CN107189494A - A kind of zirconium silicate wraps up the preparation method of nano carbon microsphere ceramic black material - Google Patents
A kind of zirconium silicate wraps up the preparation method of nano carbon microsphere ceramic black material Download PDFInfo
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- CN107189494A CN107189494A CN201710367527.1A CN201710367527A CN107189494A CN 107189494 A CN107189494 A CN 107189494A CN 201710367527 A CN201710367527 A CN 201710367527A CN 107189494 A CN107189494 A CN 107189494A
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- nano carbon
- black material
- zirconium silicate
- carbon microsphere
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- 239000004005 microsphere Substances 0.000 title claims abstract description 47
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 43
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000000919 ceramic Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 34
- 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 17
- 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
- 235000019441 ethanol Nutrition 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003086 colorant Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 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
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000012670 alkaline solution Substances 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
- 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
- -1 after stirring Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007788 liquid Substances 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
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-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
- 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
- 238000011161 development Methods 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
- 238000002156 mixing 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
- 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
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process 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
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 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 the preparation method that a kind of zirconium silicate wraps up nano carbon microsphere ceramic black material, the nano carbon microsphere prepared using biomass material by hydro-thermal method substitutes traditional carbon source, its hydrophily is added using the rich oxygen-containing functional group in carbon ball surface and residing negative potential state, the dispersiveness of carbon source is enhanced.And by adjusting and controlling the thickness and Electrostatic Absorption ability of carbon ball integument, zirconium silicate presoma is tightly wrapped in carbon ball.Under mineralizer effect, the ceramic black material that zirconium silicate wraps up nano carbon microsphere is made after high-temperature calcination.Pass through the optimization and control to the addition of glucose, hydrothermal temperature, hydro-thermal time and silicon zirconium than, the condition such as presoma mixing time, mineralizer species and consumption selection, calcining system in experimentation, the black material color development of synthesis is pure, uniform particle sizes, performance are stable, it can be used in all kinds of refractory ceramics glaze, with higher economic value.
Description
Technical field
The invention belongs to ceramic pigment technical field, and in particular to a kind of zirconium silicate parcel nano carbon microsphere ceramic black material
Preparation method.
Background technology
Ceramic pigment has far-reaching extensively as a kind of important additive indispensable in china industry, colouring agent
Using.Color generation property, the physical and chemical performance of ceramic pigment directly affect the quality of production of ceramic.At present, ceramic pigment is pressed
Temperature in use can be divided into low form and high temperature modification.High temperature modification colorant temperature in use has widely more than 1000 DEG C
Application prospect, more excellent 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 encapsulation ratio is high, colour generation is pure and stable is developed.
Zirconium silicate wraps up carbon black as the ceramics parcel black material of high temperature modification, has universality to the glaze of different systems,
And will not be influenceed by firing atmosphere, have than traditional spinel-type black material preferably colour stability, widely application.
In the prior art, wrappage --- carbon black is usually to choose acetylene carbon black, high-carbon black pigment etc. as present-color material.These carbon
Black hydrophily is poor, it is impossible to preferably keep dispersiveness in the solution.More importantly they do not have surface-active, subsequently
Parcel be almost a kind of random parcel mechanism.Therefore the encapsulation ratio of existing zirconium silicate parcel black pigment is relatively low, colour generation not
Good, colourity is partially grey（Colorant brightness value L* ＞ 30）.
The content of the invention
The mesh of the present invention is to be to overcome that current zirconium silicate parcel black pigment encapsulation ratio is relatively low, colour generation is not good, and colourity is inclined
There is provided the preparation method that a kind of zirconium silicate wraps up nano carbon microsphere ceramic black material for the deficiency of ash.
