CN102503563B - Preparation method of praseodymium-doped zirconium silicate based nano pigment - Google Patents
Preparation method of praseodymium-doped zirconium silicate based nano pigment Download PDFInfo
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- CN102503563B CN102503563B CN201110385800.6A CN201110385800A CN102503563B CN 102503563 B CN102503563 B CN 102503563B CN 201110385800 A CN201110385800 A CN 201110385800A CN 102503563 B CN102503563 B CN 102503563B
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Abstract
A preparation method of praseodymium-doped zirconium silicate based nano pigment is characterized by including: firstly, preparing strongly-acidic aqueous solution at mole ratio of Si:Zr:Pr=1:1:0.005-1:1:0.1; and secondly, directly adding the strongly-acidic aqueous solution into a hydrothermal kettle for hydrothermal reaction, obtaining intermediates by scrubbing, drying and grinding of synthetic generated in the hydrothermal reaction, and obtaining praseodymium-doped zirconium silicate based nano pigment powder after high-temperature treatment of the intermediates. Praseodymium-doped zirconium silicate based nano pigment prepared by the hydrothermal synthesis has the advantages of small particle size, regular crystal form, and high purity, dispersity, color rendering capacity and color rendering stability.
Description
Technical field
The present invention relates to a kind of beramic color and preparation method thereof, relate to particularly the preparation method of nano level silicic acid zirconium base beramic color and this nano-ceramic pigment.
Background technology
Beramic color also claims colorant or color material, is coloured pottery finishing material, is the important materials of ceramic coloring and surface decoration, usually is formulated with color base and flux or additive, is powder material.Beramic color comprises on the glaze, under the glaze and glaze and the painted pigment of base substrate.In the Production of Ceramics process, these pigment will stand the calcining of differing temps.Therefore, high-temperature stability and fullness of shade are two important indicators that characterize the high temperature ceramic pigment performance.
The preparation section of existing ceramic pigment generally includes raw material to be mixed, calcining, washing and pulverizing.Calcining is the important procedure of preparation ceramic pigment, can make colorant stable.Because the difference of feedstock property obtains the different of colorant with wishing, the reaction that occurs in the calcination process is different; And calcining temperature is minimum identical with the use temperature of colorant end article usually.Washing is for all soluble substances of Ex-all.If will to present the depth irregular for the surplus material that solubility arranged in the colorant.After the washing it is crushed to needed fineness.Pulverize and to be difficult to use because granularity is uneven when not enough, and may cause and burn till rear maculation shape.
Comparatively general ceramic decoration method is screen printing technique at present, and it requires the colorant granularity to be lower than 45 μ m.Yet the novel decorative method ceramic ink jet printing decoration technique that occurs has in recent years proposed new demand to the performance of beramic color.Inkjet technology is applied to the ceramic decoration means, can realizes the advantages such as noncontact, high output, and can realize automatically control to it by automatic control equipment.In order to guarantee the dispersion stabilization of paint ink, reduce the operating troubless such as plug nozzle, usually require the particle diameter of powder pigment less than 1 μ m, even less than 200nm.The particle diameter of commercially available powder pigment mostly between 3 ~ 15 μ m, can't meet the demands.And for the beramic color that need in the ceramic of high temperature sintering, use, its hardness is had relatively high expectations usually, therefore it is crushed to less than 1 μ m even less than 200nm by lapping mode and is difficult to carry out, and the color development of the pigment after long-time the grinding also can be affected, and therefore the vivid beramic color powder stable, high pure and ultra-fine of a kind of colour generation is provided is the development bottleneck of ceramic ink jet printing decoration technique.
