CN112479707A - Cold isostatic pressing preparation method of tungsten oxide-based ceramic target material - Google Patents

Cold isostatic pressing preparation method of tungsten oxide-based ceramic target material Download PDF

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CN112479707A
CN112479707A CN202011266668.2A CN202011266668A CN112479707A CN 112479707 A CN112479707 A CN 112479707A CN 202011266668 A CN202011266668 A CN 202011266668A CN 112479707 A CN112479707 A CN 112479707A
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mass fraction
powder
tungsten oxide
doping source
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高明
张虎
张花蕊
杨本润
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Beijing Hangda Micro Technology Co ltd
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Abstract

The invention relates to a cold isostatic pressing preparation method of a tungsten oxide-based ceramic target material, which comprises the following steps: preparing raw materials: the primary mixed powder comprises high-purity tungsten oxide and doping source powder, wherein the doping source is selected from at least three of Ti, Mo, V, Al, Li and Zr, the purity of the mixed powder is more than 99.95 percent, the average grain diameter is 500-1800 nm, and the grain diameter of D50 is 200-750 nm; m1、M2、M3、M4、M5The quantitative relationship of (a) corresponds to the formula:
Figure DDA0002776284990000011
spray drying, powder filling and compaction, pressing, bisque degumming and sintering; taking out the sintered blank after heat preservation; with or without machining as required. The preparation method of the invention can prepare the tungsten oxide-based ceramic target material with good conductivity, higher purity, fine grain size and high density.

Description

Cold isostatic pressing preparation method of tungsten oxide-based ceramic target material
Technical Field
The invention relates to a preparation method of a ceramic target material, in particular to a cold isostatic pressing preparation method of an n-type tungsten oxide-based ceramic target material.
Background
Tungsten trioxide is an important n-type tungsten oxide semiconductor, and has important application in the fields of gas-sensitive materials, photocatalysis, new energy and the like. Tungsten trioxide is an anode electrochromic material with excellent performance, a tungsten trioxide ceramic target material is prepared into a micron and submicron photoelectric film through magnetron sputtering, and the micron and submicron photoelectric film is compounded into a film photoelectric device, so that the tungsten trioxide ceramic target material has wide application prospects in the fields of large-screen display, high-density information storage and the like. In contrast to organic photochromic films, WO3The film has good stability and low cost. Doping certain elements into WO3The lattice defect density can be effectively improved in the crystal lattice, and the recombination process of electrons after light excitation is inhibited, so that the number of photon-generated carriers participating in the color change process is increased, and the WO is greatly improved3Photochromic properties of (1).
The magnetron sputtering process cannot leave the high-performance magnetron sputtering target, and from the aspect of coating process performance, the purity of the tungsten oxide-based ceramic target in the prior art is not high and is generally below 99.9 percent, and simultaneously, the tungsten oxide-based ceramic target does not contain doping elements or the amount of the doping elements is not in an optimal range, so the conductivity is not good, and only high-cost radio frequency sputtering equipment can be adopted; meanwhile, the crystal grain size is too large and uneven, so that the film coating process is unstable, the phenomenon of sparking and reverse sputtering is serious, the thickness of the film is uneven, the electrical property of the film is poor, the dyeing property is unstable, and the film-making cost is too high; and the density of the target is also lower, and the coating process is unstable and the performance of the coating is poor due to the too low density of the target.
Therefore, a tungsten oxide-based ceramic target material with good conductivity, high purity, fine grain size and high density is required for the wide application of the tungsten oxide film. However, the tungsten oxide-based ceramic target material cannot be prepared in the prior art.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cold isostatic pressing preparation method for preparing a tungsten oxide-based ceramic target material with good conductivity, high purity, fine grain size and high density aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the cold isostatic pressing preparation method of the tungsten oxide-based ceramic target material is characterized by comprising the following steps of:
A. preparing raw materials: the primary mixed powder comprises high-purity tungsten oxide and doping source powder, wherein the doping source is selected from at least three of Ti, Mo, V, Al, Li and Zr, the purity of the primary mixed powder is more than 99.95 percent, the average grain diameter is 500-1800 nm, and the grain diameter of D50 is 200-750 nm; definition M1The mass fraction of powder particles in a 50-100nm particle size range, M2Is 100-400nm granularity segment powder particle mass fraction, M3The mass fraction of powder particles in a 400-plus-700 nm particle size section, M4The mass fraction of powder particles in the 700nm-1 mu M particle size section, M5The mass fraction of powder particles in the particle size section of more than 1 mu M, M1、M2、M3、M4、M5The quantitative relationship of (a) corresponds to the formula:
Figure BDA0002776284970000021
b, spray drying: b, adding the primary mixed powder prepared in the step A into liquid for dispersion, stirring and dispersing to prepare secondary slurry;
adding a binder into the secondary slurry, and performing spray drying treatment on the secondary slurry to obtain secondary powder, wherein the secondary powder has the properties of purity of more than 99.95%, average particle size of 5-30 mu m, D50 particle size of 2-25 mu m, and apparent density of more than 1.50 g-cm-3；
The preparation of the secondary powder is to further improve the macroscopic average particle size of the powder, widen the particle size distribution, improve the apparent density and reduce the internal stress of a green body on the basis of ensuring that tungsten oxide and other doping source crystal grains in the powder are not changed, and simultaneously add a binder into the powder to facilitate the forming;
c, filling the secondary powder prepared in the step B into cold isostatic pressingIn the mould, the tap density is 2.0-3.0.g/cm3；
D, conveying the die into a cold isostatic pressing chamber for pressing, wherein the pressure is 150-230 MPa, and the pressure maintaining time is 5-30 min;
e, unglazed blank degumming: carrying out gradient heating on the biscuit, and cooling along with a furnace to obtain a degummed blank;
f, sintering: performing gradient sintering on the blank, wherein the first gradient temperature is 650-; then the temperature is increased to the second gradient temperature of 900-. Preferably, the first gradient temperature is 680-; the second gradient temperature 950-. Further preferably, the first gradient temperature is 720 ℃; a second gradient temperature of 1050 ℃;
g, after heat preservation, cooling to room temperature and taking out the sintered blank;
h with or without machining as required.
