CN103708843A - Boron nitride coating and application method - Google Patents
Boron nitride coating and application method Download PDFInfo
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- CN103708843A CN103708843A CN201310705105.2A CN201310705105A CN103708843A CN 103708843 A CN103708843 A CN 103708843A CN 201310705105 A CN201310705105 A CN 201310705105A CN 103708843 A CN103708843 A CN 103708843A
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Abstract
The invention belongs to the field of refractory materials and mainly relates to a boron nitride coating and an application method. The coating is mainly applied to special refractory materials; the coating is adhered on the surface of a refractory material or penetrated into the working layer of the refractory material to improve the application performance of the refractory material; the particle size of boron nitride ranges from 20 microns to 50 microns, the mass content of boron nitride is 30-85%, and the mass content of boron oxide in the coating is 2-5%. According to the boron nitride coating provided by the invention, boron nitride powder with large particle size and boron oxide are used as the main body, and boron oxide is melted at a low temperature stage to form high-viscosity melt so as to enhance the adhesive force of the boron nitride coating; meanwhile, boron oxide plays a combustion-supporting function due to the existence of a liquid phase, boron oxide generates a nitridation reaction at a high temperature to be converted into boron nitride, and boron nitride generated by the reaction has high activity to promote the sintering of the boron nitride coating; due to the existence of the boron nitride powder with large particle size, the finally formed coating is not densely sintered, and the firing shrinkage of the coating is small to avoid deviation with a matrix.
Description
Technical field
The invention belongs to fire resisting material field, relate generally to a kind of boron nitride coating and using method.
Background technology
Boron nitride (chemical formula: BN) without sharp melting point, maximum operation (service) temperature can reach 2800 ℃, there are six sides and cube two kinds of crystal, common is hexagonal, hexagonal boron nitride belongs to sheet hexagonal structure, it has the advantages such as fusing point is high, linear expansivity is little, thermal conductivity is large, also has that good thermal shock, high-temperature insulating quality are high, high temperature lubricating and an advantage such as resistance to fouling is good.In recent years, some researchers utilize these characteristics of boron nitride to develop various boron nitride coatings, by boron nitride being spread upon to refractory surface, utilize the above-mentioned advantage of boron nitride, because hexagonal boron nitride also exists the problem that is difficult to sintering, generally in coating, add various " easy-sintering bodies " or realize sintering with ultra-fine micropowder, shortcoming is to add " easy-sintering body " easily to introduce impurity, cause use temperature not high, as the boron nitride coating of common boron nitride-alumina system, in coating, add exactly a certain proportion of aluminum oxide, because aluminum oxide gets final product sintering at 1600 ℃, realize the sclerosis of coating, but because the resistance to elevated temperatures of aluminum oxide is low compared with boron nitride, pure alumina refractory materials use temperature is below 1800 ℃, this use temperature that just determines this coating can be over 2000 ℃, and add ultra-fine micropowder to cause to burn till contraction ratio large, as to take the boron nitride of 5 microns of following granularities be main body, with the short pure boron nitride coating burning of nm-class boron nitride, this coating advantage is in the final boron nitride coating forming, boron nitride content is high, heatproof is high, shortcoming is coating densification, burn till and shrink greatly, if the percent of firing shrinkage of zirconium white sanded brick is between 0.5% to 1%, and the coating of this easy densification is burnt till and is contracted in more than 3%, as use this coating to spread upon zirconium white sanded brick surface, two kinds of material percent of firing shrinkage are widely different, be easy to cause coating crack or depart from smeared body material layering.
Boron oxide (B
2o
3), claim again boron trioxide, boric anhydride etc., 470 ℃ of fusing points, at fire resisting material field, are often used as sintering agent and use, and as in siliceous dry type ramming material, introduce a small amount of boron oxide, form a wetting band, acceleration of sintering between particle and matrix.
At fire resisting material field, boron nitride coating in use, generally directly to spread upon on fire resistive material product surface, directly use after drying, operation is simpler, strong operability, shortcoming is not sclerosis of coating, if use temperature lower than the sintering temperature of coating, can cause strength of coating not high, easily efflorescence, come off.
Summary of the invention
The problems referred to above that in use run into for solving boron nitride coating, the present invention proposes a kind of boron nitride coating and using method, it is main body that this kind of coating be take volume particle size boron nitride powder and boron oxide, low thermophase, boron oxide fusing, form high-viscosity melt, the sticking power of strengthening boron nitride coating, while is due to the existence of liquid phase, boron oxide also plays the effect that helps burning, during high temperature, boron oxide generation nitrogenizing reaction changes into boron nitride, this boron nitride generating through reaction has higher activity, can promote the sintering of boron nitride coating, existence due to volume particle size boron nitride powder, the final coating forming can densified sintering product, coating percent of firing shrinkage is little, avoid departing from matrix.
