CN106830917A - The synthesis and the application in solar energy light absorption coating is prepared of cobalt aluminate type blueness nano-ceramic pigment - Google Patents
The synthesis and the application in solar energy light absorption coating is prepared of cobalt aluminate type blueness nano-ceramic pigment Download PDFInfo
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Abstract
The invention discloses a kind of CoAl2O4The synthesis of spinel-type blue ceramic pigment, is that transition metal cobalt salt, Metal aluminum salt are dissolved in distilled water to obtain starting soln；The mixed aqueous solution of chelating agent, esterifying agent is added drop-wise in starting soln, agitating heating obtains sol-gel precursor；To pH=6 ~ 7, continue agitating heating makes it hydrolyze to form sol solution to regulation sol-gel precursor；Sol solution evaporation solvent is obtained into xerogel, then its abundant self-propagating combustion is obtained combustion product with the absolute ethyl alcohol xerogel that ignites, combustion product is finally obtained into CoAl in being heat-treated at 400 ~ 800 DEG C2O4Spinel-type blueness nano-ceramic pigment.The blue ceramic pigment is mixed with organic binder bond, organic solvent, is sprayed to after ball milling dispersion and CoAl is obtained on metal base2O4Spinel-type blue ceramic solar energy light absorption coating, helps to realize application of the colored absorber coatings in domestic solar External building.
Description
Technical field
The present invention relates to a kind of CoAl2O4The synthetic method of spinel-type blue ceramic pigment, more particularly to a kind of colloidal sol-
Gel self-propagating combustion synthesizes CoAl2O4The method of spinel-type blue ceramic pigment, the present invention also relates to this
CoAl2O4Application of the spinel-type blue ceramic pigment in blue solar energy light absorption coating is prepared, belongs to spinel type compound
Preparation and its in the application in solar energy thermal transition field.
Background technology
Can energy crisis and environmental pollution have turned into the key factor of influence socio-economic development, obtain free of contamination energy
Source turns into one of today's society focus of attention.Solar energy is obtained as a kind of inexhaustible clean energy resource
It is increasing to pay attention to.Therefore, current new energy field is turned into using the various new materials of solar energy, new design, new technology
Study hotspot.At present, realize that most universal, most simple, most effective, the most direct mode of solar thermal utilization is by reforming unit
Solar radiant energy is converted into heat energy.Wherein, the core component of solar energy optical and thermal rotary device is that solar selectively absorbs painting
Layer, its efficient selective absorbing refers to that absorber coatings are visible in sunshine and NIR region shows absorptivity higher
（α）, and there is relatively low emissivity in infra-red radiation area（ε）.
At present, the preparation method of solar selectively absorbing coating has a lot, such as magnetron sputtering technique, the side of electrochemistry
Method, sol-gel process, galvanoplastic, chemical transformation, Coating Method etc..Above-mentioned every kind of solar energy coat preparing technology has each
Advantage and disadvantage：The better performances of coating prepared by magnetron sputtering technique, but be used in high-temperature field and need from special metal,
It is relatively costly；Coating resistance to elevated temperatures prepared by electrochemical method is nor highly desirable；Coating heatproof prepared by sol-gel process
Performance is pretty good, but needs to carry out organic matter ablation in process of production, and the adhesive force of coating is also not ideal enough；It is prepared by galvanoplastic
Coating moisture resistance properties it is poor；The heat resistance of chemical transformation prepares coating is preferable, but emissivity is higher.Although coating type
Coatings emissivity is higher, but in the consideration to Solar use integrated cost, coating spraying process be it is most simple, most effective,
The minimum solar energy absorbing coating preparation method of production cost.Patent CN102635964A with percentage by weight as 5 ~ 20% also
Former graphene oxide and 80 ~ 95% ethylene-vinyl acetate copolymers are made into coating solution, are suppressed using scraping embrane method or melting
Method in the minute surface substrate of liquid deposition to infrared external reflection, will successfully be prepared selective absorbing performance sun light absorbs high and be applied
Layer.However, the graphene oxide used by this kind of method, is not easy to reduce production cost.Additionally, coating prepared by this kind of method
It is single black, unsightly, lacks ornamental, it is impossible to realize that solar energy absorbing coating coordinates one with building on color
Cause, so as to have impact on aesthetic property of the solar energy light absorption coating out of doors in Application in Building.Therefore, it is necessary to develop and processability
Stabilization, material are cheap, practical, simple production process colored solar light-absorbing coating, so as to realize that solar energy light absorption is applied
Effect harmonious, that reach beautiful decoration of the layer in following outdoor building application with building on color.
