Black color material for ceramic substrate, and preparation method and application thereof

Abstract

This invention discloses a black pigment for ceramic substrates, its preparation method, and its application, belonging to the field of ceramic substrate technology. The black pigment comprises the following raw materials in molar mass parts: 1-3 parts V₂O₅, 3-5 parts Al₂O₃, 1-3 parts Sm₂O₃, 0.5-4 parts Y₂O₃, 0.5-4 parts Cr₂O₃, and 0.5-4 parts Fe₂O₃. The black pigment is prepared by a solid-state method. The black pigment provided by this invention is cobalt-free, low in cost, and contains low levels of heavy metals, resulting in lower harm to human health during actual production. Black ceramics with this pigment exhibit good color rendering and color stability at high temperatures of 1000℃-1600℃. Furthermore, the electrical properties of black ceramics with this pigment, such as volume resistivity, meet the requirements for encapsulation ceramics. The black pigment of this invention can be widely used in the preparation of various black ceramics, such as alumina, zirconium oxide, and aluminum nitride encapsulation ceramics.

Description

Technical Field

[0001] This invention belongs to the field of ceramic substrate technology, specifically relating to a black pigment for ceramic substrates, its preparation method, and its application. Background Technology

[0002] Microelectronics technology demands that device packaging be dense, thin, fast, and heat-dissipating. Packaging substrates must meet these requirements. Currently, there are many types of electronic packaging substrates, commonly categorized as plastic, metal, and ceramic. Commonly used ceramic substrate materials include alumina, aluminum nitride, zirconium oxide, silicon nitride, silicon carbide, boron nitride, and beryllium oxide. Because ceramic substrates require consideration of photosensitivity and light-shielding properties in applications, the selection of black pigments must comprehensively consider multiple performance requirements of ceramic materials, including but not limited to high resistivity, high-temperature color stability, reduced sintering temperature, and reduced actual production costs. Therefore, developing suitable black pigments can broaden and deepen the application fields of packaging ceramic materials.

[0003] Currently, black pigments for ceramic substrates generally fall into two main categories: cobalt black and cobalt-free black. In cobalt black pigments, a large amount of Co2O3 needs to be introduced to obtain a black pigment with a low blackness value; however, the high price of Co2O3 leads to high production costs. In cobalt-free black pigments, such as Fe-Cr and Fe-Cr-Ni-Mn spinel-type pigments, the heavy metal oxides of cobalt, nickel, chromium, and manganese pose health hazards and pollute the environment during production. Therefore, developing new black pigments that are low-cost, environmentally friendly, and have stable color development is crucial. Summary of the Invention

[0004] In view of this, the present invention provides a black pigment for ceramic substrates, which has the advantages of low cost, environmental protection and stable color development.

[0005] The present invention also provides a method for preparing the black pigment for the ceramic substrate.

[0006] The present invention also provides the application of the black pigment for the ceramic substrate.

[0007] The technical solution adopted by this invention to solve its technical problem is as follows:

[0008] A black pigment for ceramic substrates comprises the following raw materials in molar mass parts: 1-3 parts V2O5, 3-5 parts Al2O3, 1-3 parts Sm2O3, 0.5-4 parts Y2O3, 0.5-4 parts Cr2O3, and 0.5-4 parts Fe2O3.

[0009] A method for preparing a black pigment for a ceramic substrate includes the following steps:

[0010] (1) Mix V2O5, Al2O3, Sm2O3, Fe2O3, Y2O3 and Cr2O3 powders in proportion, add deionized water, and ball mill the mixture. The product is dried and ground to obtain yellowish-brown pigment raw powder.

[0011] (2) Place the yellowish-brown pigment powder in a hydrogen furnace and sinter it to obtain a black pigment for ceramic substrates.

[0012] Preferably, in step (1), deionized water is added as the grinding medium during the ball milling stage, the ball mill speed is set to 400 rpm, and the ball milling time is 4 hours.

[0013] Preferably, in step (1), the drying temperature is 100°C and the drying time is 4 to 5 hours.

[0014] Preferably, in step (2), the sintering process is as follows: the temperature is raised to 1150°C at a heating rate of 5°C / min, held for 30 minutes, and then cooled down to room temperature with the furnace before being taken out.

[0015] Preferably, in step (2), the black pigment obtained by sintering is ball-milled and then passed through a 300-mesh sieve to break up agglomerates and reduce the particle size of the pigment, thereby improving the color development performance of the pigment.