The present invention is achieved through the following technical solutions its goal of the invention:
A kind of boron nitride coating, by being attached to refractory surface or permeating in refractory materials working lining, improve the use properties of refractory materials, it is characterized in that: in described coating, there is boron nitride and boron oxide, described boron nitride granularity is between 20 microns to 50 microns, the mass content 30%～85% of described boron nitride, described boron oxide mass content is between 2% to 5%.
Described boron nitride is hexagonal boron nitride.
Described boron oxide can be directly to add, also can be by first adding boric acid to form through dehydration conversion.
The using method that the invention still further relates to a kind of boron nitride coating, mainly comprises the following steps:
1, coating is stirred 2 minutes to 15 minutes;
2, coating is evenly spread upon to matrix surface, or immerse matrix working face;
3, by smearing complete matrix, be put in loft drier, 110 ℃ are dried 2 hours to 5 hours;
4, dried matrix is put into ammonia stove, and logical ammonia carries out nitrogenizing reaction 2 hours to 5 hours in 900 ℃～1000 ℃;
5, logical nitrogen protection, continues to be heated to 1600 ℃, and is incubated 3 hours to 5 hours, and boron nitride coating is sinter-hardened;
6, nitrogen protection, continues to be heated to matrix firing temperature or completes sintering according to basic material.
Adopt this coating and using method, when temperature is over 470 ℃, boron oxide changes into liquid state, boron oxide melt has higher viscosity, the sticking power that improves boron nitride and body material prevents from coming off, boron oxide melt is present in around boron nitride, whole coating and matrix are just in liquid phase--the sintering state of solid phase, can promote boron nitride and matrix at the sintering of low-temperature zone, when temperature reaches 1000 ℃, boron oxide completes nitrogenize, forms boron nitride molecule, the boron nitride molecule that this reaction generates has high activity, can promote boron nitride at the sintering of middle hot stage.
Adopt this coating and using method, coating is burnt till through 1600 ℃～1800 ℃, has certain intensity, when the environment being applied to below 1600 ℃, can not cause coming off of coating, efflorescence; When being applied to more than 1600 ℃ environment, coating can further sintering, but because of the existence of volume particle size boron nitride can because of densified sintering product not cause shrink excessive.
Adopt this kind of coating and using method, without boron nitride is processed into ultra-fine micropowder, without adding other easy-sintering bodies, can solve the problem of boron nitride hard-to-sinter, existence because of volume particle size boron nitride prevents the excessive crackle that causes of coating sintering shrinkage again, adopt this coating and using method, the coating finally forming through pyroprocessing, be different from general boron nitride coating surface densification, this kind of coating is due to the existence of volume particle size boron nitride, between boron nitride grain, build airtight one by one little space, make whole coating have a certain amount of pore, can effectively reduce the damage of thermal stresses to coating, and can reduce the thermal conductivity of coating, boron oxide changes into boron nitride, in the final coating forming, boron nitride content can reach more than 98%, effectively improve the result of use of whole refractory materials.
Embodiment
Embodiment in conjunction with providing, is illustrated the present invention:
Embodiment 1, and the Bubble zirconia brick (ZBB-98) that Luoyang Refractory Institute Co., Ltd., SINO Steel Corporation produces of take is matrix, and this hollow ball product, zirconia content is 98%(mass percent) apparent porosity is 63%
1, first by matrix at 110 ℃ dry 3 hours standby;
2, preparation boron nitride coating, granularity is that the boron nitride of 50 microns～40 microns accounts for 30% of coating quality, granularity is that the boron nitride of 40 microns～30 microns accounts for 20% of coating quality, granularity is that the boron nitride of 30 microns～20 microns accounts for 35% of coating quality, and boron oxide accounts for 2% of coating quality, and water accounts for 10% of coating quality, additive flocculation agent polyvinyl alcohol 1%, water reducer tripoly phosphate sodium STPP 1%, defoamer isooctyl alcohol 1%, stir 15 minutes standby;
3, matrix working face is immersed in boron nitride coating to 2 hours downwards, coating infiltrates through working lining, takes out matrix, top layer is smeared smooth, puts into 110 ℃, baking oven dry 3 hours;
4, matrix is put into ammonia stove, pass into ammonia, with the speed of 5 ℃/min, be warming up to 500 ℃, at 500 ℃, be incubated 2 hours, boron oxide liquefies completely, continuation is warming up to 1000 ℃ with the speed of 2 ℃/min, at 1000 ℃, is incubated 2 hours, guarantees that boron oxide nitrogenize is complete, change logical nitrogen, continuation is warming up to 1600 ℃ with the speed of 5 ℃/min, 1600 ℃ of insulations 3 hours, completes the sintering of coating on Bubble zirconia brick.