The content of the invention
It is an object of the invention to provide a kind of sol-gel self-propagating method synthesis CoAl2O4Spinel-type blueness nano ceramics
The method of pigment；
It is a further object of the present invention to provide a kind of above-mentioned CoAl2O4Spinel-type blueness nano-ceramic pigment is preparing blue point
Application in spar type ceramic solar light-absorbing coating.
First, CoAl2O4The synthesis of spinel-type blueness nano-ceramic pigment
The present invention is using sol-gel self-propagating method synthesis CoAl2O4Spinel-type blueness nano-ceramic pigment, by transition metal
Cobalt salt, Metal aluminum salt obtain starting soln in being dissolved in distilled water；The mixed aqueous solution of chelating agent, esterifying agent is added drop-wise to starting
In solution, it is heated with stirring to 35 ~ 40 DEG C and obtains sol-gel precursor；Sol-gel precursor to pH value is adjusted with ammoniacal liquor
It is 6 ~ 7, continues to stir under conditions of 35 ~ 40 DEG C, it is hydrolyzed to form sol solution；By sol solution in 120 ~ 130 DEG C of bars
Evaporation solvent obtains xerogel under part, is then ignited xerogel with absolute ethyl alcohol, its abundant self-propagating combustion is obtained combustion product,
Combustion product is finally obtained that component is uniform, purity is high, crystalline structure good in 2 ~ 3 h are heat-treated at 400 ~ 800 DEG C
CoAl2O4Spinel-type blueness nano-ceramic pigment.
The transition metal cobalt salt is halide salt, sulfate, phosphate or the carboxylate of cobalt；Metal aluminum salt be aluminum nitrate,
Aluminum halide, alum, aluminium dihydrogen phosphate.And transition metal cobalt salt and Metal aluminum salt are with 1:2 mol ratio forms starting soln.
The intercalating agent is aminotriacetic acid, glycine, citric acid, tartaric acid, lactic acid, malic acid, gluconic acid, hydroxyl second
Any one of base ethylenediamine triacetic acid, bicine N-；It is preferred that hexamethylene tetraacetic acid, citric acid.The use of chelating agent
Measure is 0.7 ~ 1.6 times of transition metal salt integral molar quantity.
The esterifying agent is ethylene glycol, glycerine, polyethylene glycol 200, Liquid Macrogol, PEG400, poly- second two
One kind in alcohol 600 or methoxypolyethylene glycol；It is preferred that PEG400 is esterifying agent.Esterifying agent is with the mol ratio of chelating agent
0.6:1~1.4:1。
2nd, the preparation of blue spinel type ceramic solar light-absorbing coating
The CoAl of above-mentioned synthesis2O4Spinel-type blueness nano-ceramic pigment mixes with organic binder bond, organic solvent, ball milling point
The solar energy light absorption coating of different colours is formed after scattered 10 ~ 15 h；Solar energy light absorption coating is sprayed into cleaned treatment again
It is 2 ~ 6 μm of blue paste coating that thickness is obtained in metallic substrates, and then paint coatings are placed in 100 ~ 160 DEG C of temperature strip
Solidify 2 ~ 3 h under part, obtain the solar energy light absorption coating of blueness.
CoAl2O4Spinel-type blueness nano-ceramic pigment, organic binder bond, the mass percent of organic solvent are respectively：
CoAl2O4Spinel-type ceramic paint：10 ~ 20%, organic binder bond：20 ~ 40%, organic solvent：40~60%.
