CN106588029A - Novel solar heat-absorbing ceramic material and preparation method thereof - Google Patents

Novel solar heat-absorbing ceramic material and preparation method thereof Download PDF

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CN106588029A
CN106588029A CN201610955106.6A CN201610955106A CN106588029A CN 106588029 A CN106588029 A CN 106588029A CN 201610955106 A CN201610955106 A CN 201610955106A CN 106588029 A CN106588029 A CN 106588029A
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葛联峰
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Guangzhou Kai Yao Asset Management Co Ltd
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Abstract

The invention discloses a novel solar heat-absorbing ceramic material and a preparation method thereof. The novel solar heat-absorbing ceramic material is composed of the following components of, by weight, 15-40% of Si3N4, 15-40% of SiC, 5-20% of andalusite, 5-15% of alpha-Al2O3, 1-10% of Y2O3, and 1-10% of Cr2O3; the Si3N4 and the SiC serve as base materials, the andalusite, the alpha-Al2O3, the Y2O3 and the Cr2O3 serve as additives for synthesizing a high temperature resistant combination phase; polyurethane foam serves as a precursor and a polymeric foam replication process is adopted for preparing a foam Si3N4/SiC heat-absorbing ceramic body material which is good in high temperature oxidation resistance and thermal shock resistance and high in specific surface area and heat conductivity and is of a three-dimensional netty structure; and the Si3N4/SiC heat-absorbing ceramic body material is used for a tower type solar thermal power generation heat-absorbing body, the deficiencies that an existing solar heat-absorbing body material is poor in high temperature oxidation resistance and thermal shock resistance are overcome, and a new thought is provided for research and development of solar heat collection equipment.