Preferably, the step B spray drying comprises the steps of:
(a) adding 0.5-5 times volume of liquid for dispersion into the mixed powder to prepare slurry with 15-60% vol, and performing ball milling dispersion; further preferably, 4-5 times of volume of deionized water is added to prepare 17% -20% vol slurry; the liquid used for dispersion in the step is any one of proper liquids such as deionized water, alcohol, acetone, kerosene and the like;
(b) adding an organic binder solution which accounts for 0.5-3% of the total mass of the slurry into the prepared slurry, wherein the mass fraction of the organic binder solution is 1-7 wt%. The solute of the binder solution can be one or a mixture of polyvinyl alcohol, polycarbonate, maple and other common organic binders, and the solid organic binder needs to be mixed with water according to the mass ratio so as to prepare the required solute; for liquid organic binders, the solute can be used directly, so that the mass fraction of the solute itself is relatively wide, preferably 33% to 100% by weight.
(c) Spray drying to obtain secondary powder particles with a binder;
(d) and sieving and refining the secondary powder to obtain the secondary powder.
Preferably, the step C is a powder filling link, and the tap frequency is 10-50 Hz.
Preferably, the step E of the gradient temperature-raising process for biscuit degumming comprises: heating to the first gradient temperature of 120-; then the temperature is raised to the second gradient temperature of 350-. Further preferably, the first gradient temperature is 160-; the second gradient temperature is 400-550 ℃; further preferably, the first gradient temperature is 200 ℃ and the second gradient temperature is 500 ℃.
In order to obtain better conductivity, the average particle diameter of the primary mixed powder in the step A is 700nm-1.5 μm, and the particle diameter of D50 is 350-700 nm.
More preferably, the average particle size of the secondary powder is 800nm-1.3 μm, and the particle size of D50 is 300-600 nm.
More preferably, the average particle size of the secondary powder is 1 μm-1.25 μm, and the D50 particle size is 400-500 nm.
More preferably, the secondary powder has an average particle size of 1.0 μm and the D50 particle size is 0.40 μm.
Preferably, the total mass fraction of doping source elements in the primary mixed powder is 10-40%. Further preferably, the total mass fraction of doping source elements in the primary mixed powder is 10-30%.
Preferably, the mass fraction of the Ti element is in the range of 0 to 15%, the mass fraction of the Mo element is in the range of 0 to 15%, the mass fraction of the V element is in the range of 0 to 10%, the mass fraction of the Al element is in the range of 0 to 2%, the mass fraction of the Li element is in the range of 0 to 2%, and the mass fraction of the Zr element is in the range of 0 to 2%.
Further preferably, the mass fraction of the Ti element is in the range of 1 to 12%, the mass fraction of the Mo element is in the range of 1 to 12%, the mass fraction of the V element is in the range of 0.5 to 10%, the mass fraction of the Al element is in the range of 0.1 to 2%, the mass fraction of the Li element is in the range of 0.1 to 2%, and the mass fraction of the Zr element is in the range of 0.1 to 2%.
Further preferably, the mass fraction of the Ti element is in the range of 5 to 10%, the mass fraction of the Mo element is in the range of 5 to 10%, the mass fraction of the V element is in the range of 1 to 10%, the mass fraction of the Al element is in the range of 0.1 to 0.8%, the mass fraction of the Li element is in the range of 0.1 to 1.5%, and the mass fraction of the Zr element is in the range of 0.2 to 2%.
Preferably, the doping source component proportion is selected from one of the following groups:
a first group: the doping source elements are Mo, Li and Zr, and the mass fraction ranges of Mo are 5-10%, Li is 0.1-1.5% and Zr is 0.2-2%;
second group: the doping source elements are Ti, Mo and Zr, and the mass fraction ranges of Ti 5-10%, Mo 5-10% and Zr 0.3-2%;
third group: the doping source elements are Li, Al and Zr, and the mass fraction ranges of Li 1-2%, Al 0.1-1% and Zr 0.3-2%;
and a fourth group: the doping source elements are Mo, V and Al, and the mass fraction ranges of Mo 5-10%, V1-10% and Al 0.1-0.8%;
and a fifth group: the doping source elements are Ti, V, Zr and Al, and the mass fraction ranges of the doping source elements are 5-10% of Ti, 1-10% of V, 0.2-2% of Zr and 0.2-0.8% of Al;
a sixth group: the doping source elements are Mo, Ti, V and Zr, the mass fraction ranges of Mo 5-10%, Ti 5-10%, V3-6% and Zr 0.5-2%,
a seventh group: the doping source elements are Mo, Li, Ti, Al and Zr, and the mass fraction ranges of Mo are 5-10%, Li is 1-2%, Ti is 5-10%, Al is 0.2-0.8% and Zr is 0.5-2%.