The present invention is achieved by the following technical programs：A kind of zirconium silicate wraps up the preparation of nano carbon microsphere ceramic black material
Method, it is characterised in that comprise the following steps：
The first step：Prepare nano carbon microsphere powder
30~60g of biomass material is added in 350ml water, after stirring, solution is poured into reactor, then will be anti-
Answer kettle to be placed in 6~10h of hydro-thermal reaction in 160~200 DEG C of baking oven, then and by reacted solution suction filtration and with absolute ethyl alcohol go
Ionized water cleans three acquisition carbon ball particles, then carbon ball particle is dispersed in 1mol/L alkaline solution stirred at 30~70 DEG C
1~6h is mixed, then cleans with deionized water the pH value of alkaline solution to 7, most afterwards through being dried to obtain nano carbon microsphere powder；
Second step：Prepare carbon ball suspension
Nano carbon microsphere powder is added in the ammoniacal liquor that mass percent concentration is 15~30%, carbon is dispersed under ultrasonication
Ball suspension, the mass percent of the nano carbon microsphere powder and ammoniacal liquor is 1:100~300；
3rd step：Prepare silicon zirconium mixed solution
One kind in tetraethyl orthosilicate, silicon tetrachloride, sodium metasilicate is dissolved in ethanol solution, 1~6h is stirred at room temperature, so
The one kind added in the solution in zirconium oxychloride, zirconyl nitrate, zirconium iso-propoxide, zirconium chloride afterwards, continues to stir 1~6h under normal temperature,
The Zr4+With Si4+Mol ratio be 1:1~2, ethanol in ethanol solution:The volume ratio of water is 1:1；
4th step：Prepare precursor powder
Silicon zirconium mixed solution by volume 3~6 after 3rd step is stirred:1, which is added dropwise to carbon ball made from second step, suspends
In liquid, 2~6h, subsequent 2~6h of cooling and aging are stirred at 40~80 DEG C, the suspension that presoma wraps up carbon ball is obtained, then will
The suspension of presoma parcel carbon ball, which is centrifuged, obtains presoma, after 80 DEG C are dried, you can obtain precursor
End；
5th step：Prepare parcel black material
Precursor powder made from 4th step is further ground, crossed after 60~200 mesh sieves, is added according to 0.5~5% mass ratio
Mineralizer, is well mixed, is subsequently placed into crucible, under argon gas 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 and is heat-treated 1h under oxidizing atmosphere, go by 200min after natural cooling
After uncoated carbon ball powder, you can obtain the nano carbon microsphere ceramic black material of zirconium silicate parcel.
The chromatic value of the nano carbon microsphere ceramic black material of zirconium silicate parcel is made from 5th step：A*=5.1~5.8；
B*=- 0.7~0.1；L*=27~29.5.
Mineralizer in 5th step is one kind in sodium fluoride, magnesium fluoride, lithium fluoride.
The volume of reactor is 400ml in the first step.
The time of ultrasonication is 30min in the second step.
The time is centrifuged in 4th step for 10~20min.
The nano carbon microsphere that the present invention is prepared using biomass material by hydro-thermal method substitutes traditional carbon source, utilizes carbon ball surface
Rich oxygen-containing functional group and residing negative potential state add its hydrophily, enhance the dispersiveness of carbon source.And pass through
Simple soda acid processing is carried out to carbon ball can realize the regulation to integument thickness and control.Carbon ball surface by alkali process
With higher negative potential, the thickness of hydrophilic layer also accordingly increases.
Correspondingly integument thickness can also 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 tightly wrapped in carbon ball.
Under mineralizer effect, the ceramic black material that zirconium silicate wraps up nano carbon microsphere is made after high-temperature calcination.In reality
During testing by the addition of biomass material, hydrothermal temperature, hydro-thermal time and silicon zirconium ratio, presoma mixing time,
The optimization and control of the condition such as mineralizer species and consumption selection, calcining system, obtain that colorant encapsulation ratio is higher, integument more
The coated carbon ball black material better than prior art is presented in densification, colourity.The black material color development of synthesis is pure, uniform particle sizes, property
Can be stable, it can be used in all kinds of refractory ceramics glaze, with higher economic value, therefore with before wide market
Scape.
Brief description of the drawings
Fig. 1 is the SEM photograph of obtained nano carbon microsphere powder in the embodiment of the present invention two；
Fig. 2 is the TEM photos of obtained zirconium silicate parcel nano carbon microsphere ceramic black material in the embodiment of the present invention two；
Fig. 3 is the XRD of obtained zirconium silicate parcel nano carbon microsphere ceramic black material in the embodiment of the present invention two.
Embodiment
Embodiment 1：
38g glucose is dissolved in 350ml deionized water, after stirring, in the reactor that solution is poured into 400ml,
Then hydro-thermal 10h in 160 DEG C of baking oven is placed in, three acquisitions are cleaned by reacted solution suction filtration and with ethanol and deionized water
Carbon ball particle, then carbon ball particle is dispersed in 1mol/L sodium hydroxide solution 2.5h is stirred at 38 DEG C, then use deionization
The pH value of water cleaning sodium hydroxide solution is to 7, most afterwards through being dried to obtain nano carbon microsphere powder；Take the nano carbon microsphere powder prepared
0.0733g is added in the ammoniacal liquor that 14.66g mass fractions are 20%, and ultrasonic 30min is dispersed into carbon ball suspension.Weigh 0.744g
Tetraethyl orthosilicate is dissolved in 20ml ethanol and 20ml water, is stirred at room temperature after 1.5h, is added 0.826g zirconyl nitrates and is continued
1h is stirred under normal temperature.Complete silicon zirconium mixed solution will be stirred to be added dropwise in carbon ball suspension, 2h is stirred at 40 DEG C, with
Cooling and aging 3h obtains the suspension that presoma wraps up carbon ball afterwards.Forerunner's liquid suspension centrifugation 10min is isolated into presoma again
Gel, by 80 DEG C of dryings, obtains precursor powder.Precursor powder crosses 80 mesh sieves, is mixed with 0.004g mineralizers LiF
It is even.It is subsequently placed into crucible, 950 DEG C of calcining 100min, put the colorant powder of calcining after natural cooling in argon gas atmosphere
Enter 900 DEG C of electric furnace（Oxidizing atmosphere）Middle heat treatment 1h, removes uncoated carbon ball, obtains zirconium silicate parcel nano carbon microsphere ceramics
Black material.