Organic binder bond is the epoxy modified silicone of thermohardening type, acryl-modified silicone resin, acrylic acid modified poly-
Urethane or epoxide modified polyurethane.
Organic solvent is at least one in acetone, toluene, dimethylbenzene, ethyl acetate, butyl acetate, ethylene glycol.
Metallic substrates use aluminium sheet or stainless steel plate；Its cleaning treatment is：By metallic substrates respectively in absolute ethyl alcohol and third
It is cleaned by ultrasonic 10 ~ 15 min in ketone, then dries up metallic substrates with nitrogen.
The present invention has following remarkable advantage：
1st, the present invention is using sol-gel self-propagating method synthesis CoAl2O4During spinel-type blueness nano-ceramic pigment,
Chelant ties metal ion simultaneously forms macromolecular network polymer and forms colloidal sol by polymerisation, significantly improves colloidal sol
Homogeneity, stability；Chelating agent participates in redox reaction, so as to drop significantly again as incendiary agent in self-propagating reaction
It is low form crystal needed for crystallization temperature；
2nd, CoAl has successfully been prepared under 400 DEG C of cryogenic conditions2O4Spinel-type phase, so as to effectively improve preparation
CoAl2O4The harsh working condition of spinel-type ceramic paint, has saved energy consumption, reduces production cost；
3rd, the CoAl of present invention synthesis2O4Spinel-type blueness nano-ceramic pigment is used to prepare blue spinel type ceramic solar
Energy light-absorbing coating, enriches the range of application of color in solar energy light absorption coating, helps to realize colored absorber coatings in the future
Application in domestic solar External building；
4th, the present invention can be by changing the species of slaine and intercalating agent, the ratio of fuel agent and slaine, the content of solvent, forging
Temperature, calcination time are burnt, composition, purity, pattern and the particle diameter distribution of synthetic spinel type ceramic paint are controlled well.It is rich
The rich kind of spinel-type ceramic paint；
5th, by CoAl in the present invention2O4Spinel-type blueness nano-ceramic pigment is adopted after mixing with organic binder bond, organic solvent
Blue spinel type ceramic solar light-absorbing coating is prepared with spraying process, the range of application of spinel-type ceramic paint is extended；
6th, preparation method operating procedure of the present invention is simple, continuous controllable, and environmentally safe, equipment requirement is low, with low cost, just
In industrialized production.
Brief description of the drawings
Fig. 1 is the CoAl that embodiment 1 is prepared under the conditions of different calcining heats2O4Spinel-type blueness nano-ceramic pigment
X-ray diffraction spectrogram.
Fig. 2 obtains CoAl for embodiment 1 under the conditions of different calcining heats2O4Spinel-type blueness nano-ceramic pigment
Infrared external reflection spectrogram.
Fig. 3 is based on the CoAl that synthesis is calcined at 800 DEG C in embodiment 12O4Spinel-type blueness nano-ceramic pigment system
The standby reflection spectrogram for obtaining solar energy light absorption coating.
Fig. 4 is based on the CoAl that synthesis is calcined at 800 DEG C in embodiment 22O4Spinel-type blueness nano-ceramic pigment system
The standby reflection spectrogram for obtaining solar energy light absorption coating.
Fig. 5 is based on the CoAl that synthesis is calcined at 800 DEG C in embodiment 32O4Spinel-type blueness nano-ceramic pigment system
The standby reflection spectrogram for obtaining solar energy light absorption coating.
Fig. 6 is based on the CoAl that synthesis is calcined at 800 DEG C in embodiment 42O4Spinel-type blueness nano-ceramic pigment system
The standby reflection spectrogram for obtaining solar energy light absorption coating.
Specific embodiment
Below by specific embodiment to a kind of sol-gel auto-combustion synthesis CoAl of the invention2O4Spinel-type
Blue nano-ceramic pigment and its application in blue solar energy light absorption coating is prepared are described further.