Description

A kind of new type solar energy heat absorption ceramic material and preparation method thereof
Technical field
The invention belongs to field of inorganic nonmetallic material, and in particular to a kind of new type solar energy heat absorption ceramic material and its system Preparation Method.
Background technology
Solar energy is inexhaustible Renewable resource, and development and utilization solar energy is to realize that energy supply is more One of unitization, important channel of guarantee energy security.In recent years, under the policy guide and requirement of energy-saving and emission-reduction, China's building The application of middle solar energy techniques is dramatically increased, for solar building integrated requirement also more and more higher.
Tower-type solar thermal power generating system is due to focusing ratio height (200-100KW/m2), thermodynamic cycle temperature is high, thermal losses The characteristics of little, simple system and efficiency high, obtains the attention of countries in the world, is that current each state is advanced big all what is studied energetically Scale solar energy thermal-power-generating technology, as the air heat-absorbing device of tower type solar energy thermal power generation core, high temperature endothermic body material therein Material is responsible for reception sun optically focused energy, and the important function of heat absorption heat exchange, affects the stability of whole heat generating system And the height of efficiency.
In light collection solar generation technology, foamed ceramics is often used as the heat-absorbing material of air heat-absorbing device.Si3N4- SiC heat absorption ceramics have high intensity and good heterogeneous microstructure, are a kind of suitable tower type solar energy thermal power generation heat absorptions The new heat-absorbing material of device.Chinese Academy of Sciences electrician institute patent CN101122425A discloses a kind of silicon carbide foam ceramic solar energy and inhales Hot device；CN104671787A discloses a kind of solar energy thermal-power-generating heat-absorption body material-Si3N4The preparation of-SiC heat absorption ceramic materials, With high intensity and good heterogeneous microstructure, it is a kind of suitable tower type solar energy thermal power generation heat extractor heat absorption material Material.
But, due to the absorber local hot spot that tower heat extractor optically focused energy-flux density inhomogeneities and unstability are formed The problems such as causing material thermal stress damage, air flow stability difference and not high durability, thus need urgent exploitation to have High temperature oxidation resistance is good, good thermal shock, the connectivity structure with three-dimensional or two dimension, high-ratio surface and high heat conductance it is new Type absorber material.
The content of the invention
To solve drawbacks described above present in prior art, it is an object of the invention to provide a kind of heat absorption of new type solar energy Ceramic material and preparation method thereof, with Si3N4It is base material with SiC, with andalusite, α-Al2O3、Y2O3And Cr2O3For additive, Synthesis high temperature resistant combines phase, with polyurethane foam as presoma, using Foam dipping method, prepares high temperature oxidation resistance Good, good thermal shock, the foam Si with tridimensional network, high-ratio surface and high heat conductance3N4/ SiC heat absorption ceramic materials, For tower type solar energy thermal power generation absorber.
The purpose of the present invention is achieved through the following technical solutions：
A kind of new type solar energy heat absorption ceramic material, is made up of the component comprising following weight percentage：Si3N415- 40wt%, SiC15-40wt%, andalusite 5-20wt%, α-Al2O35-15wt%, Y2O31-10wt%, Cr2O31-10wt%, With Si3N4It is base material with SiC, with andalusite, α-Al2O3、Y2O3And Cr2O3Phase is combined for additive synthesis high temperature resistant, with poly- ammonia Ester foam is presoma, prepares foam Si using Foam dipping method3N4/ SiC heat absorption ceramic materials.
Described base material Si3N4, SiC, additive andalusite, α-Al2O3、Y2O3、Cr2O3It is mean diameter 1-100nm Powder.
Described polyurethane foam precursor is liquid.
A kind of new type solar energy heat absorption ceramic material and preparation method thereof, comprises the steps of：
(1) above-mentioned raw materials are weighed according to proportioning, with dehydrated alcohol as dispersant, ZrO2Ball is ball-milling medium, using cylinder Formula ball mill ball milling mixing 12-16h under conditions of rotational speed of ball-mill is 120-140r/min obtains slurry；
(2) it is 1 according to weight ratio by the slurry in step (1) and precursor solution polyurethane foam：5-100 mixes and stirs 10-30min is mixed, supersound process 1-12h is then carried out and is sufficiently mixed uniformly；
(3) mixture in step (2) is placed in hermetic container, is warming up to 150-300 DEG C；Under inert gas shielding 1-6h is to crosslinking curing for insulation, then vacuum drying；
(4) mixture after solidification drying in step (3) is placed in vacuum sintering funace, in noble gases or vacuum In be heated to 1400-1600 DEG C, pressure be 30-50Mpa under sinter 6-10h, be then cooled to 800-1200 DEG C insulation 3-5h There must be the foam Si of tridimensional network3N4/ SiC heat absorption ceramic materials.
