CN105254337B - It is a kind of that the method that high colour developing zirconium silicate wraps up carbon black colorant is prepared by carbon source of string - Google Patents
It is a kind of that the method that high colour developing zirconium silicate wraps up carbon black colorant is prepared by carbon source of string Download PDFInfo
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- CN105254337B CN105254337B CN201510639378.0A CN201510639378A CN105254337B CN 105254337 B CN105254337 B CN 105254337B CN 201510639378 A CN201510639378 A CN 201510639378A CN 105254337 B CN105254337 B CN 105254337B
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Abstract
The present invention discloses a kind of method that high colour developing zirconium silicate parcel carbon black colorant is prepared by carbon source of string, by using string loose structure in itself and spatial distribution, it can form good scattered in zirconium silicate colloidal sol, the fine and close high colour developing zirconium silicate parcel carbon black colorant of parcel is obtained after high temperature inert atmosphere heat treatment.The parcel black pigment of the present invention have the advantages that pure color, prepare simply, raw material is extensive, cheap and easy to get and environmental protection, can apply to the coloring in ceramic glaze or in base, be suitable for industrialized production.
Description
Technical field
The invention belongs to ceramic pigment technical field, and in particular to one kind prepares high colour developing silicic acid by carbon source of string
The method that zirconium wraps up carbon black colorant.
Background technology
With the continuous improvement of living standards of the people, the demand of ceramic commodity and handicraft rises steadily.Ceramics
Colorant refers to, for the coloured material in ceramic glaze or in base, be dispersed therein in the form of powder or liquid, through high temperature
There is excellent color developing effect after heat treatment.Black ceramic colorant is the important ceramic decoration colorant of a class, because its is sedate big
Gas, dignified simple and honest colouring effect and enjoy liking for people, account for the 25% of the ceramic pigment market share.Current black ceramic
Colorant is mainly the spinel oxides containing cobalt or chromium.Cobalt and chromium are variable valency metal, harmful during precipitation, in system
Environmental pollution is also brought along during standby；Cobalt is expensive simultaneously, limits the production application of black pigment.In recent years
Come, research finds that using zirconium silicate crystal parcel carbon black new black ceramic pigment can be prepared, and on the one hand make use of carbon black
Good color development ability, another aspect zirconium silicate crystal has the characteristic of high-melting-point, high refraction and high stability, can protect charcoal
It is black it is not oxidized in sintering process, resist the erosion of melten glass body and solvent, therefore prepare zirconium silicate parcel carbon black colorant
Developing direction as black pigment.
Current commercial carbon blacks powder is the primary raw material for preparing zirconium silicate occlusion pigment, but the organic functional of carbon blacksurface
Group is less, and the affinity with water or organic solvent is relatively low, while carbon black is easier to produce reunion in preparation process, therefore in silicon
It is dispersed poor in sour zirconium colloidal sol, it is unfavorable for parcel.String is not yet used to prepare zirconium silicate parcel carbon black for carbon source
The report of colorant.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of raw material sources extensively, preparation process green non-pollution, production
Low cost, the method for using string to prepare high colour developing zirconium silicate parcel carbon black colorant for carbon source.
To solve above technical problem, the technical scheme is that：One kind prepares high colour developing by carbon source of string
The method that zirconium silicate wraps up carbon black colorant, it is characterised in that：String is employed for charcoal source, is specifically comprised the following steps：
Step one：String is dried under the conditions of 100~250 DEG C；
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-gel process, the wherein molar concentration of zirconium ion is 0.3~1.5 mol/L, then
By string ultrasonic disperse in above-mentioned zirconium silicate colloidal sol, then be placed in baking oven in 80~120 DEG C drying obtain within 6~24 hours
Zirconium silicate xerogel；
Step 3：Xerogel is warming up to 650~1200 DEG C with 5 DEG C per minute in nitrogen atmosphere and is incubated 1~6 hour,
Furnace cooling；Then in air atmosphere with 5 DEG C per minute be warming up to 700~900 DEG C insulation 1~2 hour remove it is unnecessary not by
The carbon black of parcel, obtains zirconium silicate parcel carbon black colorant.
The string is cotton fiber, bamboo fibre, sisal fiber, rice straw fiber, coir fibre, flax fiber, kapok
One kind in fiber.
The addition of string is the 1~12% of zirconium silicate quality in the step 2.
The zirconium source is one kind in anhydrous zirconium chloride, acetic acid zirconium, zirconium iso-propoxide.
The silicon source is one kind in tetraethyl orthosilicate, silicon tetrachloride, silane coupler.
The mineralizer is one kind in lithium fluoride, magnesium fluoride, sodium fluoride.
The solvent is one kind in ethanol, isopropanol, n-butanol, toluene.