[0016] The application of the black pigment for ceramic substrates in the preparation of black ceramic substrates is as follows: the black pigment is mixed with encapsulated ceramic powder, and then dispersant, binder, plasticizer, solvent, etc. are added. After the mixture is completely mixed, it is degassed under vacuum, cast on a casting machine, dried, debonded, and sintered to obtain a black ceramic substrate.

[0017] Preferably, the encapsulating ceramic is any one of alumina, zirconium oxide, and aluminum nitride.

[0018] Preferably, the encapsulating ceramic is alumina, and the weight of the black pigment is 5-12 wt% of the total mass of the alumina powder.

[0019] As can be seen from the above technical solution, the present invention provides a black pigment for ceramic substrates, its preparation method, and its application. Compared with the prior art, its advantages are:

[0020] The black pigment for ceramic substrates described in this invention introduces Sm2O3, Y2O3, and V2O5 into Cr2O3 and Fe2O3. Sm2O3, Y2O3, and V2O5 react with each other in a reducing atmosphere to generate SmVO3, YVO4, and a small amount of YVO3. These three vanadates serve as the main coloring agents, enabling the ceramic material to exhibit excellent coloring effect and color stability. The introduction of Al2O3 allows for the production of a glassy phase during pigment sintering, suppressing pigment volatilization and appropriately lowering the sintering temperature of the ceramic material. Furthermore, since the transport mechanism during ceramic densification is grain boundary diffusion, the use of rare earth oxides such as Sm2O3, Y2O3, and V2O5 can reduce the densification rate of the ceramic, effectively suppressing volume shrinkage during crystal transformation. The reaction of these rare earth oxides with Al2O3 generates fine particles distributed at the grain boundaries, which can restrict grain boundary movement and prevent crack propagation, resulting in ceramics with excellent properties. The black pigment provided by this invention is a cobalt-free pigment, which is low in cost and contains a low amount of heavy metals, thus posing less harm to the human body in actual production. Black ceramics with this pigment exhibit good color rendering and color stability at high temperatures of 1000℃ to 1600℃. Furthermore, the electrical properties of black ceramics with this pigment, such as volume resistivity, meet the requirements for encapsulation ceramics. The black pigment of this invention can be widely used in the preparation of various black ceramics, such as alumina, zirconium oxide, and aluminum nitride encapsulation ceramics. Attached Figure Description

[0021] Figure 1 These are images of black pigment samples prepared in comparative examples and Examples 1-3.

[0022] Figure 2 This is the ultraviolet reflectance spectrum of the black pigments prepared in the comparative examples and Examples 1-3.

[0023] Figure 3 This is the band gap width of the black pigment prepared in the comparative example and Example 3.

[0024] Figure 4 It is the volume resistivity of a black porcelain sample prepared when the pigment addition amount is 8%wt. Detailed Implementation

[0025] The technical solutions and effects of the embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0026] This invention provides a black pigment for ceramic substrates, comprising the following molar mass parts of raw materials: 1-3 parts V2O5, 3-5 parts Al2O3, 1-3 parts Sm2O3, 0.5-4 parts Y2O3, 0.5-4 parts Cr2O3, and 0.5-4 parts Fe2O3.

[0027] The black pigment for ceramic substrates described in this invention introduces Sm2O3, Y2O3, and V2O5 into Cr2O3 and Fe2O3. Sm2O3, Y2O3, and V2O5 react with each other in a reducing atmosphere to generate SmVO3, YVO4, and a small amount of YVO3. These three vanadates serve as the main coloring substances, enabling the ceramic material to exhibit excellent coloring effect and color stability. The introduction of Al2O3 allows for the production of a glassy phase during sintering, suppressing the volatilization of the pigment and appropriately lowering the sintering temperature of the ceramic material. Furthermore, since the transport mechanism during ceramic densification is grain boundary diffusion, the use of rare earth oxides such as Sm2O3, Y2O3, and V2O5 can reduce the densification rate of the ceramic, effectively suppressing volume shrinkage during crystal transformation. The reaction of these rare earth oxides with Al2O3 generates fine particles distributed at the grain boundaries, which can restrict grain boundary movement and prevent crack propagation, resulting in ceramics with excellent properties. The black pigment provided by this invention is a cobalt-free pigment, which is low in cost and contains a low amount of heavy metals, thus posing less harm to the human body in actual production. Black ceramics with this pigment exhibit good color rendering and color stability at high temperatures of 1000℃ to 1600℃. Furthermore, the electrical properties of black ceramics with this pigment, such as volume resistivity, meet the requirements for encapsulation ceramics. The black pigment of this invention can be widely used in the preparation of various black ceramics, such as alumina, zirconium oxide, and aluminum nitride encapsulation ceramics.

