CN112521159A - Boron nitride composite ceramic and preparation method and application thereof - Google Patents

Boron nitride composite ceramic and preparation method and application thereof Download PDF

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CN112521159A
CN112521159A CN202010200849.9A CN202010200849A CN112521159A CN 112521159 A CN112521159 A CN 112521159A CN 202010200849 A CN202010200849 A CN 202010200849A CN 112521159 A CN112521159 A CN 112521159A
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boron nitride
composite ceramic
ceramic
parts
nitride composite
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侯广生
黄小红
褚宗富
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Shandong Jingyi New Material Co ltd
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Shandong Jingyi New Material Co ltd
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Abstract

The invention provides boron nitride composite ceramic and a preparation method and application thereof, belonging to the technical field of ceramic nozzles. The boron nitride composite ceramic provided by the invention comprises the following preparation raw materials in parts by weight: 60-70 parts of boron nitride, 10-20 parts of inorganic binder, 3-10 parts of modifier and 10-20 parts of zirconia. The invention adds the inorganic binder, the modifier and the zirconia on the basis of the pure-phase boron nitride ceramic, not only inherits the excellent machining performance of the pure-phase boron nitride, but also greatly improves the mechanical property and the metal erosion resistance. According to the embodiment, the density of the boron nitride composite ceramic provided by the invention can reach more than 96%; the ceramic nozzle has excellent mechanical property, thermal shock resistance and metal erosion resistance, and when the ceramic nozzle is used for the ceramic nozzle, the thermal shock resistance and the metal erosion resistance of the ceramic nozzle can be improved, the phenomenon of nozzle blockage is reduced, and the service life of the ceramic nozzle is prolonged.

Description

Boron nitride composite ceramic and preparation method and application thereof
Technical Field
The invention relates to the technical field of ceramic nozzles, in particular to boron nitride composite ceramic and a preparation method and application thereof.
Background
Glass has been used by human beings since a long time as an amorphous material, and an amorphous alloy called metallic glass is a novel soft magnetic material developed in the 60's of the 20 th century, and is called a novel functional material of the 21 st century. Due to the particularity of the internal structure of the amorphous alloy, the atomic arrangement structure is disordered in a long range and ordered in a short range, so that the amorphous alloy is different from the crystal structure of the traditional metal material, and has different performance characteristics such as soft magnetism, superconductivity, low magnetic loss, wear resistance, corrosion resistance, high strength, high hardness and the like compared with the traditional metal material.
The ceramic nozzle is a key part of an amorphous metal thin strip rapid quenching device, and the nozzle material is required to have excellent chemical stability, scouring resistance, corrosion resistance, easy machining performance and the like on molten alloy. The traditional ceramic nozzles mainly comprise silicon dioxide ceramic nozzles and pure-phase boron nitride ceramic nozzles, and the silicon dioxide ceramic nozzles have high hardness, poor machining performance and poor corrosion resistance, so that the application range of the silicon dioxide ceramic nozzles is greatly limited; although the pure-phase boron nitride ceramic nozzle has good machining performance, the hardness, toughness and thermal shock resistance are poor, and phenomena such as nozzle deformation, nozzle blockage, molten metal erosion and the like are often caused.
Patent CN 1044466500A discloses a boron nitride silicon micro powder composite ceramic nozzle and a preparation method thereof, and the steps of the invention comprise the mixing of boron nitride, potassium feldspar, sodium feldspar, alumina and silicon micro powder, demoulding and forming, hot press forming and machining. However, although the mechanical strength of the ceramic nozzle prepared by the method is improved, the ceramic nozzle has short service life mainly because the metal washing resistance is poor and certain pollution is caused to the alloy solution due to the existence of potassium ions and sodium ions.
Disclosure of Invention
The invention aims to provide boron nitride composite ceramic and a preparation method and application thereof, and a ceramic nozzle made of the boron nitride composite ceramic has the characteristics of high density, good thermal shock resistance, strong metal erosion resistance and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides boron nitride composite ceramic which comprises the following preparation raw materials in parts by weight:
60-70 parts of boron nitride, 10-20 parts of inorganic binder, 3-10 parts of modifier and 10-20 parts of zirconia.
