CN102503563A - 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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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 the preparation method of nano level silicic acid zirconium base beramic color and this nano-ceramic pigment particularly.
Background technology
Beramic color is also claimed colorant or color material, is that coloured pottery is used 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, glaze following 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 pyroceramic pigment performance.
The preparation section of existing ceramic pigment generally includes raw materials mix, calcining, washing and pulverizing.Calcining is the important procedure of preparation ceramic pigment, can make colorant stable.Because of the difference of feedstock property obtains the different of colorant with hoping, the reaction that takes place 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.Irregular in the colorant if the surplus material that solubility arranged will present the depth.After the washing it is crushed to needed fineness.Pulverize and to be difficult to use because of granularity is uneven when not enough, and possibly cause and burn till back maculation shape.
Comparatively general ceramic decoration method is a 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 advantages such as noncontact, high output, and can realize control automatically to it through automatic control equipment.In order to guarantee the dispersion stabilization of paint ink, reduce operating troubless such as plug nozzle, the particle diameter that requires the pigment powder usually is less than 1 μ m, even less than 200nm.The particle diameter of commercially available pigment powder 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 through 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 of having HMP, lower thermal conductivity, low-expansion coefficient, excellent chemical stability and good characteristics such as ion doping property; The agglomerating zirconium silicate 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 (for example praseodymium zirconium Huang, vanadium zirconium indigo plant and ferrozirconium are red) etc.Zirconium base three look colour generation abilities are strong, colour stability good, under the situation of few add-on, just can obtain soft vivid tone.And can make a series of secondary color through these three kinds of colors, so this serial pigment is one of best pyroceramic pigment variety of sales volume on the market.The traditional method for preparing above-mentioned zirconium base three look pyroceramic pigment is a solid reaction process; For example in " Foshan pottery " o. 11th disclosed " influencing the factor and the control method of zirconium praseodymium yellow quality " literary composition in 2004; Its preparation praseodymium doping zirconium silicate yellow ultramarine (the praseodymium zirconium is yellow) is with ground zirconium white, zirconium silicate, Praseodymium trioxide proportional mixing, and directly high temperature sintering, ball milling are processed into powder and obtain.But among the conventional solid state reaction preparation method, because calcination temperature is high, hardness is big, and the diameter of particle that obtains like this is excessive.Ball milling processing back fineness is not enough, inhomogeneous, existence tails over, if it is used in the ink-jet ceramic decoration method, and will plug nozzle.
Through 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 the preparation method of a kind of spray ink Printing with yellow zirconium silicate colorant, 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: use the ZrOCl of zero(ppm) water configuration concentration as 0.5mol/L
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: slow dropping ammonia in the solution that made in lasted step, high-speed stirring simultaneously, the pH value of controlling solution are between 9～10, then with static 24 hours of the colloid that obtains; The 4th step: use zero(ppm) water will go up the step obtain colloid wash to pH value of filtrate be till 7, under 100 ℃ condition, dry then; The 5th step:. go on foot in the powder that obtains, in molar ratio: Li last
+/ Si4
+=0.3: 1, add the LiF powder, made the medium ball milling 24 hours with absolute ethyl alcohol, under 100 ℃ condition, dry then; The 6th step: the powder that will go up the step oven dry is calcined under 900～1000 ℃ condition, is incubated 10 minutes, promptly obtains spray ink Printing and uses yellow colorant.Yet sol-gel method since the molecular level of reaction raw materials mixes and in gelation process the form with netted association exist, can reduce synthesis temperature effectively, 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, and discover that mineralizer plays the effect of inducing nucleation in reaction process but also have, promote the crystalline growth to increase on the contrary, 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 Preparation of common high-purity nm silicic acid zirconium powder body early has report, but because the zirconium silicate stability of structure, the energy that water-heat process is difficult to provide enough impels alloying element (the 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 said pigment.
In this preparation method that a kind of zirconium silicate base 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; Said 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 intermediate product, said intermediate product is carried out high-temperature heat treatment makes A doping silicic acid Zirconium-base nano pigment powder.
The pH value of strongly acidic aqueous solution described in the preparation method of the present invention is preferably smaller or equal to 4; More preferably smaller 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 TR 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 certain density sodium silicate aqueous solution and strongly-acid colour developing elements A at first respectively; Both are mixed into the strongly-acid mixed solution, in mixed solution, add the zirconium ion aqueous solution of normality then.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 through 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; Said particle regular crystal forms, particle diameter are evenly and less than 1 μ m.