The invention has the advantages that：
The new type solar energy heat absorption ceramic material pore of the present invention is uniform, and the porosity is 93.7%, aperture 1-3mm it Between, hole rib cage is more sturdy, is conducive to foamed ceramics intensity to improve；Rear foamed ceramics principal crystalline phase is burnt till for carborundum, silicon nitride, Comprcssive strength is 0.27MPa, and after 30 thermal shocks, comprcssive strength is 0.30Mpa, is good high temperature oxidation resistance, good thermal shock, tool There is the foam Si of tridimensional network, high-ratio surface and high heat conductance3N4/ SiC heat absorption ceramic materials, for tower-type solar thermal Power-generating heat-absorption body, solves the deficiency of current solar absorber material resistance to high temperature oxidation difference and thermal shock resistance difference, also for too The research and development of positive energy collecting apparatus provides new approaches.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
A kind of new type solar energy heat absorption ceramic material, is made up of the component comprising following weight percentage： Si3N415wt%, SiC40wt%, andalusite 20wt%, α-Al2O315wt%, Y2O35wt%, Cr2O35wt%, with Si3N4With SiC is base material, with andalusite, α-Al2O3、Y2O3And Cr2O3Phase is combined for additive synthesis high temperature resistant, with polyurethane foam is Presoma, prepares foam Si using Foam dipping method3N4/ SiC heat absorption ceramic materials；Wherein base material Si3N4, SiC, add Plus agent andalusite, α-Al2O3、Y2O3、Cr2O3The powder of mean diameter 1nm is, polyurethane foam precursor is liquid.
A kind of new type solar energy heat absorption ceramic material and preparation method thereof, comprises the steps of：
(1) above-mentioned raw materials are weighed according to proportioning, with dehydrated alcohol as dispersant, ZrO2Ball is ball-milling medium, using cylinder Formula ball mill ball milling mixing 12h under conditions of rotational speed of ball-mill is 120r/min obtains slurry；
(2) it is 1 according to weight ratio by the slurry in step (1) and precursor solution polyurethane foam：5 are mixed and stirred for 10min, then carries out supersound process 1h and is sufficiently mixed uniformly；
(3) mixture in step (2) is placed in hermetic container, is warming up to 150 DEG C；It is incubated under inert gas shielding 1h to crosslinking curing, then vacuum drying；
(4) mixture after solidification drying in step (3) is placed in vacuum sintering funace, in noble gases or vacuum In be heated to 1400 DEG C, pressure be 30Mpa under sinter 6h, be then cooled to 800 DEG C insulation 3h must have tridimensional network Foam Si3N4/ SiC heat absorption ceramic materials.
Embodiment 2
A kind of new type solar energy heat absorption ceramic material, is made up of the component comprising following weight percentage： Si3N440wt%, SiC15wt%, andalusite 15wt%, α-Al2O310wt%, Y2O310wt%, Cr2O310wt%, with Si3N4 It is base material with SiC, with andalusite, α-Al2O3、Y2O3And Cr2O3Phase is combined for additive synthesis high temperature resistant, with polyurethane foam For presoma, foam Si is prepared using Foam dipping method3N4/ SiC heat absorption ceramic materials；Wherein base material Si3N4, SiC, Additive andalusite, α-Al2O3、Y2O3、Cr2O3The powder of mean diameter 100nm is, polyurethane foam precursor is liquid.
A kind of new type solar energy heat absorption ceramic material and preparation method thereof, comprises the steps of：
(1) above-mentioned raw materials are weighed according to proportioning, with dehydrated alcohol as dispersant, ZrO2Ball is ball-milling medium, using cylinder Formula ball mill ball milling mixing 16h under conditions of rotational speed of ball-mill is 140r/min obtains slurry；
(2) it is 1 according to weight ratio by the slurry in step (1) and precursor solution polyurethane foam：100 are mixed and stirred for 30min, then carries out supersound process 12h and is sufficiently mixed uniformly；
(3) mixture in step (2) is placed in hermetic container, is warming up to 300 DEG C；It is incubated under inert gas shielding 6h to crosslinking curing, then vacuum drying；
(4) mixture after solidification drying in step (3) is placed in vacuum sintering funace, in noble gases or vacuum In be heated to 1600 DEG C, pressure be 50Mpa under sinter 10h, be then cooled to 1200 DEG C insulation 5h must have three-dimensional netted knot The foam Si of structure3N4/ SiC heat absorption ceramic materials.
Embodiment 3
A kind of new type solar energy heat absorption ceramic material, is made up of the component comprising following weight percentage： Si3N440wt%, SiC40wt%, andalusite 5wt%, α-Al2O313wt%, Y2O31wt%, Cr2O31wt%, with Si3N4With SiC is base material, with andalusite, α-Al2O3、Y2O3And Cr2O3Phase is combined for additive synthesis high temperature resistant, with polyurethane foam is Presoma, prepares foam Si using Foam dipping method3N4/ SiC heat absorption ceramic materials；Wherein base material Si3N4, SiC, add Plus agent andalusite, α-Al2O3、Y2O3、Cr2O3The powder of mean diameter 50nm is, polyurethane foam precursor is liquid.
