CN105254337A - Method for preparing high-color-developing zirconium-silicate-coated carbon black pigment by taking plant fiber as carbon source - Google Patents
Method for preparing high-color-developing zirconium-silicate-coated carbon black pigment by taking plant fiber as carbon source Download PDFInfo
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- CN105254337A CN105254337A CN201510639378.0A CN201510639378A CN105254337A CN 105254337 A CN105254337 A CN 105254337A CN 201510639378 A CN201510639378 A CN 201510639378A CN 105254337 A CN105254337 A CN 105254337A
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- zirconium silicate
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Abstract
The invention discloses a method for preparing a high-color-developing zirconium-silicate-coated carbon black pigment by taking plant fiber as a carbon source. Good dispersing can be formed in zirconium silicate sol through the porous structure and spatial distribution of the plant fiber, and the high-color-developing zirconium-silicate-coated carbon black pigment which is coated compactly is obtained through hot treatment in a high-temperature inert atmosphere. The coated black pigment has the advantages of being pure in color and luster, easy to prepare, wide in raw materials, low in price, easy to obtain, green and environmentally friendly, can be applied to coloring in glazes or blanks of ceramic products and is suitable for industrialized production.
Description
Technical field
The invention belongs to ceramic pigment technical field, be specifically related to a kind of method taking vegetable fibre as carbon source and prepare high colour developing zirconium silicate parcel carbon black colorant.
Background technology
Along with improving constantly of living standards of the people, the demand of ceramic daily necessities and artwork rises steadily.Ceramic pigment refers to for the coloured material in ceramic glaze or in base, is scattered in wherein with the form of powder or liquid, has excellent color developing effect after high-temperature heat treatment.Black ceramic colorant is the important ceramic decoration colorant of a class, due to its sedate air, dignified simple and honest colouring effect and enjoy liking of people, accounts for 25% of the ceramic pigment market share.Current black ceramic colorant is mainly the spinel oxides containing cobalt or chromium element.Cobalt and chromium are variable valency metal, harmful during precipitation, in preparation process, also can bring environmental pollution; Cobalt is expensive simultaneously, limits the production application of black pigment.In recent years; research finds to use zirconium silicate crystal parcel carbon black can prepare novel black ceramic pigment; make use of the good color development ability of carbon black on the one hand; another aspect zirconium silicate crystal has high-melting-point, height reflects and the characteristic of high stability; the erosion that carbon black is not oxidized in sintering process, resist melten glass body and solvent can be protected, therefore prepare the developing direction that zirconium silicate parcel carbon black colorant becomes black pigment.
Current commercial carbon blacks powder is the main raw material preparing zirconium silicate occlusion pigment, but the organo-functional group of carbon blacksurface is less, lower with the avidity of water or organic solvent, carbon black is easier to produce and reunites in preparation process simultaneously, therefore the dispersiveness in zirconium silicate colloidal sol is poor, is unfavorable for parcel.Not yet have and adopt vegetable fibre to be the report that carbon source prepares zirconium silicate parcel black pigment.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of raw material sources extensively, preparation process green non-pollution, production cost be low, adopt vegetable fibre to be the method that carbon source prepare that high colour developing zirconium silicate wraps up carbon black colorant.
For solving above technical problem, technical scheme of the present invention is: a kind of method taking vegetable fibre as carbon source and prepare high colour developing zirconium silicate parcel carbon black colorant, is characterized in that: have employed vegetable fibre is charcoal source, specifically comprises following steps:
Step one: vegetable fibre is dry under 100 ~ 250 DEG C of conditions;
Step 2: according to mol ratio by zirconium source: silicon source: mineralizer=1:1 ~ 1.3:0.2 ~ 0.3 adds in organic solvent, zirconium silicate colloidal sol is made through non-hydrolytic sol-gelation process, wherein the volumetric molar concentration of zirconium ion is 0.3 ~ 1.5mol/L, subsequently by vegetable fibre ultrasonic disperse in above-mentioned zirconium silicate colloidal sol, then be placed in baking oven and within 6 ~ 24 hours, obtain zirconium silicate xerogel in 80 ~ 120 DEG C of dryings;
Step 3: xerogel is warming up to 650 ~ 1200 DEG C of insulations 1 ~ 6 hour with per minute 5 DEG C in nitrogen atmosphere, furnace cooling; In air atmosphere, be warming up to 700 ~ 900 DEG C of insulations, 1 ~ 2 hour unnecessary not wrapped carbon black of removing with per minute 5 DEG C subsequently, obtain zirconium silicate parcel carbon black colorant.
