CN110723977B - With Cu2+Formation of CuAl in alumina porcelain2O4Method for preparing black alumina ceramic by using main colorant - Google Patents
With Cu2+Formation of CuAl in alumina porcelain2O4Method for preparing black alumina ceramic by using main colorant Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003086 colorant Substances 0.000 title claims abstract description 24
- 229910018565 CuAl Inorganic materials 0.000 title claims description 13
- 230000015572 biosynthetic process Effects 0.000 title claims description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 4
- 150000002505 iron Chemical class 0.000 claims abstract description 4
- 150000002696 manganese Chemical class 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 3
- 229910018576 CuAl2O4 Inorganic materials 0.000 abstract description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 1
- 229910000423 chromium oxide Inorganic materials 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 9
- 238000001308 synthesis method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 5
- 229910002549 Fe–Cu Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本发明公开了属于氧化铝陶瓷的着色技术领域的一种以Cu2+在氧化铝瓷内形成CuAl2O4为主着色剂制备黑色氧化铝陶瓷的方法。该方法是将铜盐、铁盐和锰盐按照一定摩尔比加入到适当的溶剂中溶解，与氧化铝基料充分混合形成瓷料，经过研磨、成型，在1250℃下烧结，制备所需要的黑色氧化铝陶瓷。本方法既可以成功获得颜色合格的氧化铝陶瓷，又避免了通常制备黑色氧化铝中所需的贵重的氧化钴和有毒的氧化铬，同时氧化铜的加入又可达到降低氧化铝烧结温度，在较低的温度下获得介电性能好、电阻率高、内部结构均匀、强度大的黑色氧化铝陶瓷。
The invention discloses a method for preparing black alumina ceramics by using Cu2 + in alumina ceramics to form CuAl2O4 as the main colorant, which belongs to the technical field of coloring of alumina ceramics. The method is to add copper salt, iron salt and manganese salt into a suitable solvent according to a certain molar ratio to dissolve, fully mix with alumina base material to form a porcelain material, grind, shape, and sinter at 1250 ° C to prepare the required ceramic material. Black alumina ceramic. The method can not only successfully obtain alumina ceramics with qualified color, but also avoid the precious cobalt oxide and toxic chromium oxide usually required in the preparation of black alumina. At the same time, the addition of copper oxide can reduce the alumina sintering temperature. At a lower temperature, black alumina ceramics with good dielectric properties, high resistivity, uniform internal structure and high strength can be obtained.
Description
Technical Field
The invention belongs to the technical field of coloring of alumina ceramics, and particularly relates to a coloring agent containing Cu2+Formation of CuAl in alumina porcelain2O4Preparation of black alumina ceramics as main colorantA method of making porcelain.
Background
The black alumina material has wide application and excellent performance, and is widely applied to electronic elements such as multilayer wiring ceramic substrates, electronic packaging and high-density packaging substrates. The semiconductor inheriting circuit has obvious photosensitivity, the alumina ceramic used as the packaging tube shell has light-shielding property, and the Al used for the liner plate of the nixie tube2O3Black is required to ensure clear digital display. There are many methods for producing black alumina, such as a primary synthesis method, a secondary synthesis method, a casting method, and the like.
(1) The secondary synthesis method comprises the following steps: during pre-synthesis, transition metal oxide iron oxide, cobalt oxide, nickel oxide and manganese oxide are ball milled, mixed and dried, synthesized in a small crucible at 1300 ℃ for 1 hour, sintered into hard blocks, crushed and added with Al2O3（91％）、SiO2（0.5％）、TiO2(2%), the raw materials are uniformly mixed by ball milling again, dried and formed, and sintered for 2 hours at 1350-1450 ℃. By adopting a pre-synthesis method, the oxide powder is sintered into hard blocks which are difficult to crush, because the synthesis temperature is too high (1300 ℃), the diffusion rate between transition metal oxides is increased, the reaction is fully carried out, and the dense sintering is achieved: later, when the synthesis temperature is gradually reduced (1250 ℃, 1200 ℃, 1100 ℃ and 1000 ℃), the powder shrinks into blocks, but the hardness is gradually reduced, when the synthesis temperature is below 1200 ℃, the blocks are easy to crush, the powder is ground into fine powder, and the powder shows black and bright color. In the forming process, more adhesives are needed, the lamination is easy to occur, and the tablet forming is difficult.