The Bubble zirconia of preparing with this kind of method--boron nitride coating composite brick, because hollow ball brick apparent porosity is higher, it is inner that coating is easy to be penetrated into hollow ball brick, can prepare the coating that solid content is higher, boron nitride coating had both been present in hollow ball brick surface, part is permeated in hollow ball brick working lining, on surface, boron nitride coating plays protective effect, prevent the crossed contamination between refractory materials and burner hearth, " root " of the boron nitride that boron nitride in working lining becomes top layer working lining on hollow ball brick, firmly top layer boron nitride is fixed together, prevent from peeling off.
Embodiment 2, and the zirconia brick (ZB-98) that Luoyang Refractory Institute Co., Ltd., SINO Steel Corporation produces of take is matrix, this zircite product, zirconia content is 98%(mass percent), apparent porosity is 22%
1, first by matrix at 110 ℃ dry 3 hours standby;
2, preparation boron nitride coating, granularity is that the boron nitride of 50 microns～40 microns accounts for 5% of coating quality, granularity is that the boron nitride of 40 microns～30 microns accounts for 5% of coating quality, granularity is that the boron nitride of 30 microns～20 microns accounts for 20% of coating quality, boric acid accounts for 3% of coating quality, and water accounts for 62% of coating quality, additive flocculation agent polyvinyl alcohol 3%, defoamer isooctyl alcohol 2%, stir 15 minutes standby;
3, matrix working face is immersed in boron nitride coating to 2 hours downwards, coating infiltrates through working lining, takes out matrix, top layer is smeared smooth, puts into 110 ℃, baking oven dry 3 hours;
4, matrix is put into ammonia stove, pass into ammonia, with the speed of 2 ℃/min, be warming up to 200 ℃, at 200 ℃, be incubated 2 hours, continuation is warming up to 1000 ℃ with the speed of 2 ℃/min, at 1000 ℃, be incubated 2 hours, boric acid dehydration forms boron oxide, and is nitrided into boron nitride, change logical nitrogen, continuation is warming up to 1600 ℃ with the speed of 5 ℃/min, 1600 ℃ of insulations 3 hours, completes the sintering of coating on zirconia brick.
The zirconium white of preparing with this kind of method--boron nitride coating composite brick, because zirconia brick apparent porosity is relatively little, preparation solid content is slightly little, the coating that boron nitride granularity is less than normal, be convenient to coating to the infiltration of zirconia brick, boron nitride coating had both been present in zirconia brick surface, part is permeated in zirconia brick working lining, on surface, boron nitride coating plays protective effect, prevent the crossed contamination between refractory materials and burner hearth, " root " of the boron nitride that boron nitride in working lining becomes top layer working lining on zirconia brick, firmly top layer boron nitride is fixed together, prevent from peeling off.
Embodiment 3:
1, with the mixed oxygenerating zirconium pug of simpson mill, zirconium white+stablizer >=98%(mass percent), the stable calcium oxide zirconium white that the electric smelting of take is good is raw material, calcium oxide content 4.1%, in aggregate, 5mm～3mm stable calcium oxide oxidation zircon sand 15%, 3mm～1mm stable calcium oxide oxidation zircon sand 30%, 1mm～0.5mm stable calcium oxide oxidation zircon sand 30%, matrix comprises stable calcium oxide zirconia powder 0.5mm～100 order 10%, stable calcium oxide zirconia powder 100 order～200 orders 7%, stable calcium oxide zirconia powder 200 orders following 8%, take dextrin as bonding agent, simpson mill mixes, by friction press compression moulding, it is standby after 110 ℃ are dried.
2, preparation boron nitride coating, granularity is that the boron nitride of 40 microns～30 microns accounts for 5% of coating quality, granularity is that the boron nitride of 30 microns～25 microns accounts for 10% of coating quality, granularity is that the boron nitride of 25 microns～20 microns accounts for 25% of coating quality, boron oxide accounts for 5% of coating quality, and water accounts for 47% of coating quality, additive flocculation agent polyvinyl alcohol 1.5%, defoamer isooctyl alcohol 1.5%, stir 2 minutes standby;
3, the boron nitride coating preparing is evenly spread upon on zirconium white sanded brick base substrate working face, top layer is smeared smooth, put into 110 ℃, baking oven dry 3 hours;
4, matrix is put into ammonia stove, pass into ammonia, speed with 5 ℃/min is warming up to 500 ℃, at 500 ℃, be incubated 5 hours, continue to be warming up to 1000 ℃ with the speed of 2 ℃/min, at 1000 ℃, be incubated 5 hours, continuation is warming up to 1800 ℃ with the speed of 5 ℃/min, 1800 ℃ of insulations 5 hours, complete the sintering of zirconium white sanded brick, coating also completes sintering simultaneously.