Described vegetable fibre is the one in cotton fibre, bamboo fibers, sisal fibers, rice straw fiber, coir fibre, flax fiber, bombax cotton.
In described step 2, the add-on of vegetable fibre is 1 ~ 12% of zirconium silicate quality.
Described zirconium source is the one in anhydrous chlorides of rase zirconium, acetic acid zirconium, zirconium iso-propoxide.
Described silicon source is the one in tetraethoxy, silicon tetrachloride, silane coupling agent.
Described mineralizer is the one in lithium fluoride, magnesium fluoride, Sodium Fluoride.
Described solvent is the one in ethanol, Virahol, propyl carbinol, toluene.
Described non-hydrolytic sol-gelation process adopts a kind of type of heating in backflow, solvent thermal, microwave heating, backflow, solvent thermal process Heating temperature are 90 ~ 120 DEG C, time is 6 ~ 24 hours, and microwave heating temperature is 90 ~ 120 DEG C, and the time is 0.2 ~ 2 hour.
The present invention adopts vegetable fibre to be carbon source, has wide material sources, advantage cheap and easy to get, and secondly, vegetable fibre inside there is a large amount of holes and surperficial organo-functional group is conducive to absorption zirconium silicate colloidal sol.In addition, utilize the spatial distribution of vegetable fibre originally in colloidal sol, the dispersion good to sample can be realized under surfactant-free condition, be conducive to the colorant preparing high dispersive and high encapsulation ratio.Parcel black pigment of the present invention has pure color, preparation is simple, raw material is extensive, cheap and easy to get and the advantage of environmental protection, and what can be applicable in ceramic glaze or in base is painted, therefore has the wide market space.
Accompanying drawing explanation
Fig. 1 is the SEM photo of sisal fibers in embodiment 1;
Fig. 2 is the nitrogen adsorption curve of sisal fibers in embodiment 1;
Fig. 3 is the XRD figure spectrum of the zirconium silicate parcel carbon black prepared for carbon source with cotton fibre, sisal fibers and bamboo fibers;
Fig. 4 is take cotton fibre as the chroma curve of zirconium silicate occlusion pigment prepared by carbon source.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Embodiment 1
By sisal fibers drying and dehydrating under 200 DEG C of conditions, using non-hydrolytic sol-gel process to prepare zirconium silicate colloidal sol, that is: is ZrCl with mol ratio
4: the ratio of tetraethoxy: LiF=1:1.2:0.3 is by ZrCl
4, tetraethoxy and LiF be dissolved in Virahol, wherein Zr
4+concentration is 1mol/L, and after mixing, under 110 DEG C of conditions, reflux obtains zirconium silicate colloidal sol in 20 hours; Take 0.5g sisal fibers ultrasonic disperse subsequently in 13mL zirconium silicate colloidal sol, then be placed in baking oven 100 DEG C of dryings and obtain xerogel in 6 hours; 900 DEG C of insulations 4 hours are warming up to per minute 5 DEG C subsequently, furnace cooling in nitrogen atmosphere; Then in air atmosphere, be warming up to 800 DEG C of insulations, 2 hours unnecessary not wrapped carbon blacks of removing with per minute 5 DEG C, obtain zirconium silicate parcel carbon black colorant.
Can observe sisal fibers from Fig. 1 is vesicular structure; The BET test of Fig. 2 also shows that sisal hemp surface exists a large amount of micropore, and specific surface area is 8.656m
2/ g, is therefore conducive to dipping and the absorption of zirconium silicate colloidal sol; The XRD test result of Fig. 3 shows to be that carbon source can prepare the zirconium silicate parcel carbon black colorant of pure phase by non-hydrolytic sol-gel process with sisal fibers, adopts whiteness instrument to test the colourimetric number L*=43.25 of this colorant, a*=1.22, b*=3.84.