Zirconium silicate is because having high-melting-point, lower thermal conductivity, low-expansion coefficient, good chemical stability and the good characteristics such as ion doping, the zirconium silicate of sintering has fabulous heat-shock resistance simultaneously, so also be the important candidate material of high-temperature structural ceramics, be widely used in zirconium base pigment (red such as praseodymium zirconium Huang, vanadium zirconium indigo plant and ferrozirconium) etc.Zirconium base three look colour generation abilities are strong, colour stability good, just can obtain soft vivid tone in the situation of few add-on.And can make a series of secondary color by these three kinds of colors, so this serial pigment is one of best high temperature ceramic pigment kind of sales volume on the market.The traditional method for preparing above-mentioned zirconium base three look high temperature ceramic pigments is solid reaction process, for example in " Foshan Ceramic " o. 11th disclosed " affecting factor and the control method of zirconium praseodymium yellow quality " in 2004 literary composition, its preparation praseodymium doping zirconium silicate yellow ultramarine (the praseodymium zirconium is yellow) is that ground zirconium white, zirconium silicate, Praseodymium trioxide are mixed in proportion, and directly high temperature sintering, ball milling are processed into powder and obtain.But among traditional solid state reaction preparation method, because calcination temperature is high, hardness is large, and the diameter of particle that obtains like this is excessive.The rear fineness of ball milling processing is inadequate, inhomogeneous, existence tails over, if it is used in the ink-jet ceramic decoration method, and will plug nozzle.
By reducing synthesis temperature to reduce the focus that diameter of particle is various novel methods.Application for a patent for invention publication number CN102173427A discloses a kind of spray ink Printing with the preparation method of yellow zirconium silicate pigment, with gas phase SiO
2, ZrOCl
28H
2O, hydrochloric acid, ammoniacal liquor, Praseodymium trioxide, LiF, to add PEG1000 be raw material, it is characterized in that may further comprise the steps: the 1st step: with hydrochloric acid Praseodymium trioxide is dissolved, be configured to content and be 10% praseodymium chloride solution; The 2nd step: be the ZrOCl of 0.5mol/L with the distilled water configuration concentration
28H
2O solution, in molar ratio: Si4
+/ Zr2
+=1.2: 1, with gas phase SiO
2Join ZrOCl
28H
2In the O solution, then in molar ratio: Pr3
+/ Si4
+=0.0075: 1, PEG/SiO2=0.0015～0.0045: 1 joins ZrOCl with praseodymium chloride solution, PEG1000
28H
2O solution; The 3rd step: slowly drip ammoniacal liquor in the solution that made in the upper step, high-speed stirring simultaneously, the pH value of control solution are between 9～10, then with static 24 hours of the colloid that obtains; The 4th step: with distilled water with the upper step obtain colloid wash to the pH value of filtrate be till 7, then under 100 ℃ condition, dry; The 5th step:. in the powder that obtained in the upper step, in molar ratio: Li
+/ Si4
+=0.3: 1, add the LiF powder, made the medium ball milling 24 hours with dehydrated alcohol, then under 100 ℃ condition, dry; The 6th step: the powder of oven dry was calcined under 900～1000 ℃ condition with the upper step, was incubated 10 minutes, namely obtained the yellow colorant of spray ink Printing.Yet sol-gel method since the molecular level of reaction raw materials mixes and in gelation process the form with netted association exist, can effectively reduce synthesis temperature, still, be unfavorable for the control of particle diameter.And have report to point out that the use of mineralizer can reduce synthesis temperature significantly, but also have research to find that mineralizer plays the effect of inducing nucleation in reaction process, promote on the contrary the growth of crystal to increase, be unfavorable for reducing of diameter of particle.And this process is because the adding of mineralizer makes the zirconium silicate of generation sneak into the mineralizer particle, and the zirconium silicate crystallization phases that obtains is impure.
Hydrothermal synthesis method is because temperature of reaction is low, and crystal particle diameter is little, is widely used in the preparation of nano inorganic material.The hydrothermal method preparation of common high-purity nm silicic acid zirconium powder body early has report, but because the stability of zirconium silicate structure, the energy that water-heat process is difficult to provide enough impels doped element (for example praseodymium element in the praseodymium zirconium Huang) to be doped in the zirconium silicate lattice.
Summary of the invention
Therefore, the inventor recognizes that a kind of colour generation should be provided is vivid stable, high-purity, ultra-fine and be suitable for the beramic color of ceramic ink jet printing decoration technique and be suitable for preparing the method for described pigment.
In this preparation method that a kind of zirconium silicate-based nano dye powder is provided, comprise the strongly acidic aqueous solution of preparing Si:Zr:A=1:1:0.005～1:1:0.1 mol ratio, wherein A can be praseodymium element, v element or ferro element for the colour developing element; Described strongly acidic aqueous solution directly added carries out hydro-thermal reaction in the water heating kettle, the hydro-thermal reaction synthetics through washing, dry, grind to get intermediate product, described intermediate product is carried out high-temperature heat treatment makes A doping silicic acid Zirconium-base nano powder pigment.