Embodiment 1
（1）CoAl2O4The synthesis of spinel-type blueness nano-ceramic pigment
0.2 mol cabaltous nitrate hexahydrates and 0.4 mol ANN aluminium nitrate nonahydrates are added separately in 400 ml water, under normal temperature condition
Magnetic agitation, obtains initial solution A after slaine is completely dissolved.By 0.6 mol citric acids and 0.6 mol PEG400s
It is added in 200 ml water, completely rear acquisition B solution to be dissolved；B solution is slowly added drop-wise in initial solution A, stirring adds
Heat obtains sol-gel precursor to 35 ~ 40 DEG C；Under agitation sol-gel precursor is adjusted with the ammoniacal liquor of 0.1 mol/L
It is 6 ~ 7 to pH value；Continue to stir under conditions of 35 ~ 40 DEG C, it is hydrolyzed to form sol solution；By sol solution 120 ~
Evaporation solvent obtains xerogel under conditions of 130 DEG C；Xerogel is ignited in atmosphere with a few drop absolute ethyl alcohols, makes xerogel
The self- propagating powder of grey is formed through self-propagating combustion；Finally the self- propagating powder of grey is placed in temperature programming stove, respectively
3 h are calcined at 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, CoAl is prepared2O4Spinel-type blueness nanometer
Ceramic paint.
Fig. 1 is the CoAl that preparation is calcined under the conditions of different calcining heats2O4The X- of spinel-type blueness nano-ceramic pigment
Ray diffraction spectrograms.It will be seen from figure 1 that the CoAl prepared under condition of different temperatures2O4The diffraction maximum of ceramic paint and cube knot
The CoAl of structure2O4（JCPDS 44-0160）Crystallographic plane diffraction peak it is consistent.In addition, with the increase of calcining heat, diffraction peak intensity
Gradually strengthen, half-peak breadth becomes narrow gradually, imply that the crystallinity of crystal gradually increases, strong crystallite dimension gradually increases, therefore, compared with
Contribute to obtain the preferable spinel-type CoAl of crystalline structure under annealing temperature condition high2O4Ceramic paint.The crystallinity of crystal
Better, the symmetry of crystal molecule is higher, and the INFRARED ABSORPTION that crystal molecule is showed is weaker, therefore, contribute to
CoAl2O4Spinel-type blueness nano-ceramic pigment obtains relatively low solar energy transmitted value.
Fig. 2 be different calcining heats under the conditions of prepare CoAl2O4Spinel-type blueness nano-ceramic pigment is in infrared region
The reflectance spectrum in domain and CoAl is calculated by reflectance spectrum2O4The heat emission value of spinel-type blueness nano-ceramic pigment.
As seen from Figure 2, with the increase of calcining heat, CoAl2O4The heat emission value of spinel-type blueness nano-ceramic pigment is gradually
Reduce.Therefore, it can preselect CoAl by determining the heat emission value of pigment2O4Spinel-type blueness nano-ceramic pigment is used for
Prepare spectral selective absorbing coating.
（2）The preparation of blue spinel type ceramic solar light-absorbing coating
Stainless steel base is cleaned by ultrasonic into 15 min in absolute ethyl alcohol and acetone respectively to be decontaminated, the stainless base steel after cleaning
Bottom is dried up with nitrogen.The CoAl of 3 h preparations will be calcined under the conditions of above-mentioned 800 DEG C2O4Spinel-type blueness nano-ceramic pigment, third
The modified organosilicon of olefin(e) acid, dimethylbenzene mix with the mixed solvent of ethyl acetate（The mass percent of wherein each raw material：
CoAl2O4：18%, acryl-modified silicone resin：32%th, the mixed solvent of dimethylbenzene and ethyl acetate：60%, diformazan in mixed solvent
Benzene is 5 with the volume ratio of ethyl acetate:2）, and by mixed system by after 11 h ball millings, obtaining blue solar energy light absorption coating；
Then solar energy light absorption coating sprayed to the blue paste for being made that thickness is 3.6 μm in the stainless steel base of cleaned treatment
, finally be placed in for paint coatings and solidify 3 h under 150 DEG C of temperature conditionss by coating, obtains the solar energy light absorption coating of blueness.Its
Solar absorptance and emissivity are respectively 0.813 and 0.304.The reflectance spectrum of blue solar energy light absorption coating is shown in Fig. 3.