Embodiment 2
The present embodiment is identical with preparation condition with the preparation method of above-described embodiment 1, its difference is that the cotton fibre used is carbon source, by cotton fibre drying and dehydrating under 150 DEG C of conditions, take mol ratio as acetic acid zirconium: acetic acid zirconium, silane coupling agent and MgF are dissolved in 13mL alcohol solvent by the ratio of silane coupling agent: MgF=1:1.1:0.2, then the polyethylene being placed in 25mL is the reactor of liner, after 100 DEG C of solvent thermal reactions take out for 10 hours, obtain zirconium silicate colloidal sol; Take 0.3g cotton fibre ultrasonic disperse subsequently in 13mL zirconium silicate colloidal sol, then be placed in baking oven 110 DEG C of dryings and obtain xerogel in 12 hours.1050 DEG C of insulations 4 hours are warming up to per minute 5 DEG C subsequently, furnace cooling in nitrogen atmosphere.Then in air atmosphere, be warming up to 700 DEG C of insulations, 2 hours unnecessary not wrapped carbon blacks of removing with per minute 5 DEG C, obtain zirconium silicate parcel carbon black colorant, its XRD test result as shown in Figure 3.
Adopt whiteness instrument to test the colourimetric number of this colorant, as shown in Figure 4, calcining temperature is 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, and when 1050 DEG C, the brightness value L* of occlusion pigment is respectively 41.74,39.42,39.09,41.76,43.08.
Embodiment 3
The present embodiment is identical with preparation condition with the preparation method of above-described embodiment 1, its difference is that have employed rice straw fiber is carbon source, take mol ratio as zirconium iso-propoxide: zirconium iso-propoxide, silicon tetrachloride and NaF are dissolved in solvent toluene by the ratio of silicon tetrachloride: NaF=1:1.3:0.25, wherein Zr
4+concentration is 1mol/L, and in commercially available microwave oven, 120 DEG C of microwaves obtain zirconium silicate colloidal sol in 0.5 hour, and the rice straw fiber taking 0.37g is subsequently placed in ultrasonic 1 hour of the zirconium silicate colloidal sol of 13mL, and in baking oven, 90 DEG C of dryings obtain xerogel in 20 hours; 750 DEG C of insulations 2 hours are warming up to per minute 5 DEG C subsequently, furnace cooling in nitrogen atmosphere; Then in air atmosphere, be warming up to 750 DEG C of insulations, 2 hours unnecessary not wrapped carbon blacks of removing with per minute 5 DEG C, obtain zirconium silicate parcel carbon black colorant, adopt whiteness instrument to test the colourimetric number L*=38.45 of this colorant, a*=0.58, b*=3.44.
Embodiment 4
The present embodiment is identical with preparation condition with the preparation method of above-described embodiment 1, its difference is that have employed bamboo fibers is carbon source, namely the bamboo fibers leaching of 0.13g is placed in ultrasonic 1 hour of the zirconium silicate colloidal sol of 13mL, then is placed in baking oven 100 DEG C of dryings and obtains xerogel in 8 hours; 1000 DEG C of insulations 6 hours are warming up to per minute 5 DEG C subsequently, furnace cooling in nitrogen atmosphere; Then in air atmosphere, be warming up to 900 DEG C of insulations, 2 hours unnecessary not wrapped carbon blacks of removing with per minute 5 DEG C, obtain zirconium silicate parcel carbon black colorant, its XRD test result as shown in Figure 3; Whiteness instrument is adopted to test the colourimetric number L*=36.28 of this colorant, a*=0.88, b*=2.20.
Claims (8)
1. be the method that carbon source prepares high colour developing zirconium silicate parcel carbon black colorant with vegetable fibre, it is characterized in that: have employed vegetable fibre is charcoal source, specifically comprises following steps:
Step one: vegetable fibre is dry under 100 ~ 250 DEG C of conditions;
Step 2: according to mol ratio by zirconium source: silicon source: mineralizer=1:1 ~ 1.3:0.2 ~ 0.3 adds in organic solvent, zirconium silicate colloidal sol is made through non-hydrolytic sol-gelation process, wherein the volumetric molar concentration of zirconium ion is 0.3 ~ 1.5mol/L, subsequently by vegetable fibre ultrasonic disperse in above-mentioned zirconium silicate colloidal sol, then be placed in baking oven and within 6 ~ 24 hours, obtain zirconium silicate xerogel in 80 ~ 120 DEG C of dryings;
Step 3: xerogel is warming up to 650 ~ 1200 DEG C of insulations 1 ~ 6 hour with per minute 5 DEG C in nitrogen atmosphere, furnace cooling; In air atmosphere, be warming up to 700 ~ 900 DEG C of insulations, 1 ~ 2 hour unnecessary not wrapped carbon black of removing with per minute 5 DEG C subsequently, obtain zirconium silicate parcel carbon black colorant.