Further preferably, the doping source component is selected from one of the following groups according to a molar ratio:
a first group: mo: li: zr (0-10): (0-15): (0-2);
second group: ti: mo: zr (0-15): (0-10): (0-2);
third group: li: al: zr (0-15): (0-2): (0-2);
and a fourth group: mo: v: al (0-10): 0-2;
and a fifth group: ti: v: zr: al (0-15): 0-10): 0-2;
a sixth group: mo: ti: v: zr (0-10): 0-15): 0-10): 0-2);
a seventh group: mo: li: ti: al: zr (0-10), (0-15), (0-2).
Further preferably, the doping source component is selected from one of the following groups according to a molar ratio:
a first group: mo: li: zr (1-8): (2-12): (0.2-1.5)
Second group: ti: mo: zr (1-12) to (1-8) to (0.2-1.5);
third group: li: al: zr (2-12) (0.1-1.8) (0.2-1.5);
and a fourth group: mo: v: al is (1-8): (1-8): 0.1-1.8;
and a fifth group: ti: v: zr: al (1-12), (1-8), (0.2-1.5), (0.1-1.8);
a sixth group: mo: ti: v: zr (1-8): (1-12): (1-8): (0.2-1.5)
A seventh group: mo: li: ti: al: zr (1-8): (2-12): (1-12): (0.1-1.8): (0.2-1.5).
Further preferably, the doping source component is selected from one of the following groups according to a molar ratio:
a first group: mo: li: zr 5:10:1
Second group: ti: mo: zr is 10:5: 1;
third group: li: al: zr is 10:1: 1;
and a fourth group: mo: v: al is 5:5: 1;
and a fifth group: ti: v: zr: al is 10:5:1: 1;
a sixth group: mo: ti: v: zr-5: 10:5:1
A seventh group: mo: li: ti: al: zr is 5:10:10:1: 1.
Compared with the prior art, the invention has the advantages that:
1. the primary mixed powder used in the invention contains nano and submicron powder granularity at the same time, and has wider granularity distribution, and M1、M2、M3、M4、M5The quantitative relationship of (a) corresponds to the formula:
Figure BDA0002776284970000051
can obtain more than 1.4 g.cm-3The high bulk density can be used for preparing high solid content secondary slurry, the sintering performance is improved, and the high-density ceramic green compact can be obtained by a cold isostatic pressing process, and then the high-density ceramic green compact can be obtained by sintering.
2. By doping n-type doping elements such as Li, Ti, Mo, V, Al, Zr and the like into the tungsten trioxide perovskite structure, the concentration and the mobility of current carriers in tungsten trioxide can be improved, lattice collapse is promoted, the atom mismatching degree is improved, the n-type conductivity of the material is improved, meanwhile, a low-melting-point compound is easily formed, the sintering activity is improved, and the material density is improved.
3. According to the invention, the tungsten oxide ceramic is prepared by adopting a cold isostatic pressing method, the cold isostatic pressing can bring the optimal density of the green body, the density of the core part of the green body is almost consistent with that of the periphery, and the density uniformity of the sintered tungsten oxide ceramic is optimal. The cold isostatic pressing process has very low glue content, less gas evolution in the production process and CO content2Mainly, the environmental protection is better. Meanwhile, the cold isostatic pressing is suitable for preparing large-size plane and rotary target green bodies, the obtained tungsten oxide ceramic green bodies have the highest strength, the sintering temperature is slightly lower than that of other forming processes, and the high-performance n-type tungsten oxide ceramic can be stably obtained by matching with a vacuum sintering technology, so that the energy consumption is saved, and the production cost is reduced. The cold isostatic pressing process is the most suitable technology for large-scale industrial mass production of tungsten oxide ceramic products, the product quality is stable, the production link is highly controllable, and the single-time capacity can reach the highest efficiency according to the production capacity of equipment.
3. The introduction of the spray drying process is beneficial to improving the powder fluidity and the bulk density and improving the sintering performance.
4. The tap density of the step D is 2.0 to 3.0g/cm3Step E, selecting a cold isostatic pressure of 150MPa-230 MPa; the tap density and the cold isostatic pressure can eliminate agglomeration and loose packing of powder particles, so that high density is brought; thereby enabling the second gradient sinteringThe temperature can be properly reduced, and the target hardly has the density unevenness. The density is not high due to the selection of the pressure lower than 150MPa, and the sputtering effect is influenced due to excessive air holes in the target material; the pressure higher than 230MPa increases the burden of the equipment, and can cause the rebound cracking of the green body.
5. And G, selecting the' first gradient temperature of 650-. The first gradient temperature of 650-800 ℃ of the invention can completely remove the organic residues in the green body while preventing the green body from cracking and ensure the chemical bond of the organic binder to be broken, and the lower temperature rise speed ensures that the generated CO is ensured2The gas is fully vented through the voids between the green particles and does not accumulate in the matrix increasing the C content. The first gradient temperature is lower than 650 ℃, so that C discharge is incomplete, and impurities are introduced; a first gradient temperature higher than 800 ℃ increases the energy consumption, increases the cost, and makes the substrate sintered in advance, which is not favorable for executing a second gradient temperature.
6. Step G, selecting' heating to a second gradient temperature of 900-2Gas is discharged out of the green body, and the stress of the green body is reduced; and the powder particles can be fully adhered along with the rise of the temperature to form a sintering neck, the crystal grains are fully grown, the air holes are eliminated, and the high-density ceramic sintered blank is obtained. The second gradient temperature is higher than 1200 ℃, so that crystal grains grow excessively, excessive oxygen vacancies are generated, the density is reduced, and the conductivity and the coating performance of the target material are reduced; the second gradient temperature is lower than 900 ℃, which causes the density to be reduced, the mechanical strength of the ceramic is not high, and the film coating performance is reduced.