The non-hydrolytic sol-gel process uses a kind of mode of heating in backflow, solvent heat, heating using microwave, flow back,
Solvent thermal process heating-up temperature is 90~120 DEG C, and the 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 uses string for carbon source, with wide material sources, advantage cheap and easy to get, secondly, in string
There is substantial amounts of hole in portion and surface organo-functional group is conducive to adsorbing zirconium silicate colloidal sol.In addition, being existed in itself using string
Spatial distribution in colloidal sol, can realize good to sample scattered under the conditions of surfactant-free, be conducive to preparing height
The colorant of scattered and high encapsulation ratio.The parcel black pigment of the present invention has pure color, to prepare simple, raw material extensive, inexpensive
The advantage being easy to get with environmental protection, can be applied to the coloring in ceramic glaze or in base, therefore with the wide market space.
Brief description of the drawings
Fig. 1 is the SEM photograph of sisal fiber in embodiment 1；
Fig. 2 is the nitrogen adsorption curve of sisal fiber in embodiment 1；
Fig. 3 is that the zirconium silicate prepared by carbon source of cotton fiber, sisal fiber and bamboo fibre wraps up the XRD spectrum of carbon black；
Fig. 4 is the chroma curve of the zirconium silicate occlusion pigment prepared by carbon source of cotton fiber.
Embodiment
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Embodiment 1
By sisal fiber under the conditions of 200 DEG C drying and dehydrating, prepare zirconium silicate colloidal sol using non-hydrolytic sol-gel process,
I.e.：Using mol ratio as ZrCl4:Tetraethyl orthosilicate:LiF=1:1.2:0.3 ratio is by ZrCl4, tetraethyl orthosilicate and LiF be dissolved in it is different
In propyl alcohol, wherein Zr4+Concentration is 1 mol/L, it is well mixed after be heated at reflux that to obtain zirconium silicate within 20 hours molten under the conditions of 110 DEG C
Glue；Then 0.5 g sisal fibers ultrasonic disperse is weighed in 13 mL zirconium silicate colloidal sols, then to be placed in 100 DEG C of dryings 6 in baking oven small
When obtain xerogel；Then 900 DEG C are warming up in nitrogen atmosphere with 5 DEG C per minute be incubated 4 hours, furnace cooling；Then exist
800 DEG C of insulations are warming up to 5 DEG C per minute in air atmosphere and remove unnecessary not wrapped carbon black in 2 hours, obtain zirconium silicate bag
Wrap up in carbon black colorant.
It is observed that sisal fiber is loose structure from Fig. 1；It is big that Fig. 2 BET tests also indicate that sisal hemp surface is present
Micropore is measured, specific surface area is 8.656 m2/ g, therefore be conducive to dipping and the absorption of zirconium silicate colloidal sol；Fig. 3 XRD test results
Show that the zirconium silicate that can prepare pure phase by non-hydrolytic sol-gel process by carbon source of sisal fiber wraps up carbon black colorant,
The chromatic value L*=43.25, a*=1.22, b*=3.84 of the colorant are tested using whiteness instrument.
Embodiment 2
The present embodiment is identical with preparation condition with the preparation method of above-described embodiment 1, and it is the cotton fiber used that it, which is distinguished,
For carbon source, by cotton fiber under the conditions of 150 DEG C drying and dehydrating, using mol ratio as acetic acid zirconium:Silane coupler: MgF=1:1.1:
Acetic acid zirconium, silane coupler and MgF are dissolved in 13 mL alcohol solvents by 0.2 ratio, and the polyethylene for being subsequently placed in 25 mL is
In the reactor of liner, zirconium silicate colloidal sol is obtained after being taken out within 10 hours through 100 DEG C of solvent thermal reactions；Then weigh 0.3 g cottons fine
Ultrasonic disperse is tieed up in 13 mL zirconium silicate colloidal sols, then is placed in 110 DEG C of dryings in baking oven and obtains xerogel within 12 hours.Then in nitrogen
1050 DEG C are warming up to 5 DEG C per minute be incubated 4 hours in gas atmosphere, furnace cooling.Then with 5 DEG C per minute in air atmosphere
It is warming up to 700 DEG C of insulations and removes unnecessary not wrapped carbon black in 2 hours, obtains zirconium silicate parcel carbon black colorant, its XRD test knots
Fruit is as shown in Figure 3.
The chromatic value of the colorant is tested using whiteness instrument, as shown in figure 4, calcining heat is 850 DEG C, 900 DEG C, 950 DEG C,
1000 DEG C, the brightness value L* of occlusion pigment is respectively 41.74,39.42,39.09,41.76,43.08 at 1050 DEG C.
Embodiment 3
The present embodiment is identical with preparation condition with the preparation method of above-described embodiment 1, and it is to employ rice straw fibre that it, which is distinguished,
Tie up as carbon source, using mol ratio as zirconium iso-propoxide:Silicon tetrachloride: NaF=1:1.3:0.25 ratio is by zirconium iso-propoxide, four chlorinations
Silicon and NaF are dissolved in solvent toluene, wherein Zr4+Concentration is 1 mol/L, is obtained within 0.5 hour through 120 DEG C of microwaves in commercially available micro-wave oven
Zirconium silicate colloidal sol, the rice straw fiber for then weighing 0.37g is placed in ultrasound 1 hour in 13 mL zirconium silicate colloidal sol, 90 DEG C in baking oven
Drying obtains xerogel in 20 hours；Then 750 DEG C are warming up in nitrogen atmosphere with 5 DEG C per minute be incubated 2 hours, it is cold with stove
But；Then 750 DEG C of insulations are warming up to 5 DEG C per minute in air atmosphere and remove unnecessary not wrapped carbon black in 2 hours, obtained
Zirconium silicate wraps up carbon black colorant, and the chromatic value L*=38.45, a*=0.58, b*=3.44 of the colorant are tested using whiteness instrument.