2. method according to claim 1, is characterized in that: described vegetable fibre is the one in cotton fibre, bamboo fibers, sisal fibers, rice straw fiber, coir fibre, flax fiber, bombax cotton.
3. method according to claim 1, is characterized in that: in described step 2, the add-on of vegetable fibre is 1 ~ 12% of zirconium silicate quality.
4. method according to claim 1, is characterized in that: described zirconium source is the one in anhydrous chlorides of rase zirconium, acetic acid zirconium, zirconium iso-propoxide.
5. method according to claim 1, is characterized in that: described silicon source is the one in tetraethoxy, silicon tetrachloride, silane coupling agent.
6. method according to claim 1, is characterized in that: described mineralizer is the one in lithium fluoride, magnesium fluoride, Sodium Fluoride.
7. method according to claim 1, is characterized in that: described solvent is the one in ethanol, Virahol, propyl carbinol, toluene.
8. method according to claim 1, it is characterized in that: described non-hydrolytic sol-gelation process adopts a kind of type of heating in backflow, solvent thermal, microwave heating, the Heating temperature of backflow, solvent thermal process is 90 ~ 120 DEG C, time is 6 ~ 24 hours, microwave heating temperature is 90 ~ 120 DEG C, and the time is 0.2 ~ 2 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189494A (en) * | 2017-05-23 | 2017-09-22 | 景德镇陶瓷大学 | A kind of zirconium silicate wraps up the preparation method of nano carbon microsphere ceramic black material |
| CN107312360A (en) * | 2017-06-24 | 2017-11-03 | 姚文澄 | A kind of zirconium silicate wraps up the preparation method of black material |
| CN107936618A (en) * | 2017-11-25 | 2018-04-20 | 景德镇陶瓷大学 | A kind of fused salt auxiliary prepares the method for zirconium silicate parcel carbon black colorant and its obtained product |
| CN109135337A (en) * | 2018-07-18 | 2019-01-04 | 佛山市三水金鹰无机材料有限公司 | A kind of preparation method of Portoro ceramic ink jet colorant |
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| CN103113137A (en) * | 2013-03-07 | 2013-05-22 | 景德镇陶瓷学院 | Method for preparing black pigment by wrapping carbon black with zirconium silicate |
| CN103113136A (en) * | 2013-03-07 | 2013-05-22 | 景德镇陶瓷学院 | Preparation method of zirconium silicate wrapped carbon black pigment by microwave synthesis |
| CN104370500A (en) * | 2014-04-22 | 2015-02-25 | 天津锦美碳材科技发展有限公司 | Active-carbon thermal-insulation material and preparation method thereof |
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| CN101811692A (en) * | 2010-05-05 | 2010-08-25 | 吉林大学 | New method for comprehensive utilization of straw resource |
| CN102433033A (en) * | 2011-09-02 | 2012-05-02 | 景德镇陶瓷学院 | Method for preparing carbon black inclusion pigment in situ by nonhydrolytic sol-gel process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107189494A (en) * | 2017-05-23 | 2017-09-22 | 景德镇陶瓷大学 | A kind of zirconium silicate wraps up the preparation method of nano carbon microsphere ceramic black material |
| CN107189494B (en) * | 2017-05-23 | 2018-11-30 | 景德镇陶瓷大学 | A kind of preparation method of zirconium silicate package nano carbon microsphere ceramic black material |
| CN107312360A (en) * | 2017-06-24 | 2017-11-03 | 姚文澄 | A kind of zirconium silicate wraps up the preparation method of black material |
| CN107936618A (en) * | 2017-11-25 | 2018-04-20 | 景德镇陶瓷大学 | A kind of fused salt auxiliary prepares the method for zirconium silicate parcel carbon black colorant and its obtained product |
| CN109135337A (en) * | 2018-07-18 | 2019-01-04 | 佛山市三水金鹰无机材料有限公司 | A kind of preparation method of Portoro ceramic ink jet colorant |
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