[0028] The present invention also provides a method for preparing the black pigment for the ceramic substrate, comprising the following steps:

[0029] (1) Mix V2O5, Al2O3, Sm2O3, Fe2O3, Y2O3 and Cr2O3 powders in proportion, add deionized water, and ball mill the mixture. The product is dried and ground to obtain yellowish-brown pigment raw powder.

[0030] (2) Place the yellowish-brown pigment powder in a hydrogen furnace and sinter it to obtain a black pigment for ceramic substrates.

[0031] Furthermore, in step (1), deionized water is added as the grinding medium during the ball milling stage, the ball mill speed is set to 400 rpm, and the ball milling time is 4 hours.

[0032] Furthermore, in step (1), the drying temperature is 100℃ and the drying time is 4-5h.

[0033] Furthermore, in step (2), the sintering process is as follows: the temperature is raised to 1150°C at a heating rate of 5°C / min, held for 30 minutes, and then cooled down to room temperature with the furnace before being taken out.

[0034] Furthermore, in step (2), the black pigment obtained by sintering is ball-milled and then passed through a 300-mesh sieve to break up agglomerates and reduce the particle size of the pigment, thereby improving the color rendering performance of the pigment.

[0035] The application of the black pigment for ceramic substrates in the preparation of black ceramic substrates is as follows: the black pigment is mixed with encapsulated ceramic powder, and then dispersant, binder, plasticizer, solvent, etc. are added. After the mixture is completely mixed, it is degassed under vacuum, cast on a casting machine, and then dried, debonded, and sintered to obtain a black ceramic substrate.

[0036] Specifically, the encapsulating ceramic is any one of alumina, zirconium oxide, and aluminum nitride.

[0037] Specifically, the encapsulating ceramic is alumina, and the weight of the black pigment is 5-12 wt% of the total mass of the alumina powder.

[0038] The following are specific comparative examples and embodiments:

[0039] Comparative example:

[0040] Preparation of black pigment: The molar mass ratio of V2O5:Al2O3:Sm2O3:Y2O3:Cr2O3:Fe2O3 was weighed in the form of 1:3:0:3:3:3, with a total weight of 13.382g. The mixed powder was placed in a ball mill jar, and 40g of grinding balls and 50mL of deionized water were added. The mixture was ball-milled in a planetary ball mill at 400rpm for 4h to ensure thorough mixing. The resulting mixed powder slurry was dried at 100℃ for 4-5h. After drying and grinding, the product was used to obtain a yellowish-brown pigment powder. The larger particles in the powder were ground, placed in a crucible, and sintered in a hydrogen furnace at 1150℃ for 30min. After the sintering was completed, the powder was cooled with the furnace to obtain black pigment powder. The sintered black pigment was ball-milled and crushed, passed through a 300-mesh sieve, and deionized water was added. After ball milling, the powder was dried at 100℃ to obtain the black pigment, named A01.

[0041] Preparation of black ceramic substrate: Black pigment is mixed with alumina powder, and the weight of black pigment is 5-12 wt% of the total mass of powder. Dispersant, binder, plasticizer, solvent and other organic additives are added. After the mixture is completely mixed, vacuum degassing is performed. The mixture is then cast on a casting machine, dried, debonded and sintered to obtain black ceramic substrate.

[0042] Example 1:

[0043] Preparation of black pigment: The molar ratio of V₂O₅:Al₂O₃:Sm₂O₃:Y₂O₃:Cr₂O₃:Fe₂O₃ was weighed in the range of 1:3:1.1:1.1:1.1, totaling 20.716 g. The mixed powder was placed in a ball mill jar, along with 60 g of grinding balls and 50 mL of deionized water. The mixture was then ball-milled at 400 rpm for 4 hours in a planetary ball mill to ensure thorough mixing. The resulting mixed powder slurry was then... The product was dried at 100℃ for 4-5 hours. After drying and grinding, a yellowish-brown pigment powder was obtained. The larger particles in the powder were ground, placed in a crucible, and sintered in a hydrogen furnace at 1150℃ for 30 minutes. After the holding time, the powder was cooled with the furnace to obtain a black pigment powder. The sintered black pigment was ball-milled, crushed, and passed through a 300-mesh sieve. Deionized water was added, and the mixture was ball-milled again. The product was then dried at 100℃ to obtain a black pigment, named A02.