The pH value of strongly acidic aqueous solution described in the preparation method of the present invention is preferably less than or equal to 4; More preferably less than or equal to 3.
Hydrothermal temperature described in the preparation method of the present invention is preferably 150～330 ℃; More preferably 180～280 ℃.
Preferably, the high-temperature heat treatment temperature range is preferably 700～1400 ℃; More preferably 800～1300 ℃.
In addition, can adopt method described below to prepare the strongly acidic aqueous solution of Si:Zr:A=1:1:0.005～1:1:0.1 mol ratio among the preparation method of the present invention: the aqueous solution of preparing at first respectively certain density sodium silicate aqueous solution and strongly-acid colour developing elements A, both are mixed into the strongly-acid mixed solution, then in mixed solution, add the zirconium ion aqueous solution of normality.Wherein, all right, with the aqueous solution of sodium silicate aqueous solution and strongly-acid colour developing elements A the time, add strong acid and make the throw out dissolving that occurs in the mixed solution.
The present invention also provides a kind of superfine zirconium silicate base nano dye that makes by preparation method of the present invention, and it comprises that chemical constitution is A
X-ZrSiO
4A doping zirconium silicate crystalline particle, wherein A for the colour developing element; Described particle regular crystal forms, particle diameter are evenly and less than 1 μ m.
Zirconium silicate-based nano dye powder granule provided by the invention is preferably dimensioned to be less than 500nm; More preferably less than 300nm.
Hydrothermal synthesis method of the present invention can be controlled goods diameter of particle, crystal formation, dispersiveness etc. well, and preparation is applicable to the high temperature ceramic pigment of ink-jet ceramic decoration technology.Zirconium silicate-based nano dye by hydrothermal synthesis method of the present invention preparation has that particle diameter is little, regular crystal forms, purity are high, good dispersity, and the characteristics that the colour generation ability is strong, colour stability is good.
Description of drawings
The XRD figure spectrum of the precursor liquid that Fig. 1 illustrates different PH sample of preparation when 260 ℃ of hydrothermal temperatures; (a) PH=0.5 wherein; (b) PH=1.2; (c) PH=2.0; (d) PH=3.0
Fig. 2 is that PH is the TEM figure of the intermediate product for preparing when 260 ℃ of hydrothermal temperatures of (a) precursor;
Fig. 3 is that PH is that the XRD of the sample for preparing under different hydrothermal temperatures of (a) precursor characterizes chart;
Fig. 4 A is the XRD figure spectrum of the praseodymium doping zirconium silicate powder that obtains after 800 ℃ of postheat treatment of intermediate product that 4 different precursor liquids of pH value obtain by 260 ℃ of hydro-thermal reactions;
Fig. 4 B is the XRD figure spectrum of the praseodymium doping zirconium silicate powder that obtains after 1000 ℃ of postheat treatment of intermediate product that 4 different precursor liquids of pH value obtain by 260 ℃ of hydro-thermal reactions;
The XRD figure spectrum of the praseodymium doping zirconium silicate powder that Fig. 4 C intermediate product that to be 4 different precursor liquids of pH value obtain by 260 ℃ of hydro-thermal reactions obtains after 5 hours through 1200 ℃ of postheat treatment;
Fig. 5 is that pH is that the precursor of (c) characterizes by 1000 ℃ of XRD that process resulting samples in the reaction of different hydrothermal temperatures;
Fig. 6 is the praseodymium doping zirconium silicate powder that the described embodiment of Fig. 4 C makes, and two kinds of commercial praseodymium zirconium bloom bodies are at the total reflection light spectrogram of 340 ~ 760nm;
Fig. 7 (A) is that the SEM of the praseodymium doping zirconium silicate powder of embodiment 1 acquisition characterizes;
Fig. 7 (B) is that the SEM of the praseodymium doping zirconium silicate powder of embodiment 2 acquisitions characterizes;
Fig. 7 (C) is that the SEM of the praseodymium doping zirconium silicate powder of embodiment 3 acquisitions characterizes;
Fig. 7 (D) is that the SEM of the praseodymium doping zirconium silicate powder of embodiment 4 acquisitions characterizes;
Fig. 7 (E) is that the SEM of the praseodymium doping zirconium silicate powder of embodiment 5 acquisitions characterizes.
