CN107189494B - A kind of preparation method of zirconium silicate package nano carbon microsphere ceramic black material - Google Patents
A kind of preparation method of zirconium silicate package nano carbon microsphere ceramic black material Download PDFInfo
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- CN107189494B CN107189494B CN201710367527.1A CN201710367527A CN107189494B CN 107189494 B CN107189494 B CN 107189494B CN 201710367527 A CN201710367527 A CN 201710367527A CN 107189494 B CN107189494 B CN 107189494B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 46
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 42
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002028 Biomass Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 3
- 239000008103 glucose Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229960004756 ethanol Drugs 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000003086 colorant Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002525 ultrasonication Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims 1
- 229930006000 Sucrose Natural products 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000005720 sucrose Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 230000010148 water-pollination Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000011214 refractory ceramic Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- 239000000049 pigment Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000005538 encapsulation Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000006194 liquid suspension Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0009—Pigments for ceramics
- C09C1/0012—Pigments for ceramics containing zirconium and silicon
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention discloses a kind of preparation method of zirconium silicate package nano carbon microsphere ceramic black material, traditional carbon source is substituted by nano carbon microsphere prepared by hydro-thermal method using biomass material, its hydrophily is increased using the rich oxygen-containing functional group in carbon ball surface and locating negative potential state, enhances the dispersibility of carbon source.And the thickness and Electrostatic Absorption ability for passing through regulation and control carbon ball wrapping layer, make zirconium silicate presoma tightly be wrapped in carbon ball.Under mineralizer effect, the ceramic black material of zirconium silicate package nano carbon microsphere is made after high-temperature calcination.Optimization and control by additional amount, hydrothermal temperature, hydro-thermal time and the silicon zirconium to glucose than, conditions such as presoma mixing time, mineralizer type and dosage selection, calcining system during the experiment, the black material color development of synthesis is pure, uniform particle sizes, performance are stablized, it can be used in all kinds of refractory ceramics glaze, economic value with higher.
Description
Technical field
The invention belongs to ceramic pigment technical fields, and in particular to a kind of zirconium silicate package nano carbon microsphere ceramic black material
Preparation method.
Background technique
Ceramic pigment has far-reaching extensively as a kind of important additive indispensable in china industry, colorant
Using.Color generation property, the physical and chemical performance of ceramic pigment directly affect the quality of production of ceramic.Currently, ceramic pigment is pressed
Low form and high temperature modification can be divided into using temperature.High temperature modification colorant, at 1000 DEG C or more, is had widely using temperature
Application prospect, superior color generation property.But in numerous ceramic pigments, the accounting of low form colorant is significantly larger than high temperature modification color
Material.Therefore the high temperature modification colorant important in inhibiting that exploitation encapsulation ratio is high, colour generation is pure and stable.
Zirconium silicate wraps up ceramics package black material of the carbon black as high temperature modification, has universality to the glaze of different systems,
And will not be influenced by firing atmosphere, there are preferably than traditional spinel-type black material colour stability, widely application.
In the prior art, wrappage --- carbon black is usually to choose acetylene carbon black, high-carbon black pigment etc. to be used as present-color material.These carbon
Black hydrophily is poor, cannot preferably keep dispersibility in the solution.More importantly they do not have surface-active, subsequent
Package be almost a kind of random package mechanism.Therefore the encapsulation ratio of existing zirconium silicate package black pigment is lower, colour generation not
Good, coloration is partially grey（Colorant brightness value L* > 30）.
Summary of the invention
Mesh of the invention is to be to overcome that current zirconium silicate package black pigment encapsulation ratio is lower, colour generation is bad, and coloration is inclined
The deficiency of ash provides a kind of preparation method of zirconium silicate package nano carbon microsphere ceramic black material.