Embodiment 2
（1）CoAl2O4The synthesis of spinel-type blueness nano-ceramic pigment
0.1 mol cobalt chloride hexahydrates and 0.2 mol aluminium chloride are added separately in 200 ml water, magnetic force is stirred under normal temperature condition
Mix, initial solution A is obtained after slaine is completely dissolved；By 0.4 mol ethylenediamine tetra-acetic acids and 0.6 mol PEG400s
It is added in 200 ml water, completely rear acquisition B solution to be dissolved；B solution is slowly dropped in initial solution A again, stirring adds
Heat obtains sol-gel precursor to 35 ~ 40 DEG C；Under agitation sol-gel precursor is adjusted with the ammoniacal liquor of 0.1 mol/L
It is 6 ~ 7 to pH value；Continue to stir under conditions of 35 ~ 40 DEG C, it is hydrolyzed to form sol solution；By sol solution 120 ~
Evaporation solvent obtains xerogel under conditions of 130 DEG C；Xerogel is ignited in atmosphere with a few drop absolute ethyl alcohols, makes xerogel
The self- propagating powder of Dark grey is formed through self-propagating combustion；Finally the self- propagating powder of Dark grey is placed in temperature programming stove,
3 h are calcined at 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C respectively, CoAl is obtained2O4Spinel-type blueness nanometer
Ceramic paint.
Analyze the CoAl synthesized under the conditions of different calcining heats2O4The X-ray diffraction of spinel-type blueness nano-ceramic pigment
Spectrogram and heat emission value, its result are similar to Example 1.
（2）The preparation of blue spinel type ceramic solar light-absorbing coating：By metal aluminium substrate respectively in absolute ethyl alcohol and
It is cleaned by ultrasonic 15 min in acetone to be decontaminated, the aluminium substrate after cleaning is dried up with nitrogen；3 will be calcined under the conditions of above-mentioned 800 DEG C
CoAl prepared by h2O4The mixed solvent of spinel-type blueness nano-ceramic pigment, epoxide modified organosilicon, dimethylbenzene and acetone
Mixing（The mass percent of wherein each raw material：CoAl2O4：20%th, epoxide modified organosilicon：35%th, dimethylbenzene and acetone is mixed
Bonding solvent：45%, dimethylbenzene and the volume ratio of acetone are 5 in mixed solvent:2）, and by mixed system by after 14 h ball millings, obtaining
To blue solar energy light absorption coating；Then solar energy light absorption coating is sprayed to and be made thickness in the metal aluminium substrate of cleaned treatment
The blue paste coating for 5.2 μm is spent, finally paint coatings is placed in and is solidified 3 h under 130 DEG C of temperature conditionss, obtain indigo plant
The solar energy light absorption coating of color.Its solar absorptance and emissivity are respectively 0.821 and 0.320.Blue solar energy light absorption is applied
The reflectance spectrum of layer is shown in Fig. 4.
Embodiment 3
（1）CoAl2O4The synthesis of spinel-type blueness nano-ceramic pigment
By 0.1 mol Cobalt monosulfate heptahydrates and 0.2 mol Monoaluminum monoammonium disulfate Dodecahydrates, it is added separately in 700 ml water, normal temperature
Under the conditions of magnetic agitation, initial solution A is obtained after slaine is completely dissolved.By 0.4 mol citric acids and the poly- second two of 0.4 mol
Alcohol 400 is added in 200 ml water, completely rear acquisition B solution to be dissolved；B solution is slowly added drop-wise in initial solution A, is stirred
Mix and be heated to 35 ~ 40 DEG C, obtain sol-gel precursor；Before adjusting sol-gel with the ammoniacal liquor of 0.1 mol/L under agitation
It is 6 ~ 7 to drive body to pH value；Continue to stir under conditions of 35 ~ 40 DEG C, it is hydrolyzed to form sol solution；Sol solution is existed
Evaporation solvent obtains xerogel under conditions of 120 ~ 130 DEG C；Xerogel is ignited in atmosphere with a few drop absolute ethyl alcohols, makes to do
Gel forms the self- propagating powder of grey through self-propagating combustion；Finally the self- propagating powder of grey is placed in temperature programming stove,
2 h are calcined at 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C respectively, CoAl is prepared2O4Spinel-type is blue
Nano-ceramic pigment.