Zirconium silicate made from the present embodiment wraps up nano carbon microsphere black material, and colourity is:L*=27.98, a*=5.76, b*
=-0.42.
Embodiment 2：
By 45g starch dissolutions in 350ml deionized water, after stirring, in the reactor that solution is poured into 400ml, connect
And be placed in hydro-thermal 8h in 180 DEG C of baking oven, three acquisition carbon are cleaned by reacted solution suction filtration and with ethanol and deionized water
Ball particle, then carbon ball particle is dispersed in 1mol/L sodium hydroxide solution 4h is stirred at 50 DEG C, then it is clear with deionized water
The pH value of sodium hydroxide solution is washed to 7, most afterwards through being dried to obtain nano carbon microsphere powder；Nano carbon microsphere powder is obtained after drying；Take
The nano carbon microsphere powder 0.0814g prepared is added in the ammoniacal liquor that 16.3g mass fractions are 25%, and ultrasonic 30min is dispersed into carbon
Ball suspension.Weigh 0.625g tetraethyl orthosilicates to be dissolved in 20ml ethanol and 20ml water, be stirred at room temperature after 3h, add
0.644g zirconium oxychlorides continue to stir 3h under normal temperature.Complete silicon zirconium mixed solution will be stirred and be added dropwise to carbon ball suspension
In, 4h is stirred at 60 DEG C, subsequent cooling and aging 4h obtains the suspension that presoma wraps up carbon ball.Forerunner's liquid suspension is centrifuged again
15min isolates aqueous precursor gel, by 80 DEG C of dryings, obtains precursor powder.Precursor powder is crossed after 100 mesh sieves, with
0.0086g mineralizers NaF is well mixed.It is subsequently placed into crucible, 1000 DEG C of calcining 150min, will then be forged in argon gas 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 bag
Wrap up in nano carbon microsphere ceramic black material.
Zirconium silicate made from the present embodiment wraps up nano carbon microsphere black material, and colourity is:L*=29.15, a*=5.58, b*
=-0.63.
Embodiment 3：
56g fructose is dissolved in 350ml deionized water, after stirring, in the reactor that solution is poured into 400ml, connect
And be placed in hydro-thermal 6h in 200 DEG C of baking oven, three acquisition carbon are cleaned by reacted solution suction filtration and with ethanol and deionized water
Ball particle, then carbon ball particle is dispersed in 1mol/L potassium hydroxide solution 6h is stirred at 65 DEG C, then it is clear with deionized water
The pH value of potassium hydroxide solution is washed to 7, most afterwards through being dried to obtain nano carbon microsphere powder；Nano carbon microsphere powder is obtained after drying；Take
The nano carbon microsphere powder 0.9165g prepared is added in the ammoniacal liquor that 18.33g mass fractions are 20%, and ultrasonic 30min is dispersed into
Carbon ball suspension.Weigh 0.833g tetraethyl orthosilicates to be dissolved in 20ml ethanol and 20ml water, be stirred at room temperature after 6h, add
0.862g zirconium oxychlorides continue to stir 5h under normal temperature.Complete silicon zirconium mixed solution will be stirred and be added dropwise to carbon ball suspension
In, 5h is stirred at 70 DEG C, subsequent cooling and aging 6h obtains the suspension that presoma wraps up carbon ball.Again by forerunner's liquid suspension from
Heart 10min isolates aqueous precursor gel, by 80 DEG C of dryings, obtains precursor powder.Precursor powder is crossed after 200 mesh sieves, with
Additional mineralizer MgF20.006g is mixed uniform.It is subsequently placed into crucible, 1050 DEG C of calcining 180min in argon gas atmosphere,
The colorant powder of calcining is then put into 900 DEG C of electric furnace（Oxidizing atmosphere）Middle heat treatment 1h, removes uncoated carbon ball, obtains
Zirconium silicate wraps up nano carbon microsphere ceramic black material.