[0044] Preparation of black ceramic substrate: Black pigment is mixed with alumina powder, and the weight of black pigment is 5-12 wt% of the total mass of powder. Dispersant, binder, plasticizer, solvent and other organic additives are added. After the mixture is completely mixed, vacuum degassing is performed. The mixture is then cast on a casting machine, dried, debonded and sintered to obtain black ceramic substrate.

[0045] Example 2:

[0046] Preparation of black pigment: The molar ratio of V2O5:Al2O3:Sm2O3:Y2O3:Cr2O3:Fe2O3 was weighed in a ratio of 1:3:3:1:1:1, with a total weight of 15.077g. The mixed powder was placed in a ball mill jar, and 45g of grinding balls and 50mL of deionized water were added. The mixture was ball-milled in a planetary ball mill at 400rpm for 4h to ensure thorough mixing. The resulting mixed powder slurry was dried at 100℃ for 4-5h. After drying and grinding, the product was used to obtain a yellowish-brown pigment powder. The larger particles in the powder were ground, placed in a crucible, and sintered in a hydrogen furnace at 1150℃ for 30min. After the sintering was completed, the powder was cooled with the furnace to obtain black pigment powder. The sintered black pigment was ball-milled, crushed, and passed through a 300-mesh sieve. Deionized water was added, and the mixture was ball-milled again. The powder was then dried at 100℃ to obtain the black pigment, named A03.

[0047] Preparation of black ceramic substrate: Black pigment is mixed with alumina powder, and the weight of black pigment is 5-12 wt% of the total mass of powder. Dispersant, binder, plasticizer, solvent and other organic additives are added. After the mixture is completely mixed, vacuum degassing is performed. The mixture is then cast on a casting machine, dried, debonded and sintered to obtain black ceramic substrate.

[0048] Example 3:

[0049] Preparation of black pigment: The molar ratio of V₂O₅:Al₂O₃:Sm₂O₃:Y₂O₃:Cr₂O₃:Fe₂O₃ was weighed at 2:3.5:1:0.5:0.5, totaling 21.004 g. The mixed powder was placed in a ball mill jar, along with 63 g of grinding balls and 50 mL of deionized water. The mixture was then ball-milled at 400 rpm for 4 hours in a planetary ball mill to ensure thorough mixing. The resulting mixed powder slurry was then... The product was dried at 100℃ for 4-5 hours. After drying and grinding, a yellowish-brown pigment powder was obtained. The larger particles in the powder were ground, placed in a crucible, and sintered in a hydrogen furnace at 1150℃ for 30 minutes. After the holding time, the powder was cooled with the furnace to obtain a black pigment powder. The sintered black pigment was ball-milled, passed through a 300-mesh sieve, and deionized water was added. After ball milling, the powder was dried at 100℃ to obtain a black pigment, named A04.

[0050] Preparation of black ceramic substrate: Black pigment is mixed with alumina powder, and the weight of black pigment is 5-12 wt% of the total mass of powder. Dispersant, binder, plasticizer, solvent and other organic additives are added. After the mixture is completely mixed, vacuum degassing is performed. The mixture is then cast on a casting machine, dried, debonded and sintered to obtain black ceramic substrate.

[0051] The spectral reflectance curve of the sample was measured using a UV spectrophotometer. Pigments themselves possess certain intrinsic frequencies, which can be absorbed by light and, under appropriate conditions, can also emit radiation. When their intrinsic frequencies fall within the visible light range, the pigment will exhibit the corresponding color. There is a certain relationship between the absorption and reflection spectra of a substance and the color seen; therefore, the characteristics of an object's absorption or reflection curve can identify the object's color and properties. The lower the reflectance of a black pigment, the more the sample absorbs, meaning the better the color rendering. Figure 1 These are images of black pigment samples prepared in comparative examples and Examples 1-3. Figure 2 The ultraviolet absorption spectra of the black pigments prepared in the comparative examples and Examples 1-3 are shown. Figure 2 In the middle, #1-4 represent A01-04. (This is from...) Figure 1-2 It can be seen that the black pigment prepared in the comparative example without Sm2O3 has a lighter color, while the black pigment samples prepared in each example with added Sm2O3 have better color. Among them, the black pigment prepared by the ratio in Example 3 has the best color, and its band gap result is as follows: Figure 3 .