Zirconium silicate base 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 pyroceramic pigment of ink-jet ceramic decoration technology.Zirconium silicate base nano dye through hydrothermal synthesis method of the present invention preparation has that particle diameter is little, regular crystal forms, high, the good dispersivity of purity, 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
The TEM figure of the intermediate product that Fig. 2 prepares when being 260 ℃ of hydrothermal temperatures of (a) precursor warp for PH;
Fig. 3 is the XRD sign chart of (a) precursor sample of preparation under different hydrothermal temperatures for PH;
Fig. 4 A is the XRD figure spectrum of the praseodymium doping zirconium silicate powder body that after 800 ℃ of post-heat-treated, obtains of intermediate product that 4 different precursor liquids of pH value obtain through 260 ℃ of hydro-thermal reactions;
Fig. 4 B is the XRD figure spectrum of the praseodymium doping zirconium silicate powder body that after 1000 ℃ of post-heat-treated, obtains of intermediate product that 4 different precursor liquids of pH value obtain through 260 ℃ of hydro-thermal reactions;
The XRD figure spectrum of the praseodymium doping zirconium silicate powder body that Fig. 4 C intermediate product that to be 4 different precursor liquids of pH value obtain through 260 ℃ of hydro-thermal reactions obtains after 5 hours through 1200 ℃ of post-heat-treated;
Fig. 5 be pH be the precursor of (c) in different hydro-thermal thermotonuses after 1000 ℃ of XRD that handle resulting samples characterize;
Fig. 6 is the praseodymium doping zirconium silicate powder body that the said 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 body of embodiment 1 acquisition characterizes;
Fig. 7 (B) is that the SEM of the praseodymium doping zirconium silicate powder body of embodiment 2 acquisitions characterizes;
Fig. 7 (C) is that the SEM of the praseodymium doping zirconium silicate powder body of embodiment 3 acquisitions characterizes;
Fig. 7 (D) is that the SEM of the praseodymium doping zirconium silicate powder body of embodiment 4 acquisitions characterizes;
Fig. 7 (E) is that the SEM of the praseodymium doping zirconium silicate powder body 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 Preparation of common high-purity nm silicic acid zirconium powder body early has report, but because the zirconium silicate stability of structure, the energy that water-heat process is difficult to provide enough impels the praseodymium element doping in the zirconium silicate lattice.
The present invention provides a kind of hydro-thermal reaction synthesis method of the A of preparation doping zirconium silicate base pigment powder.The first step utilizes Hydrothermal Preparation to go out the nano level intermediate product particles; In second step, this intermediate product of pyroprocessing obtains nano level A doping zirconium silicate base pigment.Existing with reference to Figure of description, and combine following embodiment to further specify the present invention, should be understood that Figure of description and following embodiment only are used to explain the present invention, and unrestricted the present invention.In addition, the present invention is the XRD figure spectrum through the D/Max 2550V type X-ray diffractometer test sample of Japanese Rigaku company; Adopt the JEM-2010 type TEM of Japanese JEOL to come crystallinity, pattern, the particle diameter of observation sample; Adopt the JSF-6700F type SEM of Japanese Hitachi company to come the pattern and the particle diameter of observation 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 under 180～280 ℃ of temperature of reaction, to carry out hydro-thermal reaction the said aqueous solution.Not special qualification of hydro-thermal reaction time, those skilled in the art can confirm as the case may be, till generally accomplishing with reaction.The colour developing elements A can be praseodymium element, v element or ferro element.As an example hydro-thermal reaction synthesis method of the present invention is described in more detail with the praseodymium element below.
Embodiment specifies the preparation of the strongly acidic aqueous solution (precursor liquid) that comprises silicon ion, zirconium ion and praseodymium ion below as an example;
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 excessive concentrated nitric acid fast 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 reaction kettle and carry out hydro-thermal reaction, hydrothermal temperature is 260 ℃ in the present embodiment.Then, hydrothermal product is cleaned, is for example used deionized water, ethanol, dry, grind 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;
Can know that from the pH value XRD result (Fig. 1) of different hydro-thermal precursors 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 pure phase zirconium silicate at (a) PH=0.5.Generally speaking, the principal phase of intermediate product was zirconium silicate, helps the zirconium silicate crystalline at low PH of hydro-thermal reaction stage and form 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, promptly praseodymium is doped in the intermediate product.And nearly all XRD result demonstrates tangible wideization, and this has shown that the particle that is obtained 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 that prepared intermediate product zirconium silicate crystal particle diameter is very little, MV 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 of preparation characterizes chart under different hydrothermal temperatures.Wherein the hydrothermal temperature of (a1) is 200 ℃; (a2) hydrothermal temperature is 230 ℃; (a3) hydrothermal temperature is 260 ℃; Can know the increase along with hydrothermal temperature from Fig. 3, the peak value of XRD is sharp-pointed, and crystallinity strengthens.
Exemplarily explain through the high-temperature heat treatment intermediate product with the method for acquisition nano level A doping zirconium silicate base pigment and the spectrum property of prepared praseodymium doping silicic acid Zirconium-base nano pigment with the form of embodiment below in conjunction with accompanying drawing.High-temperature heat treatment TR of the present invention is preferably 700～1300 ℃; More preferably 800～1200 ℃.The high-temperature heat treatment time does not have special qualification, and those skilled in the art can confirm as the case may be, till generally accomplishing with reaction.