Analyze the CoAl synthesized under the conditions of different calcining heats2O4The X-ray diffraction of spinel-type blueness nano-ceramic pigment
Spectrogram and heat emission value, its result are similar to Example 1.
（2）The preparation of blue spinel type ceramic solar light-absorbing coating
Stainless steel base is cleaned by ultrasonic into 15 min in absolute ethyl alcohol and acetone respectively to be decontaminated, the stainless base steel after cleaning
Bottom is dried up with nitrogen.The CoAl of 2 h preparations will be calcined under the conditions of above-mentioned 800 DEG C2O4Spinel-type blueness nano-ceramic pigment, ring
The modified polyurethane of oxygen, ethyl acetate mix with the mixed solvent of acetone（The mass percent of wherein each raw material：CoAl2O4：
16%th, epoxide modified polyurethane：36%th, the mixed solvent of ethyl acetate and acetone：48%；Ethyl acetate and third in mixed solvent
The volume ratio of ketone is 5:2）, and by mixed system by after 15 h ball millings, obtaining blue solar energy light absorption coating；Then by the sun
Energy light absorption paint sprays to the blue paste coating for being made that thickness is 5.8 μm in the stainless steel base of cleaned treatment, finally
Paint coatings are placed in and solidify 2 h under 150 DEG C of temperature conditionss, obtain the solar energy light absorption coating of blueness.Its solar absorption
Rate and emissivity are respectively 0.810 and 0.322.The reflectance spectrum of blue solar energy light absorption coating is shown in Fig. 5.
Embodiment 4
（1）CoAl2O4The synthesis of spinel-type blueness nano-ceramic pigment
0.3 mol cobalt acetates and 0.6 mol aluminium chloride are added separately in 600 ml water, magnetic agitation under normal temperature condition is treated
Slaine obtains initial solution A after being completely dissolved.1.0 mol ethylenediamine tetra-acetic acids and 0.8 mol PEG400s are added to
In 400 ml water, completely rear acquisition B solution to be dissolved；B solution is slowly dropped in initial solution A and is heated with stirring to 35 ~ 40
DEG C, obtain sol-gel precursor；Under agitation with the ammoniacal liquor of 0.1 mol/L adjust sol-gel precursor to pH value be 6 ~
7；Continue to stir under conditions of 35 ~ 40 DEG C, it is hydrolyzed to form sol solution；Condition by sol solution at 120 ~ 130 DEG C
Lower evaporation solvent obtains xerogel；Xerogel is ignited in atmosphere with a few drop absolute ethyl alcohols, makes xerogel through self-propagating combustion
Form grayish self- propagating powder；Finally grayish self- propagating powder is placed in temperature programming stove, respectively 400 DEG C,
500 DEG C, 600 DEG C, 700 DEG C, calcine 2 h at 800 DEG C, prepare CoAl2O4Spinel-type blueness nano-ceramic pigment.
Analyze the CoAl synthesized under the conditions of different calcining heats2O4The X-ray diffraction of spinel-type blueness nano-ceramic pigment
Spectrogram and heat emission value, its result are similar to Example 1.