Therefore, the tungsten oxide-based ceramic target material finally prepared by the invention comprises the following components in parts by weight: the purity is more than 99.95 percent, the average grain size is 1-10 mu m, no obvious doped phase exists, the density is more than 98 percent, and the conductivity is more than 15S/cm. The ceramic target material has good conductivity, so that the film prepared by using the target material also has good conductivity, and industrial application of an n-type transparent conductive film, an electrochromic film and the like which need to use the conductivity of a tungsten oxide film becomes possible; in addition, in terms of coating process performance, the target material has high conductivity, low-cost direct current sputtering equipment can be directly adopted, and the film-making cost is reduced; the grain size is reduced, the distribution of the doped phase is uniform, the density of the target material is improved, the coating process is stable, the phenomenon of sparking and back sputtering is prevented, the thickness of the film is more uniform, the strength of the ceramic structure is improved, the target material can bear higher power density during sputtering, and faster deposition rate is obtained.
Drawings
FIG. 1 is a photomicrograph of a powder of example 1 of the present invention;
FIG. 2 is a powder XRD pattern of example 1 of the present invention;
FIG. 3 is a PSD diagram of the powder of example 1 of the present invention;
FIG. 4 is an electron micrograph of a ceramic of example 1 of the present invention;
FIG. 5 is an electron micrograph of a ceramic of example 2 of the present invention;
FIG. 6 is an electron micrograph of a ceramic of example 3 of the present invention;
FIG. 7 is an electron micrograph of a ceramic of example 4 of the present invention;
FIG. 8 is an electron micrograph of a ceramic of example 5 of the present invention;
FIG. 9 is an electron micrograph of a ceramic of example 6 of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The doped tungsten oxide powders of the following examples were prepared by the following method:
(a) preparing a premixed solution: fully dissolving pure water, organic monomer and cross-linking agent according to the weight ratio of 100 (7-12) to 0.7-1.2 to form a premixed solution;
(b) preparing slurry: adding tungstate with the purity of more than or equal to 99.99% and doping source powder into the premixed solution to prepare slurry with the solid phase content of 30-70%, adding 1-3 wt% of dispersing agent, adjusting the pH value to 8-10, and performing wet ball milling dispersion;
(c) and (3) gel forming: pouring the slurry into a mold, adding an initiator for crosslinking and curing, controlling the curing temperature to be 40-70 ℃ and the humidity to be 50-70%, and drying to obtain a wet blank;
(d) and (3) calcining: calcining the wet blank at the temperature of 750-850 ℃, wherein the temperature rise speed is not higher than 2 ℃/min, and obtaining a biscuit;
(e) crushing and granulating: pulverizing the biscuit with air flow, pre-crushing to obtain micron-sized powder, and dry-grinding for 2-20hr at 1000R/min at 100-;
(f) sieving: and sieving the primary tungsten oxide-based powder by a sieve of 40-80 meshes to obtain secondary tungsten oxide-based powder, namely the finished product powder.
Preferably, the organic monomer for preparing the premix in step (a) is any one or a combination of acrylamide, polyvinyl alcohol and polyacrylic acid, and the cross-linking agent is any one or a combination of N-N' methylene bisacrylamide, polyethylene glycol and polyethylene glycol dimethacrylate; analytically pure ammonium metatungstate or ammonium paratungstate is selected as the tungstate of the slurry prepared in the step (b), and the dispersing agent is any one of JA281, ammonium citrate and polyvinyl alcohol; the initiator for gel forming in the step (c) is any one of ammonium persulfate, azodiimidazoline propane, azodiimidazole propane hydrochloride and hydrogen peroxide.
Preferably, the particle size of the ball milling dispersed grinding balls in the step (b) is 0.3-10mm, the ball-material ratio is 1.5-4, the ball milling time is 2-20hr, and the rotating speed is 150-.
Example 1
Firstly, preparing doped submicron tungsten oxide-based powder:
1) preparing raw materials: ammonium metatungstate with the purity of more than or equal to 99.99% and the doping source element components of the embodiment are Mo: li:zr is 5:10: 1; preparing MoO with corresponding element proportion2、Li2O、ZrO2Doping source powder with the purity more than or equal to 99.99 percent; the mass ratio of the added ammonium metatungstate to the doping source powder is 87: 13.
the doping source powder can purchase other simple substance metals, alloy inorganic salts and organic salts of corresponding elements, and the effect is similar.
2) Preparing a premixed solution, and fully dissolving pure water, organic monomer acrylamide and a cross-linking agent N 'N' -methylene bisacrylamide in a weight ratio of 100:10:1 to form the premixed solution;
3) preparing slurry: adding the pure ammonium metatungstate and the doping source powder prepared in the step 1) into the premixed liquid to prepare 50% solid content slurry, adding 2 wt% of ammonium citrate dispersant, adjusting the pH value to 9.5 by adopting tetramethylammonium hydroxide, and dispersing by adopting ball milling, wherein the average particle size of a milling ball is 1mm, and the ball-to-material ratio is 2: 1;
4) and (3) gel forming: pouring the slurry into a mold, adding an initiator ammonium persulfate to perform crosslinking curing at the curing temperature of 60 ℃ and controlling the humidity at 50%, and drying to obtain a wet blank;
5) and (3) calcining: calcining the dried wet blank at 800 ℃, wherein the heating rate is 1.5 ℃/min, and obtaining a biscuit;
6) crushing and granulating: pulverizing the biscuit with air flow to obtain micron-sized particles, and dry-grinding at 200R/min for 10hr to obtain primary tungsten oxide-based powder;
7) sieving: and (3) sieving the primary tungsten oxide-based powder by a 60-mesh standard sieve to obtain secondary tungsten oxide-based powder, namely submicron-grade doped tungsten oxide-based finished powder.