Embodiment
Hydrothermal synthesis method is because temperature of reaction is low, and crystal particle diameter is little, is widely used in the preparation of nano inorganic material.The hydrothermal method preparation of common high-purity nm silicic acid zirconium powder body early has report, but because the stability of zirconium silicate structure, the energy that water-heat process is difficult to provide enough impels the praseodymium element doping in the zirconium silicate lattice.
The invention provides a kind of hydro-thermal reaction synthesis method of the A of preparation doping zirconium silicate-based powder pigment.The first step utilizes hydrothermal method to prepare the nano level intermediate product particles; Second step, this intermediate product of pyroprocessing obtain nano level A doping zirconium silicate-based pigment.Referring now to Figure of description, and further specify with the following embodiments the present invention, should be understood that Figure of description and following embodiment only are used for explanation the present invention, and unrestricted the present invention.In addition, the present invention is the XRD figure spectrum by the D/Max 2550V type X-ray diffractometer test sample of Japanese Rigaku company; Adopt the JEM-2010 type TEM of Japanese JEOL to observe crystallinity, pattern, the particle diameter of sample; Adopt the JSF-6700F type SEM of Japanese Hitachi company to observe pattern and the particle diameter of sample; Adopt the Japanese Konica Minolta CM700D of company type spectrophotometric color measurement instrument to come the visible reflectance spectrum of specimen and the CIE L*a*b* parameter of calculation sample.
The strongly acidic aqueous solution that at first comprises silicon ion, zirconium ion and colour developing elements A by Si:Zr:A=1:1:0.005～1:1:0.1 mol ratio preparation places hydrothermal reaction kettle to carry out hydro-thermal reaction under 180～280 ℃ of temperature of reaction the described aqueous solution.The hydro-thermal reaction time is not particularly limited, and those skilled in the art can determine as the case may be, till generally finishing with reaction.The colour developing elements A can be praseodymium element, v element or ferro element.The below is described in more detail hydro-thermal reaction synthesis method of the present invention as example with the praseodymium element.
As example embodiment, the below describes the preparation of the strongly acidic aqueous solution (precursor liquid) that comprises silicon ion, zirconium ion and praseodymium ion in detail;
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 1.0M.The sodium silicate aqueous solution of preparation 0.2M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.2M
2Solution stirs for some time, gets precursor liquid.Mol ratio Si:Zr:Pr=1:1:0.025 wherein;
Drip NaOH solution and regulate the pH value, make the precursor liquid of different PH, wherein (a) PH=0.5; (b) PH=1.2; (c) PH=2.0; (d) PH=3.0.
Next, pour the precursor liquid that configures into reactor and carry out hydro-thermal reaction, hydrothermal temperature is 260 ℃ in the present embodiment.Then, hydrothermal product is cleaned, for example used deionized water, ethanol, dry, grind and to get the nano level intermediate product particles;
The XRD figure spectrum of the precursor liquid that Fig. 1 illustrates different PH sample of preparation when 260 ℃ of hydrothermal temperatures.(a) PH=0.5 wherein; (b) PH=1.2; (c) PH=2.0; (d) PH=3.0;
From the pH value XRD result (Fig. 1) of different hydro-thermal precursors as can be known, at (c) PH=2.0 and (d) PH=3.0, the principal phase of intermediate product is zirconium white (ZrO
2); When (b) PH=1.2, zirconium silicate is as the principal phase of intermediate product, and ZrO
2Exist on a small quantity as coexisting phase; Has the pure phase zirconium silicate at (a) PH=0.5.Generally speaking, the principal phase of intermediate product was zirconium silicate, is conducive to the formation of zirconium silicate crystallization at low PH of hydro-thermal reaction stage when pH value was low, and pH value when higher the principal phase of intermediate product be zirconium white;
And, in all XRD results, all fail to detect the diffraction peak of praseodymium related compound, namely praseodymium is doped in the intermediate product.And nearly all XRD result presents obvious broadening, and this has shown that the particle that obtains is very little;
Fig. 2 is the precursor of (a) PH=0.5 in the example embodiment of Fig. 1, the TEM of the intermediate product of preparation figure when hydrothermal temperature is 260 ℃.Can learn, prepared intermediate product zirconium silicate crystal particle diameter is very little, and mean value is 20nm.