(2) The first synthesis method comprises the following steps: the transition metal oxide is directly added into the base material of alumina and sintered into black alumina ceramic blocks at a certain proportion and temperature. However, the blackness of the sample prepared by the primary synthesis method is deeper than that of the sample prepared by the pre-synthesis method, and the sample prepared by the secondary synthesis method can be fully reacted with the synthesized transition metal oxide to form a spinel compound, so that the coloring effect is better.
(3) Tape casting: the black pigment with the spinel structure can be obtained by keeping the temperature at 50 ℃ for 2 hours, the high-temperature volatility can be effectively avoided, and the good color and luster is presented; when the addition amount of the black pigment after ball milling for 4 hours is 5%, the black pigment can present uniform black after sintering within the temperature range of 1310-1330 ℃. Determining and optimizing casting process parameters: in the first stage of ball milling and mixing, ceramic powder with uniformly mixed granularity can be obtained after ball milling and mixing for 22-24 hours; the optimized range of the volume fraction in the ceramic green sheet suitable for the lamination process is determined, a novel drying method and a double-sided drying process are provided, and the problem of component gradient caused by single-sided drying can be solved; carrying out thermogravimetric analysis on the ceramic green sheet, and formulating a reasonable glue process; the black alumina ceramic prepared by the optimized process has good dimensional accuracy. However, the scale of the tape casting method is large, the requirement on experimental equipment is high, and the performance of black alumina is seriously influenced by too much additive content.
Since semiconductor integrated circuits and some electronic products have remarkable photosensitivity, alumina ceramics as a packaging material is required to have light-shielding properties, and Al for electronic product applications2O3The choice of black pigment of ceramics, due to the particularities of their field of application, must take into account the properties of the ceramic material: the blackness and mechanical strength of the ceramic substrate are ensured, and the insulation property, the thermal property and other performances which are required to be possessed when the ceramic substrate is used as an electronic device are also ensured.
Although the black alumina can be prepared by the methods, Co is generally used as a main colorant, and Cr is also introduced into some formulas. Co is expensive, and Cr is a toxic substance. The preparation method has complex preparation process, the minimum sintering temperature is over 1250 ℃, the performance of the alumina is greatly influenced by overhigh temperature, high requirements are also put forward to experimental equipment, and the dielectric property and the resistivity of the alumina are difficult to meet the requirements. The method can realize low-temperature sintering of black alumina, can also enable the dielectric constant and the resistivity of the black alumina to reach qualified numerical values, has low manufacturing cost, is nontoxic and harmless, can realize mass production, and meets the requirements of practical use.
Disclosure of Invention
The invention aims to provide a Cu-based alloy2+Formation of CuAl in alumina porcelain2O4The method for preparing black alumina ceramics by using Cu as a main colorant is characterized in that2+Forming CuAl at the grain boundary of alumina porcelain body2O4As a main colorant, Fe3+、Mn2+The black alumina ceramic is prepared by taking the alumina ceramic as an auxiliary doping element. The method comprises the steps of adding copper salt, iron salt and manganese salt into a proper solvent according to a certain molar ratio for dissolving, and simultaneously introducing a certain amount of tetraethoxysilane as SiO2The source is fully mixed with the alumina base material to form porcelain, and the porcelain is formed and sintered into the required black alumina ceramic under certain conditions; method of Cu2+Adding into main colorant, adding iron element to make the color darker and form ceramic body with lower copper adding amount, Mn element for forming black colorant with copper element, introducing certain amount of ethyl orthosilicate as SiO2The source reduces the sintering temperature of the alumina and can adsorb impurities; the process comprises the following steps:
1) dissolving tetraethoxysilane in absolute ethyl alcohol completely to prepare SiO-containing2The solution A of (1);
2) soluble Fe with a certain molar ratio3+、Cu2+、Mn2+Dissolving the salt in a certain solvent to prepare solution B;
3) adding the solution A and the solution B into an alumina base material according to a certain proportion, fully mixing, simultaneously adjusting the pH value to be neutral by using a certain amount of ammonia water or ammonium bicarbonate, washing with water, and drying to form a porcelain material;
4) and grinding the dried porcelain, tabletting and forming, and sintering under certain conditions to obtain the black alumina ceramic.