Preferably, the inorganic binder comprises one or more of ammonium chloride, ammonium phosphate, zinc oxide, aluminum oxide, magnesium oxide, calcium silicate, aluminum hydroxide, aluminum phosphate, phosphatase, calcium borate, zinc powder and aluminum powder; the particle size of the inorganic binder is 1-20 μm.
Preferably, the modifier comprises one or more of silicon carbide, silicon nitride, aluminum nitride, silicon dioxide and titanium diboride; the particle size of the modifier is 1-20 mu m.
The invention provides a preparation method of boron nitride composite ceramic in the technical scheme, which comprises the following steps:
carrying out ball milling and mixing on boron nitride, an inorganic binder, a modifier and zirconia to obtain a mixed material;
carrying out cold press molding on the mixed material to obtain a molded body;
and carrying out hot-pressing sintering on the formed body, and cooling to obtain the boron nitride composite ceramic.
Preferably, the ball-milling mixing ball-material ratio is 2-5: 1.
Preferably, the rotation speed of the ball milling mixing is 200-500 rpm, and the time of the ball milling mixing is 6-10 h.
Preferably, the pressure of the cold press molding is 70-100 MPa, and the pressure maintaining time is 1-5 min.
Preferably, the temperature of the hot-pressing sintering is 1900-2000 ℃, the pressure is 17-20 MPa, and the heat preservation and pressure maintaining time is 2-4 h.
Preferably, the hot-pressing sintering is performed in a vacuum or inert gas environment; the heating rate of heating to the hot-pressing sintering temperature is 10-20 ℃/min, and the pressurizing rate of pressurizing to the hot-pressing sintering pressure is 0.3-0.8 MPa/min.
The invention provides application of the boron nitride composite ceramic in the technical scheme or the boron nitride composite ceramic prepared by the preparation method in the technical scheme as a ceramic nozzle material.
The invention provides boron nitride composite ceramic which comprises the following preparation raw materials in parts by weight: 60-70 parts of boron nitride, 10-20 parts of inorganic binder, 3-10 parts of modifier and 10-20 parts of zirconia.
According to the invention, on the basis of pure-phase boron nitride ceramics, an inorganic binder, a modifier and zirconia are added, and a molten phase formed by the inorganic binder at a high temperature can effectively bind boron nitride, the modifier and zirconia particles together, so that gaps among the particles are filled, and the compactness of the composite ceramics is greatly improved; the modifier silicon nitride can generate strong binding force with aluminum oxide and boron nitride, and the thermal shock property and the mechanical property of the material are effectively improved; the zirconia particles and the inorganic binder alumina can generate a co-melting phenomenon, so that tetragonal zirconia is retained, the growth of zirconia grains is greatly inhibited, the bending strength and the breaking strength of the zirconia are enhanced, the toughening effect of the zirconia is fully exerted, and the mechanical property of the composite ceramic is further enhanced. The boron nitride composite ceramic provided by the invention not only inherits the excellent machining performance of pure-phase boron nitride, but also greatly improves the mechanical property and the metal erosion resistance; according to the embodiment, the density of the boron nitride composite ceramic provided by the invention can reach more than 98%; has excellent mechanical property, thermal shock resistance, deformation resistance and metal erosion resistance.
The boron nitride composite ceramic provided by the invention is used for the ceramic nozzle, can improve the thermal shock resistance, the deformation resistance and the metal scouring resistance of the ceramic nozzle, reduce the nozzle blockage phenomenon and prolong the service life of the ceramic nozzle, and is suitable for the fields of Fe composite, FeNi composite, Co composite amorphous soft magnetic alloy, Ni composite Cu composite brazing amorphous alloy and the like.