Fig. 3 is the precursor of (a) PH=0.5 in the example embodiment of Fig. 1, and the XRD of the sample for preparing under different hydrothermal temperatures characterizes chart.Wherein the hydrothermal temperature of (a1) is 200 ℃; (a2) hydrothermal temperature is 230 ℃; (a3) hydrothermal temperature is 260 ℃; Along with the increase of hydrothermal temperature, the peak value of XRD is sharp-pointed as can be seen from Figure 3, and crystallinity strengthens.
Exemplarily illustrate by the high-temperature heat treatment intermediate product with the method for acquisition nano level A doping zirconium silicate-based pigment and the spectrum property of prepared praseodymium doping silicic acid Zirconium-base nano pigment below in conjunction with the form of accompanying drawing with embodiment.High-temperature heat treatment temperature range of the present invention is preferably 700～1300 ℃; More preferably 800～1200 ℃.The high-temperature heat treatment time, there is no particular limitation, and those skilled in the art can determine as the case may be, till generally finishing with reaction.
Fig. 4 A to Fig. 4 C be intermediate product under different temperature and times, the XRD of the powder that obtains through high-temperature heat treatment characterizes.Wherein, the intermediate product that uses during high-temperature heat treatment is 4 different intermediate products that precursor liquid makes of pH value of Fig. 1 example embodiment preparation after hydro-thermal reaction.As previously described, described 4 precursor liquid PH are respectively (a) PH=0.5; (b) PH=1.2; (c) PH=2.0; (d) PH=3.0.And the employed intermediate product of high-temperature heat treatment is the intermediate product that is prepared when hydrothermal temperature is 260 ℃ by 4 kinds of different precursor liquids of this pH value in this example embodiment.
The XRD figure spectrum of the praseodymium doping zirconium silicate powder that Fig. 4 A intermediate product that to be 4 different precursor liquids of pH value obtain by 260 ℃ of hydro-thermal reactions obtains after 5 hours through 800 ℃ of postheat treatment;
Can find out, precursor pH value is several samples of 0.5,1.2,2.0,3.0, obtains intermediate product by hydro-thermal reaction and increases through diameter of particle after 800 ℃ of thermal treatments and the crystallinity enhancing again.
The XRD figure spectrum of the praseodymium doping zirconium silicate powder that Fig. 4 B intermediate product that to be 4 different precursor liquids of pH value obtain by 260 ℃ of hydro-thermal reactions obtains after 5 hours through 1000 ℃ of postheat treatment;
Can find out that thermal treatment temp is that the diffraction peak of 1000 ℃ of powders that obtain is totally similar to the diffraction peak of the powder that obtains 800 ℃ of thermal treatments; But it is narrower that the diffraction peak of the powder that the powder that precursor pH value is 0.5,1.2 intermediate product to be obtained through 1000 ℃ of thermal treatments obtains with respect to 800 ℃ of thermal treatments becomes, and illustrate that crystallinity is stronger, and crystal grain grown up; And being 2.0,3.0 o'clock at pH, all is ZrO at the diffraction peak main peak of 800 ℃ of thermal treatment crystal
2, and in 1000 ℃, be 2.0 o'clock at pH, the ZrO of some
2Be transformed into the zirconium silicate crystal formation.