In the step 2), soluble Fe3+、Cu2+、Mn2+The salt of (A) is at least one or more of nitrate, acetate, sulfate and chloride.
In the step 3), the molar ratio of the ethyl orthosilicate to the alumina base material in the solution A is 0.01-10 mol%.
Cu as a colorant in the B solution in the step 3)2+The doping amount of (A) is 2-20 mol% and Fe3+The doping amount is 0-10% mol, Mn2+The doping amount is 0 to 10 mol%.
The solvent is at least one or more of water, methanol, ethanol and glycol.
The sintering temperature of the tabletting-formed ceramic is 1200-1300 ℃; to obtain Cu2+Forming CuAl at the grain boundary of alumina porcelain body2O4The black alumina ceramic prepared by taking the black alumina ceramic as the main colorant has the advantages of uniform internal structure, good shading degree, 5-80 of dielectric constant and resistivity>2×1010Ω·cm。
The invention has the beneficial effects that the copper, iron and manganese elements are used as raw materials, the formula is optimized, the sintering temperature of the alumina is fundamentally reduced, the requirement of the sintering furnace in the sintering process is reduced by the effect of reducing the sintering temperature, so that the resource is saved, the method can realize low-temperature sintering to obtain the black alumina ceramic which is low in manufacturing cost, non-toxic, harmless and uniform in black, the dielectric constant and the resistivity of the black alumina ceramic reach qualified numerical values, and the related performance of the black alumina ceramic is also higher. The method is simple to operate, does not need a large-scale forming machine, reduces the material cost, and can be used for large-scale industrial production of ceramics with specified functions.
Drawings
FIG. 1 is a diagram of xrd with addition of Fe-Cu in example 1.
FIG. 2 is an SEM photograph of example 1 with Fe-Cu added.
FIG. 3 is a graph of the current with Fe-Cu addition as a function of voltage for example 1.
FIG. 4 is a graph of the change of dielectric constant with frequency for the addition of Fe-Cu of example 1.