Fig. 4 A to Fig. 4 C be intermediate product under different temperature and time, 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 noted earlier, said 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 when hydrothermal temperature is 260 ℃, is prepared 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 body that Fig. 4 A intermediate product that to be 4 different precursor liquids of pH value obtain through 260 ℃ of hydro-thermal reactions obtains after 5 hours through 800 ℃ of post-heat-treated;
Can find out that precursor pH value is several samples of 0.5,1.2,2.0,3.0, obtain intermediate product through hydro-thermal reaction and increase through diameter of particle after 800 ℃ of thermal treatments again and the crystallinity enhancing.
The XRD figure spectrum of the praseodymium doping zirconium silicate powder body that Fig. 4 B intermediate product that to be 4 different precursor liquids of pH value obtain through 260 ℃ of hydro-thermal reactions obtains after 5 hours through 1000 ℃ of post-heat-treated;
Can find out that thermal treatment temp is that the diffraction peak of 1000 ℃ of powders that obtain is totally similar with 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 explain that crystallinity is stronger, and crystal grain grown up; And at pH is 2.0,3.0 o'clock, all is ZrO at 800 ℃ of thermal treatment crystalline diffraction peak main peaks
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 body that Fig. 4 C intermediate product that to be 4 different precursor liquids of pH value obtain through 260 ℃ of hydro-thermal reactions obtains after 5 hours through 1200 ℃ of post-heat-treated;
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 forms in the promptly previous hydrothermal reaction process has been transformed into zirconium silicate in heat treatment process;
Fig. 5 be pH be 2.0 precursor after different hydro-thermal thermotonuses, characterize through 1000 ℃ of XRD that handle 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, the half the 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, promptly be about under the condition of 550nm at weight break point wavelength on the spectrographic, the difference of the reflectivity at the reflectivity at 760nm place and 340nm place, spectral differences is big more, and the colour developing of sample is good more; Fig. 6 is the said embodiment of Fig. 4 C, and pH value is respectively (a) PH=0.5; (b) PH=1.2; (c) PH=2.0; (d) intermediate product that obtains through 260 ℃ of hydro-thermal reactions of 4 of PH=3.0 precursor liquids is through 1200 ℃ of praseodymium doping zirconium silicate powder bodies that post-heat-treated obtained in 5 hours, and two kinds of commercial praseodymium zirconium bloom bodies are at the total reflection light spectrogram of 340 ~ 760nm.Through spectroscopic analysis, can see that the curvilinear trend of the total reflection spectrum of the sample that different PH makes is similar fully, and reflectivity must to go up weight break point all be about 550nm.The spectral differences of 4 samples that the said 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.Promptly, the praseodymium zirconium yellow of method preparation disclosed by the invention can reach the color of commercial sample basically.
The embodiment that below enumerates out certain exemplary again is 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 excessive concentrated nitric acid fast 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, hydrothermal product with deionized water wash three times, is washed one time again oven dry with ethanol.The powder that obtains is ground, put into retort furnace and obtain the zirconium silicate powder in 1000 ℃ of following pyroprocessing;
Fig. 7 (A) characterizes for the SEM of the praseodymium doping zirconium silicate powder body that present embodiment obtains.The said diameter of particle that makes distributes more even, between 80nm ~ 260nm.And from the Electronic Speculum picture, can see crystal edge clearly, 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 excessive concentrated nitric acid fast 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, hydrothermal product with deionized water wash three times, is washed one time again oven dry with ethanol.The powder that obtains is ground, put into retort furnace and obtain the zirconium silicate powder in 1000 ℃ of following pyroprocessing;
Fig. 7 (B) characterizes for the SEM of the praseodymium doping zirconium silicate powder body that present embodiment obtains.Compare the preparation method of embodiment 1, the hydrothermal temperature of present embodiment increases to some extent.And the diameter of particle that the prepared powder comparative example 1 of present embodiment makes is littler 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 crystal edge clearly, 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 excessive concentrated nitric acid fast 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, hydrothermal product with deionized water wash three times, is washed one time again oven dry with ethanol.The powder that obtains is ground, put into retort furnace and obtain the zirconium silicate powder in 1200 ℃ of following pyroprocessing;
Fig. 7 (D) characterizes for the SEM of the praseodymium doping zirconium silicate powder body that present embodiment obtains.From the Electronic Speculum picture, can see crystal edge clearly, 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 excessive concentrated nitric acid fast 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, hydrothermal product with deionized water wash three times, is washed one time again oven dry with ethanol.The powder that obtains is ground, put into retort furnace and obtain the zirconium silicate powder in 1200 ℃ of following pyroprocessing;