Detailed Description
The invention provides boron nitride composite ceramic which comprises the following preparation raw materials in parts by weight:
60-70 parts of boron nitride, 10-20 parts of inorganic binder, 3-10 parts of modifier and 10-20 parts of zirconia.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The preparation raw material of the boron nitride composite ceramic comprises, by weight, 60-70 parts of boron nitride, preferably 62-68 parts of boron nitride, and more preferably 65-66 parts of boron nitride. The invention takes boron nitride as the basic raw material of the composite ceramic.
Based on the weight parts of the boron nitride, the preparation raw material of the boron nitride composite ceramic provided by the invention comprises 10-20 parts of inorganic binder, preferably 12-18 parts, and more preferably 15-16 parts. In the present invention, the inorganic binder preferably includes one or more of ammonium chloride, ammonium phosphate, zinc oxide, aluminum oxide, magnesium oxide, calcium silicate, aluminum hydroxide, aluminum phosphate, phosphatase, calcium borate, zinc powder, and aluminum powder, and more preferably, aluminum oxide; when the inorganic binders are a plurality of the above, the proportion of different inorganic binders is not particularly limited, and the inorganic binders can be prepared in any proportion. In the present invention, the particle size of the inorganic binder is preferably 1 to 20 μm, more preferably 5 to 15 μm, and even more preferably 8 to 12 μm. The inorganic binder used in the invention has excellent binding property and crack resistance, and a molten phase formed by the inorganic binder at high temperature can effectively bind boron nitride, silicon nitride and zirconia particles together, so that gaps among the particles are filled, and the compactness of the composite ceramic is greatly improved.
Based on the weight parts of the boron nitride, the preparation raw materials of the boron nitride composite ceramic comprise 3-10 parts of a modifier, preferably 5-8 parts, and more preferably 6-7 parts. In the invention, the modifier preferably comprises one or more of silicon carbide, silicon nitride, aluminum nitride and silicon dioxide, and more preferably silicon nitride; when the modifier is a plurality of the above, the invention has no special limitation on the proportion of different modifications, and any proportion can be used. In the invention, the particle size of the modifier is preferably 1-20 μm, more preferably 5-15 μm, and even more preferably 8-12 μm. The modifier used in the invention has excellent lubricity, wear resistance, chemical stability and thermal shock property, meanwhile, silicon nitride can generate strong binding force with inorganic binder and boron nitride, and the thermal shock property and mechanical property of the material can be effectively improved by adding the silicon nitride; in addition, when the boron nitride composite ceramic is used as a ceramic nozzle, the addition of silicon nitride can effectively prevent the metal oxidation reaction which occurs when molten metal is sprayed and contacts the nozzle.
Based on the weight parts of the boron nitride, the preparation raw material of the boron nitride composite ceramic provided by the invention comprises 10-20 parts of zirconia, preferably 12-18 parts, and more preferably 15-16 parts. Under high temperature, the inorganic binder and the zirconia particles can generate a co-melting phenomenon, so that tetragonal zirconia is retained, the growth of zirconia grains is greatly inhibited, the bending strength and the breaking strength of the zirconia are enhanced, and the toughening effect of the zirconia is fully exerted.
The invention provides a preparation method of boron nitride composite ceramic in the technical scheme, which comprises the following steps:
carrying out ball milling and mixing on boron nitride, an inorganic binder, a modifier, zirconia and alumina grinding balls to obtain a mixed material;
carrying out cold press molding on the mixed material to obtain a molded body;
and carrying out hot-pressing sintering on the formed body, and cooling to obtain the boron nitride composite ceramic.
The invention ball-milling and mixing boron nitride, inorganic binder, modifier, zirconia and alumina grinding balls to obtain a mixed material. In the invention, the grinding balls used for ball milling and mixing are preferably alumina grinding balls; the ball-milling mixing ball-material ratio is preferably 2-5: 1, namely the ratio of the mass of the alumina grinding balls to the total mass of the boron nitride, the inorganic binder, the modifier and the zirconia is preferably 2-5: 1, and more preferably 3-4: 1. The ball milling mixing is preferably carried out in an alumina ceramic pot, the rotation speed of the ball milling mixing is preferably 200-500 rpm, more preferably 250-450 rpm, further preferably 300-400 rpm, and the time of the ball milling mixing is preferably 6-10 h, more preferably 8-9 h. After the ball milling and mixing are completed, the obtained mixture is preferably sieved under a 60-100-mesh sieve, and undersize materials are taken to obtain a mixed material.