Embodiment 4
The present embodiment is identical with preparation condition with the preparation method of above-described embodiment 1, and its difference is to employ bamboo fibre
Ultrasound, which is placed in 13 mL zirconium silicate colloidal sol, for carbon source, i.e. 0.13 g bamboo fibre leaching 1 hour, then is placed in baking oven 100 DEG C does
Obtain xerogel within dry 8 hours；Then 1000 DEG C are warming up in nitrogen atmosphere with 5 DEG C per minute be incubated 6 hours, furnace cooling；
Then 900 DEG C of insulations are warming up to 5 DEG C per minute in air atmosphere and remove unnecessary not wrapped carbon black in 2 hours, obtain silicon
Sour zirconium wraps up carbon black colorant, and its XRD test result is as shown in Figure 3；The chromatic value L*=36.28 of the colorant is tested using whiteness instrument,
A*=0.88, b*=2.20.
Claims (7)
1. a kind of prepare the method that high colour developing zirconium silicate wraps up carbon black colorant by carbon source of string, it is characterised in that：Using
String is charcoal source, is specifically comprised the following steps：
Step one：String is dried under the conditions of 100~250 DEG C；
Step 2：According to mol ratio by zirconium source:Silicon source:Mineralizer=1:1~1.3:0.2~0.3 adds in organic solvent, through non-
Hydrolyzed collosol-gelatin process makes zirconium silicate colloidal sol, and the wherein molar concentration of zirconium ion is 0.3~1.5 mol/L, will then be planted
Fibres ultrasonic disperse in above-mentioned zirconium silicate colloidal sol, then be placed in baking oven in 80~120 DEG C drying obtain silicic acid within 6~24 hours
Zirconium xerogel；
Step 3：Xerogel is warming up to 650~1200 DEG C with 5 DEG C per minute in nitrogen atmosphere and is incubated 1~6 hour, with stove
Cooling；Then 700~900 DEG C of insulations being warming up in air atmosphere with 5 DEG C per minute and removing for 1~2 hour unnecessary be not wrapped
Carbon black, obtain zirconium silicate parcel carbon black colorant；
The string is cotton fiber, bamboo fibre, sisal fiber, rice straw fiber, coir fibre, flax fiber, bombax cotton
In one kind.
2. according to the method described in claim 1, it is characterised in that：The addition of string is zirconium silicate in the step 2
The 1~12% of quality.
3. according to the method described in claim 1, it is characterised in that：The zirconium source is anhydrous zirconium chloride, acetic acid zirconium, zirconium iso-propoxide
In one kind.
4. according to the method described in claim 1, it is characterised in that：The silicon source is tetraethyl orthosilicate, silicon tetrachloride, silane idol
Join one kind in agent.
5. according to the method described in claim 1, it is characterised in that：The mineralizer is in lithium fluoride, magnesium fluoride, sodium fluoride
It is a kind of.
6. according to the method described in claim 1, it is characterised in that：The solvent is in ethanol, isopropanol, n-butanol, toluene
One kind.
7. according to the method described in claim 1, it is characterised in that：The non-hydrolytic sol-gel process is using backflow, solvent
A kind of mode of heating in heat, heating using microwave, backflow, solvent thermal process heating-up temperature are 90~120 DEG C, and the time is 6~24 small
When, microwave heating temperature is 90~120 DEG C, and the time is 0.2~2 hour.
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| 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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| CN102433033B (en) * | 2011-09-02 | 2014-03-05 | 景德镇陶瓷学院 | Method for preparing carbon black inclusion pigment in situ by nonhydrolytic sol-gel process |
| CN103113136B (en) * | 2013-03-07 | 2014-07-02 | 景德镇陶瓷学院 | Preparation method of zirconium silicate wrapped carbon black pigment by microwave synthesis |
| CN103113137B (en) * | 2013-03-07 | 2014-05-07 | 景德镇陶瓷学院 | Method for preparing black pigment by wrapping carbon black with zirconium silicate |
| 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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Address after: 333000 Jiangxi city of Jingdezhen Province Pearl mountain new factory Tao Yang Road 27 Applicant after: JINGDEZHEN CERAMIC INSTITUTE Address before: 333000 Jiangxi city of Jingdezhen Province Pearl mountain new factory Tao Yang Road 27 Applicant before: Jingdezhen College of Ceramic Industry |
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Inventor after: Chen Ting Inventor after: Xu Guirong Inventor after: Liu Jianmin Inventor after: Zhang Xiaojun Inventor after: Feng Guo Inventor after: Jiang Weihui Inventor before: Chen Ting Inventor before: Jiang Weihui Inventor before: Liu Jianmin Inventor before: Zhang Xiaojun Inventor before: Feng Guo |
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