The purity of the prepared submicron-grade doped tungsten oxide-based powder is 99.99%, the mass fraction of tungsten trioxide in the powder is 85%, and the balance is a doping source oxide, wherein the doping source element components are Mo: li: zr is 5:10: 1.
The powder micrograph is shown in figure 1, the powder XRD spectrum is shown in figure 2, the powder PSD spectrum is shown in figure 3, and the average particle size of the submicron doped tungsten oxide powder prepared in the example is 1.0 mu M, the particle size of D50 is 500nm, and the particle size of M in the example is obtained from the figure1At 4%, M 220% of M 330% of, M 440% of M5Is 6%, according to the formula
Figure BDA0002776284970000081
The bulk density of the powder of this example was > 1.4 g.cm-3。
Secondly, preparing doped tungsten oxide based ceramics
1) Weighing the mixed powder prepared in the first step by using a digital electronic balance, adding deionized water with 4.5 times of volume, and preparing secondary slurry with 18% vol solid phase fraction;
2) spray drying
(2.1) adding a2 wt% of aqueous binder solution in mass fraction into the secondary slurry, wherein the binder consists of polyvinyl alcohol and polycarbonate in a ratio of 3:1, the addition amount of the aqueous binder solution is 2% of the total weight of the slurry, and stirring for 18 hours for dispersing;
(2.2) carrying out spray drying on the slurry at the inlet temperature of 300 ℃ and the outlet temperature of 100 ℃ to obtain secondary powder;
(2.3) passing the powder through a 80-mesh sieve to obtain a bulk density of 1.60 g.cm-3The secondary powder of (4), the average particle size is 20 μm, and the particle size of D50 is 15 μm;
3) filling the secondary powder prepared by spray drying in the step 2) into a cold isostatic pressing die, and compacting the powder under the vibration frequency of 25Hz to reach 3.0 g.cm-3Tap density.
4) The die is sent into a cold isostatic pressing chamber for pressing, the pressure is 180MPa, the pressure maintaining time is 25min, and the green body is taken out after the pressing and the demolding;
5) heating the biscuit in a flowing air furnace for degumming, firstly, heating the furnace to a first gradient temperature of 250 ℃, heating at a speed of 0.8 ℃/min, and keeping the temperature for 3 hours;
then the temperature is increased to 600 ℃ of the second gradient temperature, the heat preservation time is 5 hours, and the temperature increasing speed is 0.9 ℃/min. And cooling to room temperature along with the furnace to obtain the degummed blank.
6) And (3) sintering: placing the degummed blank in a ventilation air furnace for sintering, firstly heating the furnace to 700 ℃ of first gradient temperature, heating up at a speed of 1 ℃/min, keeping the temperature for 3 hours, then heating up to 1100 ℃, keeping the temperature for 5 hours at a speed of 0.5 ℃/min, and cooling to room temperature along with the furnace.
7) And machining according to requirements to obtain a ceramic finished product.
The relative density is measured by a drainage method to be 99.5 percent, the average grain size is 3 mu m, the doping elements enter the ceramic crystal lattice, no obvious second phase exists, the conductivity of the ceramic body is measured by cutting samples to be 25S/cm, the microstructure is uniform, and the micro-anoxic state is achieved.
An electron micrograph of the ceramic prepared in this example is shown in FIG. 4.
Example 2
The difference between the present example and example 1 is that the mass fraction of the tungsten component in the powder calculated by tungsten oxide is 85%, the mass fraction of the doping source is 15%, and the doping source component is, in terms of mole ratio, Ti: mo: zr is 10:5: 1;
the rest steps are the same as the example 1, the obtained tungsten oxide-based ceramic has the relative density of 98.5 percent measured by a drainage method, the average grain size is 4.5 mu m, the doping elements enter the ceramic crystal lattice, no obvious second phase exists, and the conductivity of the ceramic body is 15S/cm measured by cutting samples.
An electron micrograph of the ceramic prepared in this example is shown in FIG. 5.
Example 3
Firstly, preparing doped submicron tungsten oxide-based powder:
1) preparing raw materials: preparing ammonium metatungstate with the purity of more than or equal to 99.99 percent, wherein the doping source element components of the embodiment are Ti: mo: zr is 10:1: 1; preparing titanium oxide, molybdenum oxide and zirconium oxide doping source powder with corresponding element proportion, wherein the purity is more than or equal to 99.999 percent; the mass ratio of the added ammonium metatungstate to the doping source powder is 92.2: 7.8.
the doping source powder can purchase other simple substance metals, alloy inorganic salts and organic salts of corresponding elements, and the effect is similar.
