CN110723977A - With Cu2+Formation of black CuAl in alumina porcelain2O4Method for preparing black alumina ceramic by using main colorant - Google Patents

With Cu2+Formation of black CuAl in alumina porcelain2O4Method for preparing black alumina ceramic by using main colorant Download PDF

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CN110723977A
CN110723977A CN201910783835.1A CN201910783835A CN110723977A CN 110723977 A CN110723977 A CN 110723977A CN 201910783835 A CN201910783835 A CN 201910783835A CN 110723977 A CN110723977 A CN 110723977A
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alumina
porcelain
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马振伟
谢佳琪
周吉祥
韩秀梅
李妍
余路平
张昊
谢佳慧
齐建全
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Northeastern University Qinhuangdao Branch
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Abstract

The invention discloses a Cu-based coloring agent, which belongs to the technical field of coloring of alumina ceramics2+Formation of black CuAl in alumina porcelain2O4A method for preparing black alumina ceramics by using the black alumina ceramics as a main colorant. 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, fully mixing with an alumina base material to form a porcelain, grinding, forming, and sintering at 1250 ℃ in an abstract manner to prepare the required black alumina ceramic. The method can successfully obtain alumina ceramics with qualified color, avoids the expensive cobalt oxide and toxic chromium oxide which are required in the common preparation of black alumina, and can reduce the sintering temperature of alumina by adding the copper oxide to obtain the alumina ceramics at a lower temperatureThe black alumina ceramic has good dielectric property, high resistivity, uniform internal structure and high strength.

Description

Method for preparing black alumina ceramic by taking Cu2+ to form black CuAl2O4 in alumina ceramic as main colorant
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 black CuAl in alumina porcelain2O4A method for preparing black alumina ceramics by using the black alumina ceramics as a main colorant.
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 the pre-synthesis method, the oxide powder is sintered into hard blocks and is difficult to crush because the synthesis temperature is too high (1300 ℃), the diffusion rate between transition metal oxides is increased and is sufficientAnd (3) reacting to achieve dense sintering: 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: not only ensure ceramic baseThe blackness and mechanical strength of the plate color are also required to ensure the insulation and thermal properties of the ceramic substrate and other properties required for use as an electronic device.
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 black CuAl in alumina porcelain2O4The method for preparing black alumina ceramics by using Cu as a main colorant is characterized in that2+Black CuAl is formed 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 molded 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-containing2Solution A of (A)；
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+Black CuAl is formed 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*1010·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.
FIG. 5 is a xrd graph showing the addition of Fe-Cu-Mn in example 2.
FIG. 6 is an SEM photograph of example 2 with Fe-Cu added.
FIG. 7 is a graph of the current with the addition of Fe-Cu-Mn as a function of voltage for example 1.
FIG. 8 is a graph of the dielectric constant with frequency for the addition of Fe-Cu-Mn of example 2.
Detailed Description
The invention provides a Cu-based alloy2+Formation of black CuAl in alumina porcelain2O4Method for preparing black alumina ceramic by using Cu as main colorant2+Black CuAl is formed 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 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
Adding 3g of ethyl orthosilicateDissolving in absolute ethanol to obtain 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 CuAl2O4It is the main colorant we need, CuO is the auxiliary colorant, both are black materials. 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 calculated10. FIG. 4 shows the dielectric constant as a function of frequency, and it can be seen that at 50Hz power frequency, the dielectric constant is about 70, and rapidly decreases to below 20 at 1 kHz.
Example 2
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 7.3g 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 pieces under 2MPa and sintered at 1230 ℃. The fired sample appeared completely black and uniform in color and luster, and satisfied the opacity requirement of the ceramic body, and FIG. 1 is an XRD pattern of the sintered ceramic sample, in which three main crystal phases are presentRespectively is CuMnAlO4、Fe3O4And CuO. Wherein CuMnAlO4Is the main colorant we need, can be regarded as CuAl2O4One Al atom in the alloy is replaced by one Mn atom. CuO is a secondary colorant, both of which are black materials. Trace amount of Fe3O4Color depth may also be increased. FIG. 2 is an SEM image of a ceramic cross section, and it can be seen that the material fracture belongs to transgranular fracture, and the alumina ceramic has high strength, so that the strength of the material can meet the requirement. FIG. 3 is a plot of the current versus voltage of a sample from which a resistivity of about 4X 10 can be calculated10. FIG. 4 is a graph of the dielectric constant as a function of frequency, and it can be seen that the dielectric constant is about 65 at 50Hz power frequency and rapidly decreases to 40 or less at 1 kHz.

Claims (6)

1. With Cu2+Formation of black CuAl in alumina porcelain2O4The method for preparing black alumina ceramics by using Cu as a main colorant is characterized in that2+Black CuAl is formed 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 molded 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 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.
2. Cu according to claim 12+Formation of black CuAl in alumina porcelain2O4The method for preparing the black alumina ceramic by taking the black alumina ceramic as the main colorant is characterized in that in the step 2), soluble Fe3+、Cu2+、Mn2+The salt of (A) is at least one or more of nitrate, acetate, sulfate and chloride.
3. Cu according to claim 12+Formation of black CuAl in alumina porcelain2O4The method for preparing the black alumina ceramic by taking the tetraethoxysilane as the main colorant is characterized in that in the step 3), the molar ratio of the tetraethoxysilane to the alumina base material in the solution A is 0.01-10 mol%.
4. Cu according to claim 12+Formation of black CuAl in alumina porcelain2O4The method for preparing the black alumina ceramic by taking the Cu as the main colorant is characterized in that in the step 3), the Cu as the colorant in the B solution2+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%.
5. Cu according to claim 12+Formation of black CuAl in alumina porcelain2O4The method for preparing the black alumina ceramic by taking the black alumina ceramic as the main colorant is characterized in that the solvent is at least one or more of water, methanol, ethanol and glycol.
6. Cu according to claim 12+Formation of black 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 1200-1300 ℃; to obtain Cu2+Black CuAl is formed 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*1010·cm。
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CN112851310A (en) * 2021-01-26 2021-05-28 西安钛斗金属制品科技有限公司 Preparation method of composite black ceramic
CN114262212A (en) * 2021-12-27 2022-04-01 广东泛瑞新材料有限公司 Black alumina ceramic particle material and preparation method and application thereof
CN117585990A (en) * 2023-12-04 2024-02-23 新化县正能精细陶瓷有限公司 Black alumina-based ceramic substrate and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112851310A (en) * 2021-01-26 2021-05-28 西安钛斗金属制品科技有限公司 Preparation method of composite black ceramic
CN114262212A (en) * 2021-12-27 2022-04-01 广东泛瑞新材料有限公司 Black alumina ceramic particle material and preparation method and application thereof
CN114262212B (en) * 2021-12-27 2022-10-28 广东泛瑞新材料有限公司 Black alumina ceramic particle material and preparation method and application thereof
CN117585990A (en) * 2023-12-04 2024-02-23 新化县正能精细陶瓷有限公司 Black alumina-based ceramic substrate and preparation method thereof
CN117585990B (en) * 2023-12-04 2024-05-17 新化县正能精细陶瓷有限公司 Black alumina-based ceramic substrate and preparation method thereof

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