Detailed Description
The invention provides a Cu-based alloy2+Formation of CuAl in alumina porcelain2O4Method for preparing black alumina ceramic by using Cu as main colorant2+Forming CuAl at the grain boundary of alumina porcelain body2O4As a main colorant, Fe3+、Mn2+Preparation as auxiliary doping elementBlack alumina ceramic. The method comprises the steps of adding copper salt, iron salt and manganese salt into a proper solvent according to a certain molar ratio for dissolving, and simultaneously introducing tetraethoxysilane as SiO2The source is fully mixed with the alumina base material to form porcelain, and the porcelain is formed and sintered into the required black alumina ceramic under certain conditions. Method of Cu2+Adding into main colorant, adding iron element to make the color darker and form ceramic body with lower copper adding amount, Mn element for forming black colorant with copper element, introducing certain amount of ethyl orthosilicate as SiO2The source reduces the sintering temperature of the alumina and can adsorb impurities at the same time. The invention is further illustrated by the following examples:
example 1
Dissolving 3g of ethyl orthosilicate in absolute ethyl alcohol to prepare SiO-containing solution2The solution A of (1.56 g) of Cu (NO) was weighed3)2·6H2O and 5.82gFe (NO)3)3·9H2Dissolving O in 30ml of absolute ethyl alcohol to prepare solution B, weighing 20g of alumina powder, adding 1ml of deionized water into the alumina powder, and mixing the solution A and the solution B with the alumina powder; then 5.2g of 25% ammonia water is added to adjust the pH value to be neutral, after uniform mixing, the mixture is washed and dried to prepare porcelain, and then the porcelain is ground, pressed into a piece by 2MPa, and sintered at 1250 ℃. The fired sample is completely black and uniform in color and luster, and meets the requirement of ceramic body on opacity. FIG. 1 shows the XRD pattern of a sintered ceramic sample with three major secondary phases, CuAl, in addition to the primary crystalline phase2O4、Fe3O4And CuO. Wherein CuAl2O4Is the main colorant needed, CuO is the auxiliary colorant, and a trace amount of Fe3O4Color depth may also be increased. Fig. 2 is an SEM image of a cross section of the ceramic, and it can be seen that the material fracture is a transgranular fracture, and the alumina ceramic has high strength, so that the strength of the material is satisfactory. FIG. 3 is a graph of the current versus voltage of the sample from which a resistivity of about 2X 10 can be calculated10Omega cm. FIG. 4 is a graph showing the variation of dielectric constant with frequency, and it can be seen that at 50Hz power frequency, the dielectric constant is about 70 atThe 1kHz drops rapidly below 20.
Claims (2)
1. With Cu2+Formation of CuAl in alumina porcelain2O4The method for preparing black alumina ceramics by using Cu as a main colorant is characterized in that2+Forming CuAl at the grain boundary of alumina porcelain body2O4As a main colorant, Fe3+ 、Mn2+Preparing black alumina ceramic as an auxiliary doping element; the method comprises the steps of adding copper salt, iron salt and manganese salt into a proper solvent according to a certain molar ratio for dissolving, and simultaneously introducing a certain amount of tetraethoxysilane as SiO2The source is fully mixed with the alumina base material to form porcelain, and the porcelain is formed and sintered into the required black alumina ceramic under certain conditions; the Cu2+Adding into main colorant, adding iron element to make the color darker and form ceramic body with lower copper adding amount, Mn element for forming black colorant with copper element, introducing certain amount of ethyl orthosilicate as SiO2The source reduces the sintering temperature of the alumina and can adsorb impurities; the specific process steps are as follows:
1) dissolving tetraethoxysilane in absolute ethyl alcohol completely to prepare SiO-containing2The solution A of (1); the molar ratio of the ethyl orthosilicate to the alumina base material in the solution A is 0.01-10 mol%;
2) soluble Fe with a certain molar ratio3+ 、Cu2+ 、Mn2+Dissolving the salt in a certain solvent to prepare solution B; cu as a colorant in solution B2+The doping amount of (A) is 2-20 mol% and Fe3+The doping amount is 0-10% mol, Mn2+The doping amount is 0-10% mol;
3) adding the solution A and the solution B into an alumina base material according to a certain proportion, fully mixing, simultaneously adjusting the pH value to be neutral by using a certain amount of ammonia water or ammonium bicarbonate, washing with water, and drying to form a porcelain material;
4) and grinding the dried porcelain, tabletting and forming, and sintering at 1200-1300 ℃ to obtain the black alumina ceramic.
2. Cu according to claim 12+Formation of CuAl in alumina porcelain2O4The method for preparing the black alumina ceramic by taking the black alumina ceramic as a main colorant is characterized in that the sintering temperature of the ceramic formed by tabletting is 1250 ℃; to obtain Cu2+Forming CuAl at the grain boundary of alumina porcelain body2O4The black alumina ceramic prepared by taking the black alumina ceramic as the main colorant has the advantages of uniform internal structure, good shading degree, 5-80 of dielectric constant and resistivity>2×1010Ω·cm。
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