The XRD figure spectrum of the praseodymium doping zirconium silicate powder that Fig. 4 C intermediate product that to be 4 different precursor liquids of pH value obtain by 260 ℃ of hydro-thermal reactions obtains after 5 hours through 1200 ℃ of postheat treatment;
The principal phase that can find out all samples when thermal treatment temp is 1200 ℃ all is the zirconium silicate crystal formation, and the zirconium white that namely forms in the previous hydrothermal reaction process has been transformed into zirconium silicate in heat treatment process;
Fig. 5 be pH be 2.0 precursor after different hydrothermal temperatures reactions, characterize through 1000 ℃ of XRD that process resulting samples; Wherein the hydrothermal temperature of (a) is 260 ℃; (b) hydrothermal temperature is 230 ℃; (c) hydrothermal temperature is 200 ℃.When hydrothermal temperature is 200 ℃ and 230 ℃, all be zirconium white through the product that obtains after 1000 ℃ of thermal treatments.And under 260 ℃ of hydrothermal conditions, after heat treatment, half zirconium silicate diffraction peak of total amount has appearred accounting for.The raising that is to say hydrothermal temperature can reduce the temperature that subsequent heat treatment generates zirconium silicate effectively, reduces the particle diameter that generates powder.
In order to characterize the quality of Pigment Yellow 73 value, defined spectral differences, namely the upper weight break point wavelength at spectrum is about under the condition of 550nm, the difference of the reflectivity at the reflectivity at 760nm place and 340nm place, spectral differences is larger, and the colour developing of sample is better; Fig. 6 is the described embodiment of Fig. 4 C, and pH value is respectively (a) PH=0.5; (b) PH=1.2; (c) PH=2.0; (d) the praseodymium doping zirconium silicate powder that obtained in 5 hours through 1200 ℃ of postheat treatment of the intermediate product that obtains by 260 ℃ of hydro-thermal reactions of 4 of PH=3.0 precursor liquids, and two kinds of commercial praseodymium zirconium bloom bodies are at the total reflection light spectrogram of 340 ~ 760nm.By spectroscopic analysis, can see, the curvilinear trend of the total reflection spectrum of the sample that different PH makes is fully similar, and reflectivity must to go up weight break point all be about 550nm.The spectral differences of 4 samples that the described embodiment of Fig. 4 C of the present invention makes is respectively (a)=51, (b)=63, (c)=55, (d)=61; And the spectral differences of the yellow sample 1 of commercially available commercial praseodymium zirconium is 65; The spectral differences of the yellow sample 2 of commercial praseodymium zirconium is 68.Namely, the praseodymium zirconium yellow of method preparation disclosed by the invention can reach the color of commercial sample substantially.
Below list again some exemplary embodiments with explanation the present invention.
Embodiment 1:
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 0.5M.The sodium silicate aqueous solution of preparation 0.1M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.1M
2Solution stirs for some time, gets precursor liquid; Wherein, Si:Zr:Pr=1:1:0.025 mol ratio;
Drip NaOH solution and regulate the pH value, make the precursor liquid of PH=0.6;
Pouring the solution that configures into liner is that the stainless steel cauldron of tetrafluoroethylene carries out hydro-thermal reaction under 230 ℃ of temperature;
Then,, wash one time again oven dry with hydrothermal product deionized water wash three times with ethanol.The powder that obtains is ground, put into retort furnace and obtain zirconium silicate powder in 1000 ℃ of lower pyroprocessing;
Fig. 7 (A) characterizes for the SEM of the praseodymium doping zirconium silicate powder that the present embodiment obtains.The described diameter of particle that makes distributes more even, between 80nm ~ 260nm.And from the Electronic Speculum picture, can see clearly crystal edge, therefore, have good monodispersity.
Embodiment 2:
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 0.5M.The sodium silicate aqueous solution of preparation 0.1M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.1M
2Solution stirs for some time, gets precursor liquid; Wherein, Si:Zr:Pr=1:1:0.025 mol ratio;
Drip NaOH solution and regulate the pH value, make the precursor liquid of PH=0.6;
Pouring the solution that configures into liner is that the stainless steel cauldron of tetrafluoroethylene carries out hydro-thermal reaction under 260 ℃ of temperature;
Then,, wash one time again oven dry with hydrothermal product deionized water wash three times with ethanol.The powder that obtains is ground, put into retort furnace and obtain zirconium silicate powder in 1000 ℃ of lower pyroprocessing;
Fig. 7 (B) characterizes for the SEM of the praseodymium doping zirconium silicate powder that the present embodiment obtains.Compare the preparation method of embodiment 1, the hydrothermal temperature of the present embodiment increases to some extent.And the diameter of particle that the prepared powder comparative example 1 of the present embodiment makes is less more even, and its particle size distribution range is about 30nm ~ 100nm, and monocrystalline shows as the regular octahedron of rule.And from the Electronic Speculum picture, can see clearly crystal edge, therefore, have good monodispersity.