The zirconium white sanded brick of preparing with this kind of method, when burning till zirconium white base substrate, also completed burning till of coating, the boron nitride that reaction in－situ generates can synchronously promote between boron nitride and boron nitride, the sintering between boron nitride and zirconium white, coating and matrix are sintered together, and reach the object that improves refractory materials result of use.
Claims (4)
1. a boron nitride coating, this coating is mainly used in special refractories, by being attached to refractory surface or permeating in refractory materials working lining, improve the use properties of refractory materials, it is characterized in that: in described coating, there is boron nitride and boron oxide, described boron nitride granularity between 20 microns to 50 microns, the mass content 30%～85% of described boron nitride, described boron oxide mass content is between 2% to 5%.
2. a kind of boron nitride coating as claimed in claim 1, is characterized in that: described boron oxide is direct interpolation, or by first adding boric acid to form through dehydration conversion.
3. a kind of boron nitride coating as claimed in claim 1, is characterized in that: described boron nitride is hexagonal boron nitride.
4. the using method of boron nitride coating described in claim 1, is characterized in that: mainly comprise the following steps:
1) coating is stirred 2 minutes to 15 minutes;
2) coating is evenly spread upon to refractory material matrix surface, or immerse refractory materials working face;
3) by smearing complete matrix, be put in loft drier, 110 ℃ are dried 2 hours to 5 hours;
4) dried refractory material matrix is put into ammonia stove, and logical ammonia carries out nitrogenizing reaction 2 hours to 5 hours in 900 ℃～1000 ℃;
5) logical nitrogen protection, continues to be heated to 1600 ℃, and is incubated 3 hours to 5 hours, and boron nitride coating is sinter-hardened;
6) nitrogen protection, continues to be heated to matrix firing temperature or completes sintering according to refractory material matrix material.
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Cited By (5)
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| CN104399874A (en) * | 2014-12-01 | 2015-03-11 | 上海交通大学 | Hexagonal boron nitride type mold shell investment precoat for precision casting of magnesium alloy investment |
| CN104991298A (en) * | 2015-03-27 | 2015-10-21 | 林嘉佑 | Vacuum coating equipment target material cavity containing boron nitride coating and preparation method |
| CN109021628A (en) * | 2018-07-12 | 2018-12-18 | 商丘师范学院 | It is a kind of can low temperature bonding applied at elevated temperature aqueous boron nitride coating |
| CN110357647A (en) * | 2018-10-08 | 2019-10-22 | 湖南德智新材料有限公司 | A kind of ceramic matric composite and preparation method thereof of silicon carbide nanometer line enhancing |
| CN116285443A (en) * | 2023-04-04 | 2023-06-23 | 广州粤能轻合金技术服务有限公司 | Pollution-free nonferrous metal water-based boron nitride coating and preparation method thereof |
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| CN1449876A (en) * | 2003-05-08 | 2003-10-22 | 上海交通大学 | Zinc liquid corrosion-resistant coating and use method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399874A (en) * | 2014-12-01 | 2015-03-11 | 上海交通大学 | Hexagonal boron nitride type mold shell investment precoat for precision casting of magnesium alloy investment |
| CN104991298A (en) * | 2015-03-27 | 2015-10-21 | 林嘉佑 | Vacuum coating equipment target material cavity containing boron nitride coating and preparation method |
| CN109021628A (en) * | 2018-07-12 | 2018-12-18 | 商丘师范学院 | It is a kind of can low temperature bonding applied at elevated temperature aqueous boron nitride coating |
| CN109021628B (en) * | 2018-07-12 | 2020-09-04 | 商丘师范学院 | Water-based boron nitride coating capable of being bonded at low temperature and used at high temperature |
| CN110357647A (en) * | 2018-10-08 | 2019-10-22 | 湖南德智新材料有限公司 | A kind of ceramic matric composite and preparation method thereof of silicon carbide nanometer line enhancing |
| CN110357647B (en) * | 2018-10-08 | 2022-05-03 | 湖南德智新材料有限公司 | Silicon carbide nanowire reinforced ceramic matrix composite and preparation method thereof |
| CN116285443A (en) * | 2023-04-04 | 2023-06-23 | 广州粤能轻合金技术服务有限公司 | Pollution-free nonferrous metal water-based boron nitride coating and preparation method thereof |
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Application publication date: 20140409 |