After the mixed material is obtained, the mixed material is subjected to cold press molding to obtain a molded body. The invention preferably places the mixed material in a rubber sleeve for cold press molding; the pressure of the cold press molding is preferably 70-100 MPa, more preferably 80-90 MPa, and the pressure maintaining time is preferably 1-5 min, more preferably 2-3 min.
After a forming body is obtained, the forming body is subjected to hot-pressing sintering and is cooled to obtain the boron nitride composite ceramic. The hot-pressing sintering is preferably carried out in a medium-frequency hot-pressing sintering furnace; before the hot-pressing sintering is carried out, the furnace of the medium-frequency hot-pressing sintering furnace is in a vacuum state of-0.8 MPa. In the present invention, the hot press sintering process is preferably: and (2) heating the medium-frequency hot-pressing sintering furnace from room temperature, filling inert gas (preferably nitrogen gas) into the medium-frequency hot-pressing sintering furnace when the temperature is raised to 1450 ℃, keeping the pressure in the furnace (0.3-0.7 MPa), gradually pressurizing, keeping the temperature at 1900-2000 ℃, keeping the pressure at 17-20 MPa, and performing hot-pressing sintering.
The invention can effectively prevent air from entering by filling the inert gas, avoid the oxidation of the nitride, and simultaneously can ensure that the incompletely reacted oxide in the nitride participates in the nitridation reaction in the nitrogen environment.
In the present invention, the hot press sintering is preferably performed under an inert gas atmosphere; the heating rate of heating to the hot-pressing sintering temperature is 10-20 ℃/min, and the pressurizing rate of boosting to the hot-pressing sintering pressure is 0.3-0.8 MPa/min; the temperature of the hot-pressing sintering is preferably 1900-2000 ℃, more preferably 1950-1980 ℃, the pressure is preferably 17-20 MPa, more preferably 18-19 MPa, and the heat preservation and pressure maintaining time is preferably 2-4 h, more preferably 2.5-3.5 h. According to the invention, all the preparation raw materials are refractory substances, and the blank obtained by sintering is actually in a solid solution system.
After the hot-pressing sintering is finished, the boron nitride composite ceramic is preferably cooled along with the furnace to obtain the boron nitride composite ceramic.
The boron nitride composite ceramic is prepared by adopting a vacuum hot-pressing sintering process, and before 1450 ℃, the inorganic binder alumina added under normal pressure begins to generate a softening and melting phenomenon, so that the mutual adhesion of boron nitride, silicon nitride and zirconia is promoted; meanwhile, the existence of the inorganic binder alumina keeps tetragonal zirconia, so that the toughness of the material is enhanced; after the temperature of 1450 ℃, pressurization is started, because the fusion and adhesion phenomena occur among all phases, the cracking of the ceramic caused by the pressure is avoided, meanwhile, the excessive elongation of the ceramic crystal lattice is prevented, and the sintering density of the composite ceramic is improved. Therefore, the boron nitride composite ceramic material prepared by the invention can improve the thermal shock resistance, the deformation resistance and the toughness of the ceramic nozzle, improve the compactness of the composite ceramic and prolong the service life of the nozzle.