Embodiment 3:
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 0.5M.The sodium silicate aqueous solution of preparation 0.1M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.1M
2Solution stirs for some time, gets precursor liquid; Wherein, Si:Zr:Pr=1:1:0.025 mol ratio;
Drip NaOH solution and regulate the pH value, make the precursor liquid of PH=1.0;
Pouring the solution that configures into liner is that the stainless steel cauldron of tetrafluoroethylene carries out hydro-thermal reaction under 260 ℃ of temperature;
Then,, wash one time again oven dry with hydrothermal product deionized water wash three times with ethanol.The powder that obtains is ground, put into retort furnace and obtain zirconium silicate powder in 1200 ℃ of lower pyroprocessing;
Fig. 7 (D) characterizes for the SEM of the praseodymium doping zirconium silicate powder that the present embodiment obtains.From the Electronic Speculum picture, can see clearly crystal edge, therefore, have good monodispersity.Its particle diameter is less than 500nm.
Embodiment 4:
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 0.5M.The sodium silicate aqueous solution of preparation 0.1M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.1M
2Solution stirs for some time, gets precursor liquid; Wherein, Si:Zr:Pr=1:1:0.025 mol ratio;
Drip NaOH solution and regulate the pH value, make the precursor liquid of PH=2.0;
Pouring the solution that configures into liner is that the stainless steel cauldron of tetrafluoroethylene carries out hydro-thermal reaction under 260 ℃ of temperature;
Then,, wash one time again oven dry with hydrothermal product deionized water wash three times with ethanol.The powder that obtains is ground, put into retort furnace and obtain zirconium silicate powder in 1200 ℃ of lower pyroprocessing;
Fig. 7 (E) characterizes for the SEM of the praseodymium doping zirconium silicate powder that the present embodiment obtains.Its particle diameter is less than 300nm.
Embodiment 5:
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 0.5M.The sodium silicate aqueous solution of preparation 0.1M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.1M
2Solution stirs for some time, gets precursor liquid; Wherein, Si:Zr:Pr=1:1:0.025 mol ratio;
Drip NaOH solution and regulate the pH value, make the precursor liquid of PH=3.0;
Pouring the solution that configures into liner is that the stainless steel cauldron of tetrafluoroethylene carries out hydro-thermal reaction under 260 ℃ of temperature;
Then,, wash one time again oven dry with hydrothermal product deionized water wash three times with ethanol.The powder that obtains is ground, put into retort furnace and obtain zirconium silicate powder in 1200 ℃ of lower pyroprocessing;
Fig. 7 (C) characterizes for the SEM of the praseodymium doping zirconium silicate powder that the present embodiment obtains.Its particle diameter is less than 500nm.
Embodiment 6:
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 0.1M.The sodium silicate aqueous solution of preparation 0.1M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.1M
2Solution stirs for some time, gets precursor liquid; Wherein, Si:Zr:Pr=1:1:0.005 mol ratio;
Drip NaOH solution and regulate the pH value, make the precursor liquid of PH=3.5;
Pouring the solution that configures into liner is that the stainless steel cauldron of tetrafluoroethylene carries out hydro-thermal reaction under 260 ℃ of temperature;
Then,, wash one time again oven dry with hydrothermal product deionized water wash three times with ethanol.The powder that obtains is ground, put into retort furnace and obtain praseodymium doping zirconium silicate powder in 1300 ℃ of lower pyroprocessing;
Adopt pattern and the particle diameter of the powder that SEM observation makes, narrower size distribution and monodispersity are preferably arranged.Its particle diameter is less than 1um.