2) Preparing a premixed solution, namely mixing pure water and an organic monomer which is the combination of polyvinyl alcohol and polyacrylic acid, wherein the ratio of the polyvinyl alcohol to the polyacrylic acid is 1:1, and a cross-linking agent which is the combination of polyethylene glycol and polyethylene glycol dimethacrylate, wherein the ratio of the polyethylene glycol to the polyethylene glycol dimethacrylate is 1: 1; fully dissolving pure water, organic monomer and cross-linking agent in a weight ratio of 100:11:1.1 to form a premixed solution;
3) preparing slurry: adding the pure ammonium metatungstate and the doping source powder prepared in the step 1) into the premixed liquid to prepare slurry with the solid content of 45%, adding 0.05 wt% of ammonium citrate dispersant, adjusting the pH value to 10 by adopting ammonia water, and performing ball milling dispersion, wherein the average particle size of a milling ball is 1.5mm, and the ball-to-material ratio is 2: 1;
4) and (3) gel forming: pouring the slurry into a mold, adding an initiator azodiimidazoline propane for crosslinking and curing, controlling the curing temperature at 60 ℃ and the humidity at 60%, and drying to obtain a wet blank;
5) and (3) calcining: calcining the dried wet blank at 750 ℃ at the heating rate of 1.0 ℃/min to obtain a biscuit;
6) crushing and granulating: jet milling the biscuit, pre-milling the biscuit into micron-sized particles, and dry-milling the micron-sized particles at 1000R/min for 2hr to obtain primary tungsten oxide-based powder;
7) sieving: and (3) sieving the primary tungsten oxide-based powder by a 60-mesh standard sieve to obtain secondary tungsten oxide-based powder, namely submicron-grade doped tungsten oxide-based finished powder.
The purity of the prepared submicron-grade doped tungsten oxide-based powder is 99.99%, the mass fraction of tungsten trioxide in the powder is 90%, and the balance is doping source oxide, wherein the doping source element components are Ti: mo: zr is 10:1: 1.
The submicron doped tungsten oxide powder prepared in this example has an average particle size of 0.8 μ M, the particle size of D50 is 400nm, and M in this example1At 5%, M235% of M315% of M435% of M5Is 10%, and meets the formula
Figure BDA0002776284970000101
The bulk density of the powder of this example was > 1.4 g.cm-3。
Secondly, preparing doped tungsten oxide based ceramics
1) Weighing the mixed powder prepared in the first step by using a digital electronic balance, and adding deionized water with 0.8 time of volume to prepare secondary slurry with 56% vol solid phase fraction;
2) spray drying:
(2.1) adding a2 wt% aqueous solution of a binder into the secondary slurry, wherein the binder consists of polyvinyl alcohol and polycarbonate in a ratio of 3:1, the addition amount of the aqueous solution of the binder is 2% of the total weight of the slurry, and stirring for 10 hours to disperse;
(2.2) carrying out spray drying on the slurry at the inlet temperature of 300 ℃ and the outlet temperature of 110 ℃ to obtain secondary powder;
(2.3) sieving the powder with a 60-mesh sieve; obtaining a bulk density with a flowability parameter of 1.50g cm-3The secondary powder (2) had an average particle size of 5 μm and a D50 particle size of 2 μm.
3) Putting the mixed powder prepared in the step 2) into a cold isostatic pressing die, and compacting the mixed powder under the vibration frequency of 10Hz to reach 2.2 g.cm-3Tap density;
4) the die is sent into a cold isostatic pressing chamber for pressing, the pressure is 150MPa, the pressure maintaining time is 30min, and the green body is taken out after the pressing and the demolding;
5) degumming biscuit: heating the biscuit in a flowing air furnace for degumming, firstly, heating the furnace to a first gradient temperature of 250 ℃, heating at a speed of 0.5 ℃/min, and keeping the temperature for 4 hours;
then the temperature is increased to 600 ℃ of the second gradient temperature, the heat preservation time is 6 hours, and the temperature increasing speed is 0.8 ℃/min. And cooling to room temperature along with the furnace to obtain the degummed blank.
6) And (3) sintering: placing the degummed blank in a ventilation air furnace for sintering, firstly heating the furnace to 600 ℃ of a first gradient temperature, heating at a speed of 1 ℃/min, keeping the temperature for 2 hours, then heating to 1000 ℃, keeping the temperature for 10 hours at a speed of 0.6 ℃/min, and cooling to room temperature along with the furnace.
7) And machining according to requirements to obtain a ceramic finished product.
The obtained tungsten oxide-based ceramic has the relative density of 98.2 percent and the average grain size of 5 mu m measured by a drainage method, doping elements enter a ceramic crystal lattice, no obvious second phase exists, and the conductivity of the ceramic body is 22S/cm measured by cutting samples.
An electron micrograph of the ceramic prepared in this example is shown in FIG. 6.
Example 4
This example differs from example 3 in that the doping sources used were molybdenum oxide, vanadium oxide and aluminum oxide, and the doping source components of the preparation step were, in terms of mole ratios, Mo: v: al is 5:5: 1;
the obtained ceramic target finished product has the relative density of 98.0 percent, the average grain size of 3.5 mu m, doping elements enter ceramic crystal lattices, no obvious second phase exists, and the bulk conductivity is 18S/cm, which is measured by a drainage method.
An electron micrograph of the ceramic prepared in this example is shown in FIG. 7.
Example 5
Firstly, preparing doped submicron tungsten oxide-based powder:
1) preparing raw materials: preparing ammonium metatungstate with the purity of more than or equal to 99.99 percent, wherein the doping source element components of the embodiment are Ti: v: zr: al is 10:5:1: 1; preparing titanium oxide, molybdenum oxide and zirconium oxide doping source powder with corresponding element proportion, wherein the purity is more than or equal to 99.999 percent; the mass ratio of the added ammonium metatungstate to the doping source powder is 87: 13
The doping source powder can purchase other simple substance metals, alloy inorganic salts and organic salts of corresponding elements, and the effect is similar.