（2）The preparation of blue spinel type ceramic solar light-absorbing coating
Metal aluminium substrate is cleaned by ultrasonic into 15 min in absolute ethyl alcohol and acetone respectively to be decontaminated, the aluminium substrate after cleaning is used
Nitrogen is dried up；The CoAl of 2 h preparations will be calcined under the conditions of above-mentioned 800 DEG C2O4Spinel-type blueness nano-ceramic pigment, acrylic acid
Modified polyurethane, dimethylbenzene mix with the mixed solvent of acetone（The mass percent of wherein each raw material：CoAl2O4：17%, third
The modified polyurethane of olefin(e) acid：33%th, the mixed solvent of dimethylbenzene and acetone：50%；The volume of dimethylbenzene and acetone in mixed solvent
Than being 5:1）, and by mixed system by after 14 h ball millings, obtaining blue solar energy light absorption coating；Then solar energy light absorption is applied
Material sprays to the blue paste coating for being made that thickness is 4.6 μm in the metal aluminium substrate of cleaned treatment, finally applies coating
It is placed under 150 DEG C of temperature conditionss and solidifies 2 h, obtains the solar energy light absorption coating of blueness.Its solar absorptance and transmitting
Rate is respectively 0.817 and 0.331.The reflectance spectrum of blue solar energy light absorption coating is shown in Fig. 6.
Claims (10)
1. sol-gel auto-combustion synthesizes CoAl2O4The method of spinel-type blue ceramic pigment, by transition metals cobalt
Salt, Metal aluminum salt obtain starting soln in being dissolved in distilled water；The mixed aqueous solution of chelating agent, esterifying agent is added drop-wise to starting molten
In liquid, it is heated with stirring to 35 ~ 40 DEG C and obtains sol-gel precursor；It is 6 to adjust sol-gel precursor to pH value with ammoniacal liquor
~ 7, continue to stir under conditions of 35 ~ 40 DEG C, it is hydrolyzed to form sol solution；By sol solution under the conditions of 120 ~ 130 DEG C
Evaporation solvent obtains xerogel, is then ignited xerogel with absolute ethyl alcohol, its abundant self-propagating combustion is obtained combustion product, finally
By combustion product in 2 ~ 3 h are heat-treated at 400 ~ 800 DEG C, the CoAl that component is uniform, purity is high, crystalline structure is good is obtained2O4Point
Spar type blueness nano-ceramic pigment.
2. sol-gel auto-combustion as claimed in claim 1 synthesizes CoAl2O4The side of spinel-type blue ceramic pigment
Method, it is characterised in that：The transition metal cobalt salt is halide salt, sulfate, phosphate, the carboxylate of cobalt；The Metal aluminum salt
It is aluminum nitrate, aluminum halide, alum, aluminium dihydrogen phosphate；And transition metal cobalt salt and Metal aluminum salt with mol ratio be 1:2 form
Starting soln.
3. sol-gel auto-combustion as claimed in claim 1 synthesizes CoAl2O4The side of spinel-type blue ceramic pigment
Method, it is characterised in that：The intercalating agent be hexamethylene tetraacetic acid, aminotriacetic acid, glycine, citric acid, tartaric acid, lactic acid,
Any one of malic acid, gluconic acid, hydroxyethylethylene diamine tri-acetic acid, bicine N-；The consumption of chelating agent is
0.7 ~ 1.6 times of transition metal cobalt salt and Metal aluminum salt integral molar quantity.
4. sol-gel auto-combustion as claimed in claim 1 synthesizes CoAl2O4The side of spinel-type blue ceramic pigment
Method, it is characterised in that：The esterifying agent be ethylene glycol, glycerine, polyethylene glycol 200, Liquid Macrogol, PEG400,
One kind in Macrogol 600 or methoxypolyethylene glycol.
5. sol-gel auto-combustion as claimed in claim 1 synthesizes CoAl2O4The side of spinel-type blue ceramic pigment
Method, it is characterised in that：The esterifying agent is 0.6 with the mol ratio of chelating agent:1~1.4:1.
6. sol-gel self-propagating method as claimed in claim 1 synthesizes CoAl2O4Spinel-type blueness nano-ceramic pigment is used for
Prepare blue spinel type ceramic solar light-absorbing coating, it is characterised in that：By CoAl2O4Spinel-type blueness nano ceramics face
Material mixes with organic binder bond, organic solvent, and ball milling forms blue solar energy light absorption coating after disperseing 10 ~ 15 h；Again will too
Positive energy light absorption paint sprays to the blue paste coating for obtaining that thickness is for 2 ~ 6 μm in the metallic substrates of cleaned treatment, then will
Paint coatings solidify 2 ~ 3 h under being placed in 100 ~ 160 DEG C of temperature conditionss, obtain the solar energy light absorption coating of blueness.