A kind of new type solar energy heat absorption ceramic material and preparation method thereof, comprises the steps of：
(1) above-mentioned raw materials are weighed according to proportioning, with dehydrated alcohol as dispersant, ZrO2Ball is ball-milling medium, using cylinder Formula ball mill ball milling mixing 14h under conditions of rotational speed of ball-mill is 130r/min obtains slurry；
(2) it is 1 according to weight ratio by the slurry in step (1) and precursor solution polyurethane foam：50 are mixed and stirred for 20min, then carries out supersound process 6h and is sufficiently mixed uniformly；
(3) mixture in step (2) is placed in hermetic container, is warming up to 200 DEG C；It is incubated under inert gas shielding 4h to crosslinking curing, then vacuum drying；
(4) mixture after solidification drying in step (3) is placed in vacuum sintering funace, in noble gases or vacuum In be heated to 1500 DEG C, pressure be 40Mpa under sinter 8h, be then cooled to 1000 DEG C insulation 4h must have tridimensional network Foam Si3N4/ SiC heat absorption ceramic materials.
Embodiment 4
A kind of new type solar energy heat absorption ceramic material, is made up of the component comprising following weight percentage： Si3N430wt%, SiC40wt%, andalusite 5wt%, α-Al2O35wt%, Y2O310wt%, Cr2O310wt%, with Si3N4With SiC is base material, with andalusite, α-Al2O3、Y2O3And Cr2O3Phase is combined for additive synthesis high temperature resistant, with polyurethane foam is Presoma, prepares foam Si using Foam dipping method3N4/ SiC heat absorption ceramic materials；Wherein base material Si3N4, SiC, add Plus agent andalusite, α-Al2O3、Y2O3、Cr2O3The powder of mean diameter 80nm is, polyurethane foam precursor is liquid.
A kind of new type solar energy heat absorption ceramic material and preparation method thereof, comprises the steps of：
(1) above-mentioned raw materials are weighed according to proportioning, with dehydrated alcohol as dispersant, ZrO2Ball is ball-milling medium, using cylinder Formula ball mill ball milling mixing 16h under conditions of rotational speed of ball-mill is 125r/min obtains slurry；
(2) it is 1 according to weight ratio by the slurry in step (1) and precursor solution polyurethane foam：80 are mixed and stirred for 15min, then carries out supersound process 8h and is sufficiently mixed uniformly；
(3) mixture in step (2) is placed in hermetic container, is warming up to 250 DEG C；It is incubated under inert gas shielding 5h to crosslinking curing, then vacuum drying；
(4) mixture after solidification drying in step (3) is placed in vacuum sintering funace, in noble gases or vacuum In be heated to 1500 DEG C, pressure be 35Mpa under sinter 6h, be then cooled to 1200 DEG C insulation 4h must have tridimensional network Foam Si3N4/ SiC heat absorption ceramic materials.
Embodiment 5
A kind of new type solar energy heat absorption ceramic material, is made up of the component comprising following weight percentage： Si3N430wt%, SiC30wt%, andalusite 10wt%, α-Al2O315wt%, Y2O37wt%, Cr2O38wt%, with Si3N4With SiC is base material, with andalusite, α-Al2O3、Y2O3And Cr2O3Phase is combined for additive synthesis high temperature resistant, with polyurethane foam is Presoma, prepares foam Si using Foam dipping method3N4/ SiC heat absorption ceramic materials；Wherein base material Si3N4, SiC, add Plus agent andalusite, α-Al2O3、Y2O3、Cr2O3The powder of mean diameter 90nm is, polyurethane foam precursor is liquid.
A kind of new type solar energy heat absorption ceramic material and preparation method thereof, comprises the steps of：
(1) above-mentioned raw materials are weighed according to proportioning, with dehydrated alcohol as dispersant, ZrO2Ball is ball-milling medium, using cylinder Formula ball mill ball milling mixing 12h under conditions of rotational speed of ball-mill is 120r/min obtains slurry；
(2) it is 1 according to weight ratio by the slurry in step (1) and precursor solution polyurethane foam：100 are mixed and stirred for 30min, then carries out supersound process 12h and is sufficiently mixed uniformly；
(3) mixture in step (2) is placed in hermetic container, is warming up to 300 DEG C；It is incubated under inert gas shielding 2h to crosslinking curing, then vacuum drying；
(4) mixture after solidification drying in step (3) is placed in vacuum sintering funace, in noble gases or vacuum In be heated to 1500 DEG C, pressure be 30Mpa under sinter 6h, be then cooled to 800 DEG C insulation 3h must have tridimensional network Foam Si3N4/ SiC heat absorption ceramic materials.
Jing is tested, and in above-described embodiment, material pore is uniform, and the porosity is more than 93.7%, aperture between 1-3 mm, hole Rib cage is more sturdy, and comprcssive strength is 0.27-0.30MPa, and after 30 thermal shocks, comprcssive strength is still 0.30Mpa, is high temperature resistance oxygen The good, good thermal shock of the property changed, the foam Si with tridimensional network, high-ratio surface and high heat conductance3N4The ceramic material of/SiC heat absorptions Material, can be used for tower type solar energy thermal power generation absorber.
Although the present invention is described in detail above to have used general explanation and specific embodiment, at this On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore, These modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.