2) Preparing a premixed solution, and fully dissolving pure water, organic monomer polyacrylic acid and cross-linking agent polyethylene glycol in a weight ratio of 100:12:1.2 to form the premixed solution;
3) preparing slurry: adding the pure ammonium metatungstate prepared in the step 1) and the doping source powder into the premixed solution to prepare slurry with the solid content of 50%, adding 0.1 wt% of JA281 dispersant, adjusting the pH value to 9.5 by using ammonia water, and performing ball milling dispersion, wherein the average particle size of grinding balls is 2mm, and the ball-to-material ratio is 2: 1;
4) and (3) gel forming: pouring the slurry into a mold, adding an initiator azodimidepropane hydrochloride for crosslinking and curing, wherein the curing temperature is 65 ℃, the humidity is controlled at 70%, and drying to obtain a wet blank;
5) and (3) calcining: calcining the dried wet blank at 700 ℃, and heating at a speed of 1.0 ℃/min to obtain a biscuit;
6) crushing and granulating: pulverizing the biscuit with air flow to obtain primary pulverized micrometer powder, and dry-grinding at 500R/min for 10hr to obtain primary tungsten oxide-based powder;
7) sieving: and (3) sieving the primary tungsten oxide-based powder by a 60-mesh standard sieve to obtain secondary tungsten oxide-based powder, namely submicron-grade doped tungsten oxide-based finished powder.
The purity of the prepared submicron-grade doped tungsten oxide-based powder is 99.99%, the mass fraction of tungsten trioxide in the powder is 85%, and the balance is doping source oxide, wherein the doping source element components are Ti: v: zr: al is 10:5:1: 1.
The submicron doped tungsten oxide powder prepared in this example has an average particle size of 1.0 μ M, the particle size of D50 is 550nm, and M in this example1At 5%, M235% of M 320% of M425% of M5Is 15%, and meets the formula
Figure BDA0002776284970000111
The bulk density of the powder of this example was > 1.4 g.cm-3。
Secondly, preparing doped tungsten oxide-based ceramic:
1) weighing the powder prepared in the step one by using a digital electronic balance, adding deionized water with 0.7 time of volume, and preparing slurry with 59% vol solid phase fraction;
2) spray drying:
(2.1) adding a2 wt% aqueous solution of a binder into the secondary slurry, wherein the binder consists of polyvinyl alcohol and polycarbonate in a ratio of 3:1, the addition amount of the aqueous solution of the binder is 2% of the total weight of the slurry, and stirring for 8 hours to disperse;
(2.2) carrying out spray drying on the slurry at the inlet temperature of 300 ℃ and the outlet temperature of 105 ℃ to obtain secondary powder;
(2.3) sieving the powder with a 60-mesh sieve; the bulk density of the obtained fluidity parameter is 1.52 g.cm-3The secondary powder (2) had an average particle size of 30 μm and a D50 particle size of 25 μm.
3) Putting the mixed powder prepared in the step 2) into a cold isostatic pressing die, and compacting the mixed powder under the vibration frequency of 50Hz to reach 2.0 g.cm-3Tap density;
4) the die is sent into a cold isostatic pressing chamber for pressing, the pressure is 230MPa, the pressure maintaining time is 5min, and the green body is taken out after the pressing and the demolding;
5) degumming biscuit: heating the biscuit in a circulating air furnace for degumming, firstly, heating the furnace to a first gradient temperature of 220 ℃, heating at a speed of 0.8 ℃/min, and keeping the temperature for 3 hours;
then the temperature is increased to 600 ℃ of the second gradient temperature, the heat preservation time is 8 hours, and the temperature increasing speed is 0.9 ℃/min. And cooling to room temperature along with the furnace to obtain the degummed blank.
6) And (3) sintering: placing the degummed blank in a ventilation air furnace for sintering, firstly heating the furnace to the first gradient temperature of 750 ℃, heating up to the speed of 0.5 ℃/min, keeping the temperature for 5 hours, then heating up to 950 ℃, keeping the temperature for 15 hours, heating up to the speed of 0.5 ℃/min, and cooling to the room temperature along with the furnace.
7) And (5) processing by a cleaning machine to obtain a ceramic finished product.
The obtained tungsten oxide-based ceramic has the relative density of 98.5 percent and the average grain size of 4 mu m measured by a drainage method, doping elements enter a ceramic crystal lattice, no obvious second phase exists, and the conductivity of the ceramic body is 20S/cm measured by cutting samples.
An electron micrograph of the ceramic prepared in this example is shown in FIG. 8.
Example 6
The difference between this example and example 5 is that molybdenum oxide, titanium oxide, vanadium oxide and zirconium oxide are used as the doping source, the mass fraction of tungsten calculated as tungsten oxide is 80%, the mass fraction of the doping source is 20%, and the doping source component in the preparation step is Mo: ti: v: zr is 5:10:5: 1;
the obtained ceramic target finished product has the relative density of 98.3 percent and the average grain size of 3.5 mu m measured by a drainage method, the doping elements enter a ceramic crystal lattice, no obvious second phase exists, and the bulk conductivity is 21S/cm.
An electron micrograph of the ceramic prepared in this example is shown in FIG. 9.
The technical means disclosed in the invention scheme are not limited to the technical means disclosed in the above embodiments, but also include the technical scheme formed by any combination of the above technical features. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and such improvements and modifications are also considered to be within the scope of the present invention.