The present invention is achieved by the following technical programs：A kind of system of zirconium silicate package nano carbon microsphere ceramic black material
Preparation Method, it is characterised in that include the following steps：
The first step：Prepare nano carbon microsphere powder
30~60g of biomass material is added in the water of 350ml after mixing evenly to pour into solution in reaction kettle, then
Reaction kettle is placed in 6~10h of hydro-thermal reaction in 160~200 DEG C of baking oven, then the solution after reaction is filtered and uses dehydrated alcohol
Carbon ball particle is obtained three times with deionized water cleaning, then carbon ball particle is dispersed in the alkaline solution of 1mol/L at 30~70 DEG C
1~6h of lower stirring, then the pH value for cleaning alkaline solution with deionized water are most dried to obtain nano carbon microsphere powder to 7 afterwards；
Second step：Prepare carbon ball suspension
Nano carbon microsphere powder is added in the ammonium hydroxide that mass percent concentration is 15~30%, is dispersed under ultrasonication
At carbon ball suspension, the mass percent of the nano carbon microsphere powder and ammonium hydroxide is 1:100~300；
Third step：Prepare silicon zirconium mixed solution
One of ethyl orthosilicate, silicon tetrachloride, sodium metasilicate are dissolved in ethanol solution, it is stirred at room temperature 1~
Then one of zirconium oxychloride, zirconyl nitrate, zirconium iso-propoxide, zirconium chloride is added in 6h in the solution, continue to stir 1 under room temperature
~6h, the Zr4+With Si4+Molar ratio be 1:1~2, ethyl alcohol in ethanol solution:The volume ratio of water is 1:1；
4th step：Prepare precursor powder
Silicon zirconium mixed solution after third step is stirred by volume 3~6:1 is added dropwise to carbon ball made from second step
In suspension, 2~6h, subsequent 2~6h of cooling and aging are stirred at 40~80 DEG C, obtain the suspension of presoma package carbon ball,
It is centrifuged the suspension of presoma package carbon ball to obtain presoma again, after 80 DEG C dry, forerunner can be obtained
Body powder；
5th step：Preparation package black material
Precursor powder made from 4th step is further ground, after crossing 60~200 meshes, according to 0.5~5% mass ratio
Mineralizer is added, is uniformly mixed, is subsequently placed into crucible, under argon atmosphere protection, is warming up to 950~1050 DEG C, calcining 90
Burnt colorant powder is put into 900 DEG C of electric furnace after natural cooling and is heat-treated 1h under oxidizing atmosphere by~200min,
After removing uncoated carbon ball powder, the nano carbon microsphere ceramic black material of zirconium silicate package can be obtained.
The chromatic value of nano carbon microsphere ceramic black material of the package of zirconium silicate made from 5th step is：A*=5.1~5.8；
B*=- 0.7~0.1；L*=27~29.5.
Mineralizer in 5th step is one of sodium fluoride, magnesium fluoride, lithium fluoride.
The volume of reaction kettle is 400ml in the first step.
The time of ultrasonication is 30min in the second step.
It is 10~20min that the time is centrifuged in 4th step.
The present invention substitutes traditional carbon source by nano carbon microsphere prepared by hydro-thermal method using biomass material, utilizes carbon ball surface
Rich oxygen-containing functional group and locating negative potential state increase its hydrophily, enhance the dispersibility of carbon source.And pass through
Simple soda acid is carried out to carbon ball and handles the regulation and control that may be implemented to wrapping layer thickness.Carbon ball surface by alkali process
With higher negative potential, the thickness of hydrophilic layer is also increased accordingly.
Correspondingly wrapping layer thickness also will increase, therefore carbon ball can be protected preferably at high temperature.Pass through carbon ball sheet
Zr has efficiently been adsorbed in the electrostatic adsorption of body4+、Si4+, zirconium silicate presoma is made tightly to be wrapped in carbon ball.
Under mineralizer effect, the ceramic black material of zirconium silicate package nano carbon microsphere is made after high-temperature calcination.In reality
During testing by additional amount, hydrothermal temperature, hydro-thermal time and silicon zirconium ratio to biomass material, presoma mixing time,
The optimization and control of the conditions such as mineralizer type and dosage selection, calcining system, obtain colorant encapsulation ratio is higher, wrapping layer more
The coated carbon ball black material for being better than the prior art is presented in densification, coloration.The black material color development of synthesis is pure, uniform particle sizes, property
It can stablize, can be used in all kinds of refractory ceramics glaze, economic value with higher, therefore before having a vast market
Scape.
Detailed description of the invention
Fig. 1 is the SEM photograph that nano carbon microsphere powder is made in the embodiment of the present invention two；
Fig. 2 is the TEM photo that zirconium silicate is made in the embodiment of the present invention two and wraps up nano carbon microsphere ceramic black material；
Fig. 3 is the XRD diagram that zirconium silicate is made in the embodiment of the present invention two and wraps up nano carbon microsphere ceramic black material.