7. CoAl as claimed in claim 62O4Spinel-type blueness nano-ceramic pigment is used to prepare blue spinel type ceramics too
Positive energy light-absorbing coating, it is characterised in that：CoAl2O4Spinel-type blueness nano-ceramic pigment, organic binder bond, organic solvent
Mass percent is respectively：Spinel type nanometer ceramic paint：10 ~ 20%, organic binder bond：20 ~ 40%, organic solvent：40~
60%。
8. CoAl as claimed in claims 6 or 72O4Spinel-type blueness nano-ceramic pigment is used to prepare blue spinel type pottery
Porcelain solar energy light absorption coating, it is characterised in that：The organic binder bond is the epoxy modified silicone of thermohardening type, acrylic acid changes
Property organosilicon, acrylic acid modified polyurethane or epoxide modified polyurethane.
9. CoAl as claimed in claims 6 or 72O4Spinel-type blueness nano-ceramic pigment is used to prepare blue spinel type pottery
Porcelain solar energy light absorption coating, it is characterised in that：The solvent is acetone, toluene, dimethylbenzene, ethyl acetate, butyl acetate, second two
At least one in alcohol.
10. the CoAl as described in claim 6 or 72O4Spinel-type blueness nano-ceramic pigment is used to prepare blue spinel type
Ceramic solar light-absorbing coating, it is characterised in that：The cleaning treatment of the metallic substrates is：By metallic substrates respectively in anhydrous second
It is cleaned by ultrasonic 10 ~ 15 min in alcohol and acetone, then dries up metallic substrates with nitrogen.
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| CN107057408A (en) * | 2017-06-22 | 2017-08-18 | 中国科学院兰州化学物理研究所 | Regulate and control the method for cobalt blue/tectosilicate hybrid pigment color using metal ion mixing |
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| CN107057408A (en) * | 2017-06-22 | 2017-08-18 | 中国科学院兰州化学物理研究所 | Regulate and control the method for cobalt blue/tectosilicate hybrid pigment color using metal ion mixing |
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| CN108359270A (en) * | 2018-02-13 | 2018-08-03 | 华北水利水电大学 | Ultra-fine Preen nono ceramic paint of spinel-type and preparation method thereof |
| CN109385627A (en) * | 2018-12-07 | 2019-02-26 | 郴州市泰益表面涂层技术有限公司 | Suitable for micro- stomata film of high temperature solar selectively and preparation method thereof |
| CN110028811A (en) * | 2019-04-25 | 2019-07-19 | 山东国瓷康立泰新材料科技有限公司 | A kind of high near infrared reflectivity blue pigment and preparation method thereof |
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| ES2802419A1 (en) * | 2019-07-11 | 2021-01-19 | Consejo Superior Investigacion | Catalyst for soot combustion (Machine-translation by Google Translate, not legally binding) |
| CN112443991A (en) * | 2019-08-28 | 2021-03-05 | 香港科技大学 | Selective solar energy absorbing coating processed based on solution method and preparation method thereof |
| CN110655094A (en) * | 2019-11-08 | 2020-01-07 | 吉林大学 | Method for preparing cobalt aluminate pigment with spinel structure by solution combustion method |
| CN112521143A (en) * | 2020-12-09 | 2021-03-19 | 江苏大学镇江流体工程装备技术研究院 | Spinel-type PbAl2O4Preparation method of ferroelectric ceramic powder |
| CN113292086A (en) * | 2021-07-06 | 2021-08-24 | 浙江工业大学 | CoAl2O4Nano powder, preparation method and application |
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Effective date of registration: 20171107 Address after: 410100 Hunan province Changsha Longhua road Changsha County State Grid Hunan electric power company disaster prevention and Mitigation Center Applicant after: State Grid Hunan Electric Power Company prevents and reduces natural disasters center Applicant after: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Address before: Chengguan District of Gansu city of Lanzhou province Tianshui road 730000 No. 18 Applicant before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences |
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