Zirconium silicate made from the present embodiment wraps up nano carbon microsphere black material, and colourity is:L*=29.35, a*=5.17, b*=
0.04。
Claims (8)
1. a kind of zirconium silicate wraps up the preparation method of nano carbon microsphere ceramic black material, it is characterised in that comprise the following steps：
The first step：Prepare nano carbon microsphere powder
30~60g of biomass material is added in 350ml water, after stirring, solution is poured into reactor, then will be anti-
Answer kettle to be placed in 6~10h of hydro-thermal reaction in 160~200 DEG C of baking oven, then and by reacted solution suction filtration and with absolute ethyl alcohol go
Ionized water cleans three acquisition carbon ball particles, then carbon ball particle is dispersed in 1mol/L alkaline solution stirred at 30~70 DEG C
1~6h is mixed, then cleans with deionized water the pH value of alkaline solution to 7, most afterwards through being dried to obtain nano carbon microsphere powder；
Second step：Prepare carbon ball suspension
Nano carbon microsphere powder is added in the ammoniacal liquor that mass percent concentration is 15~30%, carbon is dispersed under ultrasonication
Ball suspension, the mass percent of the nano carbon microsphere powder and ammoniacal liquor is 1:100~300；
3rd step：Prepare silicon zirconium mixed solution
One kind in tetraethyl orthosilicate, silicon tetrachloride, sodium metasilicate is dissolved in ethanol solution, 1~6h is stirred at room temperature, so
The one kind added in the solution in zirconium oxychloride, zirconyl nitrate, zirconium iso-propoxide, zirconium chloride afterwards, continues to stir 1~6h under normal temperature,
The Zr4+With Si4+Mol ratio be 1:1~2, ethanol in ethanol solution:The volume ratio of water is 1:1；
4th step：Prepare precursor powder
Silicon zirconium mixed solution by volume 3~6 after 3rd step is stirred:1, which is added dropwise to carbon ball made from second step, suspends
In liquid, 2~6h, subsequent 2~6h of cooling and aging are stirred at 40~80 DEG C, the suspension that presoma wraps up carbon ball is obtained, then will
The suspension of presoma parcel carbon ball, which is centrifuged, obtains presoma, after 80 DEG C are dried, you can obtain precursor
End；
5th step：Prepare parcel black material
Precursor powder made from 4th step is further ground, crossed after 60~200 mesh sieves, is added according to 0.5~5% mass ratio
Mineralizer, is well mixed, is subsequently placed into crucible, under argon gas 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 and is heat-treated 1h under oxidizing atmosphere, go by 200min after natural cooling
After uncoated carbon ball powder, you can obtain the nano carbon microsphere ceramic black material of zirconium silicate parcel.
2. zirconium silicate according to claim 1 wraps up the preparation method of nano carbon microsphere ceramic black material, it is characterised in that：Institute
The chromatic value for stating the nano carbon microsphere ceramic black material that zirconium silicate made from the 5th step is wrapped up is：A*=5.1~5.8；B*=- 0.7~
0.1；L*=27~29.5.
3. zirconium silicate according to claim 1 wraps up the preparation method of nano carbon microsphere ceramic black material, it is characterised in that：Institute
It is one kind in sodium fluoride, magnesium fluoride, lithium fluoride to state the mineralizer in the 5th step.
4. zirconium silicate according to claim 1 wraps up the preparation method of nano carbon microsphere ceramic black material, it is characterised in that：Institute
The volume for stating reactor in the first step is 400ml.
5. zirconium silicate according to claim 1 wraps up the preparation method of nano carbon microsphere ceramic black material, it is characterised in that：Institute
The time for stating ultrasonication in second step is 30min.
6. zirconium silicate according to claim 1 wraps up the preparation method of nano carbon microsphere ceramic black material, it is characterised in that：Institute
State and the time is centrifuged in the 4th step for 10~20min.
7. zirconium silicate according to claim 1 wraps up the preparation method of nano carbon microsphere ceramic black material, it is characterised in that：Institute
It is one kind in glucose, fructose, sucrose, starch, cellulose to state biomass material used in the first step.
8. zirconium silicate according to claim 1 wraps up the preparation method of nano carbon microsphere ceramic black material, it is characterised in that：Institute
First step neutral and alkali solution is stated for sodium hydroxide solution or potassium hydroxide solution.
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| CN114162829B (en) * | 2022-01-13 | 2024-03-08 | 武汉市格勒特新材料有限公司 | Preparation method of zirconium silicate nano powder |
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