2, grinding the solid in the raw material into powder and mixing the powder with the rest powder to obtain raw material powder;

s3, filling the raw material powder into a die, and sintering by pulse current to obtain alumina ceramic;

s4, taking polyoxosilane as a precursor, and carrying out vacuum impregnation and inert atmosphere cracking on the alumina ceramic to obtain a primary blank;

s5, processing the primary blank into a semi-finished product according to the requirements of the screw;

and S6, performing vacuum impregnation and inert atmosphere cracking treatment on the semi-finished product for 8 times to finally obtain the finished ceramic nail.

The corrosion resistance test was performed by using a neutral salt spray test (NSS test), the ceramic nails of the first to third examples and the fourth to comparative examples were placed in a salt spray box for the test, and the time for the surface of the ceramic nail to start to be corroded within five days (120h) was observed and recorded, which is specifically shown in the following table:

as can be seen from the data in the above table, the ceramic nail manufactured in the example was more delayed in the time to start being corroded than the ceramic nail manufactured in the comparative example, that is, the ceramic nail manufactured by the formulation of the example and the process steps thereof was superior in corrosion resistance.

And (3) test III: determination of the Mass ratio of alumina powder to Corrosion-inhibiting additive

Comparative example seven:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 120 parts of alumina powder, 2 parts of titanium dioxide powder, 2 parts of magnesia powder, 0.5 part of nano ceramic powder, 1.5 parts of nano silicon dioxide, 12 parts of methyl methacrylate and 40 parts of anti-corrosion additive.

Comparative example eight:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 40 parts of alumina powder, 2 parts of titanium dioxide powder, 2 parts of magnesia powder, 0.5 part of nano ceramic powder, 1.5 parts of nano silicon dioxide, 12 parts of methyl methacrylate and 40 parts of anti-corrosion additive.

Comparative example nine:

a ceramic nail used in an ultra-high temperature environment comprises the following raw materials in parts by mass: 160 parts of alumina powder, 2 parts of titanium dioxide powder, 2 parts of magnesia powder, 0.5 part of nano ceramic powder, 1.5 parts of nano silicon dioxide, 12 parts of methyl methacrylate and 40 parts of anti-corrosion additive.

The method for preparing the ceramic nail from the raw materials in each embodiment comprises the following steps:

s1, weighing the raw materials according to the weight for later use;

s2, grinding the solid in the raw material into powder with the granularity less than or equal to 1 mu m, mixing the powder with the rest powder to obtain raw material powder, pouring the raw material powder into the anti-corrosion additive, and uniformly stirring to obtain raw material;

s3, loading the raw material into a die, and sintering by pulse current to obtain alumina ceramic;

s4, taking polyoxosilane as a precursor, and carrying out vacuum impregnation and inert atmosphere cracking on the alumina ceramic to obtain a primary blank;

s5, processing the primary blank into a semi-finished product according to the requirements of the screw;

and S6, performing vacuum impregnation and inert atmosphere cracking treatment on the semi-finished product for 8 times to finally obtain the finished ceramic nail.

The ceramic nail of the above comparative example and example one was subjected to an experiment according to the test method of test one, in which only two sets of organic dye solutions of eosin and methyl orange were designed, and then the degradation rate thereof was measured in the same procedure as that of test one, and the specific results are shown in the following table.

Percent of degradation/%)	Mass ratio of	Dawn (dawn of dawn colour)	Methyl orange
				Example one	2:1	97.3	99.2
Comparative example seven	3:1	96.9	98.8
				Comparative example eight	1:1	88.1	89.3
Comparative example No. nine	4:1	87.9	88.1

As can be seen from the data in the table above, when the mass ratio of the alumina powder to the anti-corrosion additive is in the range of 2:1 to 3:1, the degradation rate is higher than that of the alumina powder and the anti-corrosion additive at other ratios.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.