Fig. 7 (E) characterizes for the SEM of the praseodymium doping zirconium silicate powder body that 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 excessive concentrated nitric acid fast 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, hydrothermal product with deionized water wash three times, is washed one time again oven dry with ethanol.The powder that obtains is ground, put into retort furnace and obtain the zirconium silicate powder in 1200 ℃ of following pyroprocessing;
Fig. 7 (C) characterizes for the SEM of the praseodymium doping zirconium silicate powder body that 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 excessive concentrated nitric acid fast 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, hydrothermal product with deionized water wash three times, is washed one time again oven dry with ethanol.The powder that obtains is ground, put into retort furnace and obtain praseodymium doping zirconium silicate powder body in 1300 ℃ of following pyroprocessing;
Adopt the 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 excessive concentrated nitric acid fast 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, hydrothermal product with deionized water wash three times, is washed one time again oven dry with ethanol.The powder that obtains is ground, put into retort furnace and obtain praseodymium doping zirconium silicate powder body in 1200 ℃ of following pyroprocessing;
Adopt the 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 excessive concentrated nitric acid fast 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, hydrothermal product with deionized water wash three times, is washed one time again oven dry with ethanol.The powder that obtains is ground, put into retort furnace and obtain praseodymium doping zirconium silicate powder body in 1200 ℃ of following pyroprocessing;
Adopt the pattern and the particle diameter of the powder that SEM observation makes, its size distribution narrower with monodispersity is preferably arranged.Its particle diameter is less than 800nm.
Preparing method provided by the invention, the first step utilizes Hydrothermal Preparation to go out nano level intermediate product powder; In second step, this intermediate product of pyroprocessing obtains 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 pyroceramic pigment of ink-jet ceramic decoration technology.Zirconium silicate base nano dye through hydrothermal synthesis method of the present invention preparation has that particle diameter is little, regular crystal forms, high, the good dispersivity of purity, and the characteristics that the colour generation ability is strong, colour stability is good.
Claims (10)
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; Said 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 intermediate product, said intermediate product is carried out high-temperature heat treatment makes praseodymium doping silicic acid Zirconium-base nano pigment powder.
2. preparation method according to claim 1 is characterized in that, the pH value of said strongly acidic aqueous solution is smaller or equal to 4.
3. preparation method according to claim 2 is characterized in that, the pH value of said strongly acidic aqueous solution is smaller or equal to 3.
4. preparation method according to claim 1 and 2 is characterized in that, said hydrothermal temperature is 180～280 ℃.
5. preparation method according to claim 1 and 2 is characterized in that, said high-temperature heat treatment TR is 800～1300 ℃.
6. preparation method according to claim 1 and 2 is characterized in that, said strongly acidic aqueous solution makes through following steps:
The prepare silicon acid sodium aqueous solution;
With Pr
6O
11Be dissolved in concentrated acid configuration praseodymium ion strongly acidic aqueous solution;
Two aqueous solution are become mixed solution, in mixed solution, add the zirconium ion aqueous solution then.
7. preparation method according to claim 1 and 2 is characterized in that, through with a certain amount of ZrOCl
2Be dissolved in water and make the said zirconium ion aqueous solution.
8. preparation method according to claim 6 is characterized in that, through adding the throw out dissolving that generates when strong acid mixes sodium silicate aqueous solution and praseodymium ion strongly acidic aqueous solution, in mixed solution, adds the zirconium ion aqueous solution then.
9. a praseodymium doping silicic acid Zirconium-base nano pigment that makes according to one of any method of claim 1 to 8 is characterized in that comprising praseodymium doping zirconium silicate crystalline particle, and said grain diameter is less than 1 μ m.
10. praseodymium doping silicic acid Zirconium-base nano pigment according to claim 9 is characterized in that said grain diameter is less than 500nm.
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| CN105110345A (en) * | 2015-08-03 | 2015-12-02 | 景德镇陶瓷学院 | Preparation method for Pr doped ZrSiO4 yellow ceramic pigment, product prepared thereby and application thereof |
| CN108862294A (en) * | 2017-05-08 | 2018-11-23 | 上海大学 | A kind of nanometer of praseodymium zirconium yellow material and preparation method thereof |
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| CN102173427A (en) * | 2011-03-04 | 2011-09-07 | 景德镇陶瓷学院 | Preparation method of yellow zirconium silicate pigment for ink-jet printing and product prepared by same |
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| CN105110345A (en) * | 2015-08-03 | 2015-12-02 | 景德镇陶瓷学院 | Preparation method for Pr doped ZrSiO4 yellow ceramic pigment, product prepared thereby and application thereof |
| CN108862294A (en) * | 2017-05-08 | 2018-11-23 | 上海大学 | A kind of nanometer of praseodymium zirconium yellow material and preparation method thereof |
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