The invention provides application of the boron nitride composite ceramic in the technical scheme or the boron nitride composite ceramic prepared by the preparation method in the technical scheme as a ceramic nozzle material. The application method of the boron nitride composite ceramic as the ceramic nozzle is not specially limited, and the ceramic nozzle is directly prepared according to the raw materials and the preparation process of the boron nitride composite ceramic. After the boron nitride composite ceramic is used for the ceramic nozzle, the working principle is that the molten alloy is contacted with a fast moving cooling device through a slit of the nozzle and then is fast cooled and solidified at the cooling speed of 105 ℃/s, and finally, a continuous amorphous strip is obtained.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Putting 67kg of boron nitride, 15kg of alumina, 5kg of silicon nitride, 13kg of zirconia and 300kg of alumina grinding balls into a 500L alumina grinding tank, carrying out ball milling and mixing for 10h at the rotating speed of 300rmp, sieving the obtained mixture by using a 100-mesh sieve, and taking the undersize to obtain a mixed material; placing the mixed material in a rubber sleeve, and keeping the pressure for 1min under the pressure of 90MPa for cold press molding to obtain a molded body; putting the formed body into a medium-frequency hot-pressing sintering furnace, vacuumizing to-0.8 MPa, and heating at the speed of 10 ℃/min; and when the temperature is increased to 1450 ℃, filling nitrogen (keeping the pressure in the furnace at 0.4MP), starting to apply mechanical pressure at the pressurizing rate of 0.3MPa/min until the temperature reaches 1900 ℃ and the pressure is 17MPa, keeping the temperature and the pressure for 4h, performing hot-pressing sintering, and cooling along with the furnace to obtain the boron nitride composite ceramic.
The boron nitride composite ceramic prepared in example 1 was subjected to mechanical property test using an electronic densitometer, an electronic universal testing machine, and a thermal shock resistance test method, and the results showed that the density of the prepared boron nitride composite ceramic was 2.78g/cm3The theoretical density is more than 96%, the bending strength is 260MPa, and the composite material has excellent comprehensive mechanical properties; repeatedly carrying out hundreds of thermal shock tests at the temperature difference of 800 ℃, and having excellent thermal shock resistance without thermal shock fracture phenomenon; meanwhile, the prepared boron nitride composite ceramic has good metal erosion resistance, under the erosion condition of 1000 ℃, the iron alloy molten liquid is adopted for erosion for 40 minutes, the erosion depth is less than 600 mu m, and the service life exceeds 40 hours.
Example 2
Placing 60kg of boron nitride, 15kg of alumina, 10kg of silicon nitride, 15kg of zirconia and 300kg of alumina grinding balls in a 500L alumina grinding tank, carrying out ball milling and mixing for 10h at the rotating speed of 300rmp, sieving the obtained mixture by using a 100-mesh sieve, and taking the undersize to obtain a mixed material; placing the mixed material in a rubber sleeve, and keeping the pressure for 1min under the pressure of 90MPa for cold press molding to obtain a molded body; putting the formed body into a medium-frequency hot-pressing sintering furnace, vacuumizing to-0.8 MPa, and heating at the speed of 10 ℃/min; and when the temperature is increased to 1450 ℃, filling nitrogen (keeping the pressure in the furnace at 0.4MP), starting to apply mechanical pressure at the pressurizing rate of 0.3MPa/min until the temperature reaches 1900 ℃ and the pressure is 17MPa, keeping the temperature and the pressure for 4h, performing hot-pressing sintering, and cooling along with the furnace to obtain the boron nitride composite ceramic.
According to the method of the embodiment 1, the boron nitride composite ceramic prepared in the embodiment 2 is subjected to mechanical property test, and the result shows that the density of the prepared boron nitride composite ceramic is 2.9g/cm3The theoretical density is more than 95%, the bending strength is 300MPa, and the composite material has excellent comprehensive mechanical properties; repeatedly carrying out hundreds of thermal shock tests at the temperature difference of 1000 ℃, and having excellent thermal shock resistance without thermal shock fracture phenomenon; meanwhile, the prepared boron nitride composite ceramic has good metal erosion resistance, and is eroded by using the iron alloy molten liquid for 40 minutes under the erosion condition of 1000 ℃, the erosion depth is less than 500 mu m, and the service life exceeds 50 hours.