Claims (10)

1. A cold isostatic pressing preparation method of a tungsten oxide-based ceramic target material is characterized by comprising the following steps:
A. preparing raw materials: the primary mixed powder comprises high-purity tungsten oxide and doping source powder, wherein the doping source is selected from at least three of Ti, Mo, V, Al, Li and Zr, the purity of the primary mixed powder is more than 99.95 percent, the average grain diameter is 500-1800 nm, and the grain diameter of D50 is 200-750 nm; definition M1The mass fraction of powder particles in a 50-100nm particle size range, M2Is 100-400nm granularity segment powder particle mass fraction, M3The mass fraction of powder particles in a 400-plus-700 nm particle size section, M4The mass fraction of powder particles in the 700nm-1 mu M particle size section, M5The mass fraction of powder particles in the particle size section of more than 1 mu M, M1、M2、M3、M4、M5The quantitative relationship of (a) corresponds to the formula:
Figure FDA0002776284960000011
b, spray drying: b, adding the primary mixed powder prepared in the step A into liquid for dispersion, stirring and dispersing to prepare secondary slurry;
adding a binder into the secondary slurry, and performing spray drying treatment on the secondary slurry to obtain secondary powder, wherein the secondary powder has the properties of purity of more than 99.95%, average particle size of 5-30 mu m, D50 particle size of 2-25 mu m, and apparent density of more than 1.50 g-cm-3；
C preparing the step BThe obtained secondary powder is loaded into a cold isostatic pressing die, and the tap density is 2.0-3.0.g/cm3；
D, conveying the die into a cold isostatic pressing chamber for pressing, wherein the pressure is 150-230 MPa, and the pressure maintaining time is 5-30 min;
e, unglazed blank degumming: carrying out gradient heating on the biscuit, and cooling along with a furnace to obtain a degummed blank;
f, sintering: performing gradient sintering on the blank, wherein the first gradient temperature is 650-; then heating to a second gradient temperature of 900-;
g, after heat preservation, cooling to room temperature and taking out the sintered blank;
h with or without machining as required.
2. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing according to claim 1, wherein the method comprises the following steps: the step E is that the biscuit degumming gradient heating process comprises the following steps: heating to the first gradient temperature of 120-; then the temperature is raised to the second gradient temperature of 350-. .
3. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing according to claim 1, wherein the method comprises the following steps: the step B of spray drying comprises the following steps:
(a) adding 0.5-5 times volume of liquid for dispersion into the mixed powder to prepare slurry with 15-60% vol, and performing ball milling dispersion; adding an organic binder solution which accounts for 0.5-3% of the total mass of the slurry into the prepared slurry, wherein the mass fraction of the organic binder solution is 1-7 wt%;
(b) spray drying to obtain secondary powder particles with a binder;
(c) and sieving and refining the secondary powder to obtain the secondary powder.
4. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing sintering according to claim 1, wherein the method comprises the following steps: and D, the tap frequency of the step D is 10-50 Hz.
5. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing sintering according to any one of claims 1 to 4, wherein: the average particle size of the primary mixed powder prepared by the raw material in the step A is 800-1200nm, and the particle size of D50 is 350-500 nm.
6. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing according to any one of claims 1 to 4, wherein: and B, the total mass fraction of doping source elements in the primary mixed powder prepared by the raw material in the step A is 10-30%.
7. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing according to any one of claims 1 to 4, wherein: the mass fraction range of the Ti element, the mass fraction range of the Mo element, the mass fraction range of the V element, the mass fraction range of the Al element, the mass fraction range of the Li element and the mass fraction range of the Zr element prepared from the raw materials of the step A are respectively 0-15%, 0-10%, 0-2% and 0-2%.
8. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing according to claim 7, wherein the method comprises the following steps: the mass fraction of the Ti element is in the range of 1-12%, the mass fraction of the Mo element is in the range of 1-12%, the mass fraction of the V element is in the range of 0.5-10%, the mass fraction of the Al element is in the range of 0.1-2%, the mass fraction of the Li element is in the range of 0.1-2%, and the mass fraction of the Zr element is in the range of 0.1-2%.
9. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing according to any one of claims 1 to 4, wherein: the component proportion of the doping source is selected from one of the following groups:
a first group: the doping source elements are Mo, Li and Zr, and the mass fraction ranges of Mo are 5-10%, Li is 0.1-1.5% and Zr is 0.2-2%;
second group: the doping source elements are Ti, Mo and Zr, and the mass fraction ranges of Ti 5-10%, Mo 5-10% and Zr 0.3-2%;
third group: the doping source elements are Li, Al and Zr, and the mass fraction ranges of Li 1-2%, Al 0.1-1% and Zr 0.3-2%;
and a fourth group: the doping source elements are Mo, V and Al, and the mass fraction ranges of Mo 5-10%, V1-10% and Al 0.1-0.8%;
and a fifth group: the doping source elements are Ti, V, Zr and Al, and the mass fraction ranges of the doping source elements are 5-10% of Ti, 1-10% of V, 0.2-2% of Zr and 0.2-0.8% of Al;
a sixth group: the doping source elements are Mo, Ti, V and Zr, the mass fraction ranges of Mo 5-10%, Ti 5-10%, V3-6% and Zr 0.5-2%,
a seventh group: the doping source elements are Mo, Li, Ti, Al and Zr, and the mass fraction ranges of Mo are 5-10%, Li is 1-2%, Ti is 5-10%, Al is 0.2-0.8% and Zr is 0.5-2%.
10. The method for preparing the tungsten oxide-based ceramic target material by cold isostatic pressing according to claim 9, wherein the method comprises the following steps: the doping source component is selected from one of the following groups according to a molar ratio:
a first group: mo: li: zr (0-10): (0-15): (0-2);
second group: ti: mo: zr (0-15): (0-10): (0-2);
third group: li: al: zr (0-15): (0-2): (0-2);
and a fourth group: mo: v: al (0-10): 0-2;
and a fifth group: ti: v: zr: al (0-15): 0-10): 0-2;
a sixth group: mo: ti: v: zr (0-10): 0-15): 0-10): 0-2);
a seventh group: mo: li: ti: al: zr (0-10), (0-15), (0-2).
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