Specific embodiment
Embodiment 1：
38g glucose is dissolved in the deionized water of 350ml, after mixing evenly, solution is poured into the reaction kettle of 400ml
In, it is then placed in hydro-thermal 10h in 160 DEG C of baking oven, the solution after reaction is filtered and is cleaned three times with ethyl alcohol and deionized water
Carbon ball particle is obtained, then carbon ball particle is dispersed in the sodium hydroxide solution of 1mol/L at 38 DEG C and stirs 2.5h, then is spent
Ionized water cleans the pH value of sodium hydroxide solution to 7, is most dried to obtain nano carbon microsphere powder afterwards；Take the nano carbon microsphere prepared
Powder 0.0733g is added in the ammonium hydroxide that 14.66g mass fraction is 20%, and ultrasonic 30min is dispersed into carbon ball suspension.It weighs
0.744g ethyl orthosilicate is dissolved in 20ml ethyl alcohol and 20ml water, and after 1.5h is stirred at room temperature, 0.826g Nitric Acid Oxidation is added
Zirconium continues to stir 1h under room temperature.Complete silicon zirconium mixed solution will be stirred to be added dropwise in carbon ball suspension, stirred at 40 DEG C
2h is mixed, subsequent cooling and aging 3h obtains the suspension of presoma package carbon ball.Forerunner's liquid suspension centrifugation 10min is isolated again
Aqueous precursor gel obtains precursor powder by 80 DEG C of dryings.Precursor powder crosses 80 meshes, mixed with 0.004g mineralizer LiF
It closes uniform.It is subsequently placed into crucible, 950 DEG C of calcining 100min in argon atmosphere, by the colorant powder of calcining after natural cooling
End is put into 900 DEG C of electric furnace（Oxidizing atmosphere）Middle heat treatment 1h, removes uncoated carbon ball, obtains zirconium silicate package nano carbon microsphere
Ceramic black material.
Zirconium silicate made from the present embodiment wraps up nano carbon microsphere black material, and coloration is:L*=27.98, a*=5.76, b*
=-0.42.
Embodiment 2：
By 45g starch dissolution in the deionized water of 350ml, after mixing evenly, solution is poured into the reaction kettle of 400ml
In, it is then placed in hydro-thermal 8h in 180 DEG C of baking oven, the solution after reaction is filtered and cleaned with ethyl alcohol and deionized water and is obtained three times
Carbon ball particle is obtained, then carbon ball particle is dispersed in the sodium hydroxide solution of 1mol/L at 50 DEG C and stirs 4h, then uses deionization
Water cleans the pH value of sodium hydroxide solution to 7, is most dried to obtain nano carbon microsphere powder afterwards；Nano carbon microsphere powder is obtained after drying
End；The nano carbon microsphere powder 0.0814g prepared is taken to be added in the ammonium hydroxide that 16.3g mass fraction is 25%, ultrasonic 30min points
Dissipate into carbon ball suspension.0.625g ethyl orthosilicate is weighed to be dissolved in 20ml ethyl alcohol and 20ml water, after 3h is stirred at room temperature,
0.644g zirconium oxychloride is added to continue to stir 3h under room temperature.Complete silicon zirconium mixed solution will be stirred and be added dropwise to carbon ball suspension
In liquid, 4h is stirred at 60 DEG C, subsequent cooling and aging 4h obtains the suspension of presoma package carbon ball.Again by forerunner's liquid suspension from
Heart 15min isolates aqueous precursor gel, by 80 DEG C of dryings, obtains precursor powder.After precursor powder sieves with 100 mesh sieve, with
0.0086g mineralizer NaF is uniformly mixed.It is subsequently placed into crucible, 1000 DEG C of calcining 150min, will then forge in argon atmosphere
The colorant powder of burning is put into 900 DEG C of electric furnace（Oxidizing atmosphere）Middle heat treatment 1h, removes uncoated carbon ball, obtains zirconium silicate packet
Wrap up in nano carbon microsphere ceramic black material.
Zirconium silicate made from the present embodiment wraps up nano carbon microsphere black material, and coloration is:L*=29.15, a*=5.58, b*
=-0.63.
Embodiment 3：
56g fructose is dissolved in the deionized water of 350ml, after mixing evenly, solution is poured into the reaction kettle of 400ml
In, it is then placed in hydro-thermal 6h in 200 DEG C of baking oven, the solution after reaction is filtered and cleaned with ethyl alcohol and deionized water and is obtained three times
Carbon ball particle is obtained, then carbon ball particle is dispersed in the potassium hydroxide solution of 1mol/L at 65 DEG C and stirs 6h, then uses deionization
Water cleans the pH value of potassium hydroxide solution to 7, is most dried to obtain nano carbon microsphere powder afterwards；Nano carbon microsphere powder is obtained after drying
End；The nano carbon microsphere powder 0.9165g prepared is taken to be added in the ammonium hydroxide that 18.33g mass fraction is 20%, ultrasonic 30min points
Dissipate into carbon ball suspension.0.833g ethyl orthosilicate is weighed to be dissolved in 20ml ethyl alcohol and 20ml water, after 6h is stirred at room temperature,
0.862g zirconium oxychloride is added to continue to stir 5h under room temperature.Complete silicon zirconium mixed solution will be stirred and be added dropwise to carbon ball suspension
In liquid, 5h is stirred at 70 DEG C, subsequent cooling and aging 6h obtains the suspension of presoma package carbon ball.Again by forerunner's liquid suspension
Centrifugation 10min isolates aqueous precursor gel, by 80 DEG C of dryings, obtains precursor powder.After precursor powder crosses 200 meshes,
With additional mineralizer MgF20.006g is mixed uniformly.It is subsequently placed into crucible, 1050 DEG C of calcinings in argon atmosphere
The colorant powder of calcining is then put into 900 DEG C of electric furnace by 180min（Oxidizing atmosphere）Middle heat treatment 1h, removes uncoated carbon
Ball obtains zirconium silicate package nano carbon microsphere ceramic black material.