[0052] Table 1 shows the volume resistivity test results of the black pigment samples prepared in comparative examples and Examples 1-3. It can be seen that the black pigment formulations with a certain molar ratio produce pigments with high volume resistivity at room temperature, all exceeding 10⁻⁶. 10 Ω·cm.

[0053] Table 1. Results of volume resistivity test on pigment samples

[0054]

[0055] The pigment formulation with higher resistivity, as described in Example 1, was selected and added to alumina at a ratio of 5% wt-12% wt to prepare black porcelain via casting. Its resistivity was then tested. The results are shown in Table 2. The resistivity of the prepared black porcelain sample was greater than 10 Ω·cm. 13 Ω·cm.

[0056] Table 2 Resistivity test results of black porcelain samples

[0057]

[0058]

[0059] When the amount of pigment added is 8%wt, the volume resistivity of the black ceramic substrate sample is... Figure 4 As shown, this pigment formulation can be used in the preparation of black ceramic substrates, and it can give the black ceramic substrates good electrical properties.

[0060] The above-disclosed embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of the invention. Those skilled in the art will understand that implementing all or part of the above-described embodiments and making equivalent changes in accordance with the claims of the present invention are still within the scope of the invention.

Claims

1. A black color material for a ceramic substrate, characterized by: The raw materials include the following molar mass parts: 1-3 parts V2O5, 3-5 parts Al2O3, 1-3 parts Sm2O3, 0.5-4 parts Y2O3, 0.5-4 parts Cr2O3, and 0.5-4 parts Fe2O3. The above raw materials are prepared into a black pigment for ceramic substrates according to the following steps: (1) Mix V2O5, Al2O3, Sm2O3, Fe2O3, Y2O3, and Cr2O3 powders in proportion, add deionized water, and ball mill the mixture. The product is dried and ground to obtain a yellowish-brown pigment powder. (2) Place the yellowish-brown pigment powder in a hydrogen furnace for sintering to obtain a black pigment for ceramic substrates.

2. The method of producing a black color material for a ceramic substrate according to claim 1, characterized by: Includes the following steps: (1) Mix V2O5, Al2O3, Sm2O3, Fe2O3, Y2O3 and Cr2O3 powders in proportion, add deionized water, and ball mill the mixture. The product is dried and ground to obtain yellowish-brown pigment raw powder. (2) Place the yellowish-brown pigment powder in a hydrogen furnace for sintering to obtain a black pigment for ceramic substrates.

3. The method for preparing black pigment for ceramic substrates as described in claim 2, characterized in that: In step (1), deionized water is added as the grinding medium during the ball milling stage, the ball mill speed is set to 400 rpm, and the ball milling time is 4 hours.

4. The method for preparing black pigment for ceramic substrates as described in claim 2, characterized in that: In step (1), the drying temperature is 100℃ and the drying time is 4-5h.

5. The method for preparing black pigment for ceramic substrates as described in claim 2, characterized in that: In step (2), the sintering process is as follows: the temperature is raised to 1150°C at a heating rate of 5°C / min, held for 30 minutes, and then cooled down to room temperature with the furnace before being taken out.

6. The method for preparing black pigment for ceramic substrates as described in claim 2, characterized in that: In step (2), the black pigment obtained by sintering is ball-milled and then passed through a 300-mesh sieve to break up agglomerates and reduce the particle size of the pigment, thereby improving the color rendering performance of the pigment.

7. The application of the black pigment for ceramic substrates as described in claim 1 in the preparation of black ceramic substrates, characterized in that: The ceramic substrate is mixed with black pigment and encapsulated ceramic powder, and then dispersant, binder, plasticizer and solvent are added. After the mixture is completely mixed, it is degassed under vacuum and cast on a casting machine. After drying, debinding and sintering, a black ceramic substrate is obtained.

8. The application of the black pigment for ceramic substrates as described in claim 7 in the preparation of black ceramic substrates, characterized in that: The encapsulating ceramic is any one of alumina, zirconium oxide, and aluminum nitride.

9. The application of the black pigment for ceramic substrates as described in claim 8 in the preparation of black ceramic substrates, characterized in that: The encapsulating ceramic is alumina, and the weight of the black pigment is 5-12 wt% of the total mass of the alumina powder.

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