Embodiment 7:
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 1.0M.The sodium silicate aqueous solution of preparation 0.1M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.1M
2Solution stirs for some time, gets precursor liquid; Wherein, Si:Zr:Pr=1:1:0.1 mol ratio;
Drip NaOH solution and regulate the pH value, make the precursor liquid of PH=1.0;
Pouring the solution that configures into liner is that the stainless steel cauldron of tetrafluoroethylene carries out hydro-thermal reaction under 280 ℃ of temperature;
Then,, wash one time again oven dry with hydrothermal product deionized water wash three times with ethanol.The powder that obtains is ground, put into retort furnace and obtain praseodymium doping zirconium silicate powder in 1200 ℃ of lower pyroprocessing;
Adopt pattern and the particle diameter of the powder that SEM observation makes, narrower size distribution and monodispersity are preferably arranged.Its particle diameter is less than 800nm.
Embodiment 8:
With Pr
6O
11Being dissolved in the concentrated nitric acid configuration concentration is the praseodymium ion strongly acidic aqueous solution of 0.5M.The sodium silicate aqueous solution of preparation 0.1M.In above-mentioned sodium silicate aqueous solution, add an amount of praseodymium ion solution, occur adding fast excessive concentrated nitric acid behind the white opacity thing, make muddy thing dissolving.Adding concentration is the ZrOCl of 0.1M
2Solution stirs for some time, gets precursor liquid; Wherein, Si:Zr:Pr=1:1:0.05 mol ratio;
Drip NaOH solution and regulate the pH value, make the precursor liquid of PH=1.0;
Pouring the solution that configures into liner is that the stainless steel cauldron of tetrafluoroethylene carries out hydro-thermal reaction under 260 ℃ of temperature;
Then,, wash one time again oven dry with hydrothermal product deionized water wash three times with ethanol.The powder that obtains is ground, put into retort furnace and obtain praseodymium doping zirconium silicate powder in 1200 ℃ of lower pyroprocessing;
Adopt pattern and the particle diameter of the powder that SEM observation makes, its size distribution is narrower and preferably monodispersity arranged.Its particle diameter is less than 800nm.
Preparation method provided by the invention, the first step utilizes hydrothermal method to prepare nano level intermediate product powder; Second step, this intermediate product of pyroprocessing obtain nano level praseodymium zirconium yellow pigment.Hydrothermal synthesis method has the advantages that temperature of reaction is low, crystal particle diameter is little.Hydrothermal synthesis method of the present invention can be controlled goods diameter of particle, crystal formation, dispersiveness etc. well, and preparation is applicable to the high temperature ceramic pigment of ink-jet ceramic decoration technology.Zirconium silicate-based nano dye by hydrothermal synthesis method of the present invention preparation has that particle diameter is little, regular crystal forms, purity are high, good dispersity, and the characteristics that the colour generation ability is strong, colour stability is good.
Claims (7)
1. the preparation method of a praseodymium doping silicic acid Zirconium-base nano pigment is characterized in that comprising the strongly acidic aqueous solution of preparing Si:Zr:Pr=1:1:0.005～1:1:0.1 mol ratio; Described strongly acidic aqueous solution directly added carries out hydro-thermal reaction in the water heating kettle, the hydro-thermal reaction synthetics through washing, dry, grind to get intermediate product, described intermediate product is carried out high-temperature heat treatment makes praseodymium doping silicic acid Zirconium-base nano powder pigment; The pH value of wherein said strongly acidic aqueous solution is less than or equal to 4.
2. preparation method according to claim 1 is characterized in that, the pH value of described strongly acidic aqueous solution is less than or equal to 3.
3. preparation method according to claim 1 is characterized in that, described hydrothermal temperature is 180～280 ℃.
4. preparation method according to claim 1 is characterized in that, described high-temperature heat treatment temperature range is 800～1300 ℃.
5. preparation method according to claim 1 is characterized in that, described strongly acidic aqueous solution makes by following steps:
The prepare silicon acid sodium aqueous solution;
With Pr
6O
11Be dissolved in concentrated acid preparation praseodymium ion strongly acidic aqueous solution;
Two aqueous solution are become mixed solution, then in mixed solution, add the zirconium ion aqueous solution.
6. preparation method according to claim 5 is characterized in that, by with a certain amount of ZrOCl
2Be dissolved in water and make the described zirconium ion aqueous solution.
7. preparation method according to claim 5 is characterized in that, by adding the throw out dissolving that generates when strong acid mixes sodium silicate aqueous solution and praseodymium ion strongly acidic aqueous solution, then adds the zirconium ion aqueous solution in mixed solution.
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