Zirconium silicate made from the present embodiment wraps up nano carbon microsphere black material, and coloration is:L*=29.35, a*=5.17, b*=
0.04。
Claims (7)
1. a kind of preparation method of zirconium silicate package nano carbon microsphere ceramic black material, it is characterised in that include the following steps：
The first step：Prepare nano carbon microsphere powder
30~60g of biomass material is added in the water of 350ml after mixing evenly to pour into solution in reaction kettle, it then will be anti-
It answers kettle to be placed in 6~10h of hydro-thermal reaction in 160~200 DEG C of baking oven, then and by the solution suction filtration after reaction and with dehydrated alcohol go
Ionized water cleaning obtains carbon ball particle three times, then carbon ball particle is dispersed in the alkaline solution of 1mol/L and is stirred at 30~70 DEG C
1~6h is mixed, then the pH value for cleaning alkaline solution with deionized water is most dried to obtain nano carbon microsphere powder to 7 afterwards；
Second step：Prepare carbon ball suspension
Nano carbon microsphere powder is added in the ammonium hydroxide that mass percent concentration is 15~30%, is dispersed into carbon under ultrasonication
The mass percent of ball suspension, the nano carbon microsphere powder and ammonium hydroxide is 1:100~300；
Third step：Prepare silicon zirconium mixed solution
One of ethyl orthosilicate, silicon tetrachloride, sodium metasilicate are dissolved in ethanol solution, 1~6h is stirred at room temperature, so
One of zirconium oxychloride, zirconyl nitrate, zirconium iso-propoxide, zirconium chloride is added in the solution afterwards, continues to stir 1~6h under room temperature,
The Zr4+With Si4+Molar ratio be 1:1~2, ethyl alcohol in ethanol solution:The volume ratio of water is 1:1；
4th step：Prepare precursor powder
Silicon zirconium mixed solution after third step is stirred by volume 3~6:1 is added dropwise to the suspension of carbon ball made from second step
In liquid, 2~6h, subsequent 2~6h of cooling and aging are stirred at 40~80 DEG C, obtain the suspension of presoma package carbon ball, then will
The suspension of presoma package carbon ball is centrifuged to obtain presoma, and after 80 DEG C dry, precursor can be obtained
End；
5th step：Preparation package black material
Precursor powder made from 4th step is further ground, after crossing 60~200 meshes, is added according to 0.5~5% mass ratio
Mineralizer is uniformly mixed, is subsequently placed into crucible, under argon atmosphere protection, is warming up to 950~1050 DEG C, and calcining 90~
Burnt colorant powder is put into 900 DEG C of electric furnace after natural cooling and is heat-treated 1h under oxidizing atmosphere, goes by 200min
After uncoated carbon ball powder, the nano carbon microsphere ceramic black material of zirconium silicate package can be obtained；
The chromatic value of nano carbon microsphere ceramic black material of the package of zirconium silicate made from 5th step is：A*=5.1~5.8；b*=-
0.7~0.1；L*=27~29.5.
2. the preparation method of zirconium silicate package nano carbon microsphere ceramic black material according to claim 1, it is characterised in that：Institute
Stating the mineralizer in the 5th step is one of sodium fluoride, magnesium fluoride, lithium fluoride.
3. the preparation method of zirconium silicate package nano carbon microsphere ceramic black material according to claim 1, it is characterised in that：Institute
The volume for stating reaction kettle in the first step is 400ml.
4. the preparation method of zirconium silicate package nano carbon microsphere ceramic black material according to claim 1, it is characterised in that：Institute
The time for stating ultrasonication in second step is 30min.
5. the preparation method of zirconium silicate package nano carbon microsphere ceramic black material according to claim 1, it is characterised in that：Institute
It states and the time is centrifuged in the 4th step as 10~20min.
6. the preparation method of zirconium silicate package nano carbon microsphere ceramic black material according to claim 1, it is characterised in that：Institute
Stating biomass material used in the first step is one of glucose, fructose, sucrose, starch, cellulose.
7. the preparation method of zirconium silicate package nano carbon microsphere ceramic black material according to claim 1, it is characterised in that：Institute
Stating first step neutral and alkali solution is sodium hydroxide solution or potassium hydroxide solution.
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| CN113479895B (en) * | 2021-07-05 | 2022-10-04 | 江西金环颜料有限公司 | Method for preparing superfine zirconium silicate and zirconium silicate-based coating pigment by one-step precipitation method |
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