Claims (4)

1. a kind of new type solar energy absorbs heat ceramic material, it is characterised in that be made up of the component comprising following weight percentage： Si3N415-40wt%, SiC 15-40wt%, andalusite 5-20wt%, α-Al2O35-15wt%, Y2O31-10wt%, Cr2O31-10wt%, with Si3N4It is base material with SiC, with andalusite, α-Al2O3、Y2O3And Cr2O3Synthesize resistance to height for additive Temperature combines phase, with polyurethane foam as presoma, prepares foam Si using Foam dipping method3N4The ceramic material of/SiC heat absorptions Material.
2. a kind of new type solar energy as claimed in claim 1 absorbs heat ceramic material, it is characterised in that described base material Si3N4、 SiC, additive andalusite, α-Al2O3、Y2O3、Cr2O3It is the powder of mean diameter 1-100nm.
3. a kind of new type solar energy as claimed in claim 1 absorbs heat ceramic material, it is characterised in that described polyurethane foam Precursor is liquid.
4. a kind of new type solar energy described in any one of claim 1-3 absorbs heat the preparation method of ceramic material, it is characterised in that Comprise the steps of：
(1) above-mentioned raw materials are weighed according to proportioning, with dehydrated alcohol as dispersant, ZrO2Ball is ball-milling medium, using roller milling Machine ball milling mixing 12-16h under conditions of rotational speed of ball-mill is 120-140r/min obtains slurry；
(2) it is 1 according to weight ratio by the slurry in step (1) and precursor solution polyurethane foam：5-100 is mixed and stirred for 10-30min, then carries out supersound process 1-12h and is sufficiently mixed uniformly；
(3) mixture in step (2) is placed in hermetic container, is warming up to 150-300 DEG C；It is incubated under inert gas shielding 1-6h to crosslinking curing, then vacuum drying；
(4) mixture after solidification drying in step (3) is placed in vacuum sintering funace, is added in noble gases or vacuum Heat, to 1400-1600 DEG C, is to sinter 6-10h under 30-50Mpa in pressure, and being then cooled to 800-1200 DEG C of insulation 3-5h must have There is the ceramic absorber material of foam Si3N4/SiC heat absorptions of tridimensional network.
CN201610955106.6A 2016-11-03 2016-11-03 Novel solar heat-absorbing ceramic material and preparation method thereof Withdrawn CN106588029A (en)

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CN107162623A (en) * 2017-05-22 2017-09-15 江苏中路交通科学技术有限公司 A kind of low-cost solar ceramic material applied to solar heat power generation system
CN107162577A (en) * 2017-05-22 2017-09-15 江苏中路交通科学技术有限公司 A kind of solar energy ceramic material applied to tower-type solar thermal power generating system
CN109694252A (en) * 2019-01-12 2019-04-30 西安交通大学 A kind of preparation method of the porous media solar heat absorber of structure gradual change
CN111536830A (en) * 2020-04-22 2020-08-14 西安交通大学 High heat-resistant coil cannon armature structure

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107162623A (en) * 2017-05-22 2017-09-15 江苏中路交通科学技术有限公司 A kind of low-cost solar ceramic material applied to solar heat power generation system
CN107162577A (en) * 2017-05-22 2017-09-15 江苏中路交通科学技术有限公司 A kind of solar energy ceramic material applied to tower-type solar thermal power generating system
CN107162577B (en) * 2017-05-22 2020-05-22 江苏中路交通科学技术有限公司 Solar ceramic material applied to tower type solar thermal power generation system
CN107162623B (en) * 2017-05-22 2020-05-22 江苏中路交通科学技术有限公司 Low-cost solar ceramic material applied to solar thermal power generation system
CN109694252A (en) * 2019-01-12 2019-04-30 西安交通大学 A kind of preparation method of the porous media solar heat absorber of structure gradual change
CN111536830A (en) * 2020-04-22 2020-08-14 西安交通大学 High heat-resistant coil cannon armature structure
CN111536830B (en) * 2020-04-22 2022-06-07 西安交通大学 High heat-resistant coil cannon armature structure

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