Example 3
Placing 60kg of boron nitride, 20kg of alumina, 5kg of silicon nitride, 15kg of zirconia and 300kg of alumina grinding balls in a 500L alumina grinding tank, carrying out ball milling and mixing for 10h at the rotating speed of 300rmp, sieving the obtained mixture by using a 100-mesh sieve, and taking the undersize to obtain a mixed material; placing the mixed material in a rubber sleeve, and keeping the pressure for 1min under the pressure of 90MPa for cold press molding to obtain a molded body; putting the formed body into a medium-frequency hot-pressing sintering furnace, vacuumizing to-0.8 MPa, and heating at the speed of 10 ℃/min; and when the temperature is increased to 1450 ℃, filling nitrogen (keeping the pressure in the furnace at 0.4MP), starting to apply mechanical pressure at the pressurizing rate of 0.3MPa/min until the temperature reaches 1900 ℃ and the pressure is 17MPa, keeping the temperature and the pressure for 4h, performing hot-pressing sintering, and cooling along with the furnace to obtain the boron nitride composite ceramic.
According to the method of the embodiment 1, the boron nitride composite ceramic prepared in the embodiment 3 is subjected to mechanical property test, and the result shows that the density of the prepared boron nitride composite ceramic is 2.98g/cm3The theoretical density is more than 97 percent, the bending strength is 320MPa, and the composite material has excellent comprehensive mechanical properties; repeatedly carrying out hundreds of thermal shock tests at the temperature difference of 700 ℃, and having excellent thermal shock resistance without thermal shock fracture phenomenon; meanwhile, the prepared boron nitride composite ceramic has good metal erosion resistance, is eroded by using iron alloy molten liquid for 40 minutes under the erosion condition of 1000 ℃, has the erosion depth of less than 800 mu m and has the service life of more than 30h。
According to the embodiments, the boron nitride composite ceramic and the preparation method and the application thereof are provided, and the compactness of the boron nitride composite ceramic provided by the invention can reach more than 98%; has excellent mechanical property, thermal shock resistance, deformation resistance and metal erosion resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The boron nitride composite ceramic is characterized by comprising the following preparation raw materials in parts by weight:
60-70 parts of boron nitride, 10-20 parts of inorganic binder, 3-10 parts of modifier and 10-20 parts of zirconia.
2. The boron nitride composite ceramic of claim 1, wherein the inorganic binder comprises one or more of ammonium chloride, ammonium phosphate, zinc oxide, aluminum oxide, magnesium oxide, calcium silicate, aluminum hydroxide, aluminum phosphate, phosphatase, calcium borate, zinc powder, and aluminum powder; the particle size of the inorganic binder is 1-20 μm.
3. The boron nitride composite ceramic of claim 1, wherein the modifier comprises one or more of silicon carbide, silicon nitride, aluminum nitride, silicon dioxide, and titanium diboride; the particle size of the modifier is 1-20 mu m.
4. The method for producing the boron nitride composite ceramic according to any one of claims 1 to 3, characterized by comprising the steps of:
carrying out ball milling and mixing on boron nitride, an inorganic binder, a modifier and zirconia to obtain a mixed material;
carrying out cold press molding on the mixed material to obtain a molded body;
and carrying out hot-pressing sintering on the formed body, and cooling to obtain the boron nitride composite ceramic.
5. The preparation method of claim 4, wherein the ball-milling mixing ratio of balls to materials is 2-5: 1.
6. The preparation method of claim 4 or 5, wherein the rotation speed of the ball milling and mixing is 200-500 rpm, and the time of the ball milling and mixing is 6-10 h.
7. The preparation method according to claim 4, wherein the pressure of the cold press molding is 70 to 100MPa, and the dwell time is 1 to 5 min.
8. The preparation method according to claim 4, wherein the hot press sintering temperature is 1900-2000 ℃, the pressure is 17-20 MPa, and the holding time is 2-4 h.
9. The production method according to claim 8, wherein the hot press sintering is performed under an inert gas atmosphere; the heating rate of heating to the hot-pressing sintering temperature is 10-20 ℃/min, and the pressurizing rate of pressurizing to the hot-pressing sintering pressure is 0.3-0.8 MPa/min.
10. Use of the boron nitride composite ceramic according to any one of claims 1 to 3 or the boron nitride composite ceramic prepared by the preparation method according to any one of claims 4 to 9 as a material for preparing a ceramic nozzle.
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