Alumina ceramic composite colloid metallized tungsten slurry and preparation method and application thereof

Abstract

The invention provides aluminum oxide ceramic composite colloid metallized tungsten slurry and a preparation method and application thereof.The tungsten slurry comprises, by mass, 70%-90% of conductive metal tungsten powder, 1%-15% of an inorganic bonding phase, 5%-25% of an organic carrier A and 1%-10% of an organic carrier B; wherein the organic carrier A comprises 10%-25% of an organic binder, 5%-40% of a plasticizer, 5%-90% of a solvent and 1%-5% of modified montmorillonite; the organic carrier B comprises 5%-20% of an organic binder, 10%-60% of a plasticizer and 5%-90% of a solvent; the modified montmorillonite is polyether polyol modified montmorillonite. By compounding the organic carrier A and the organic carrier B, the flowability, thixotropy and printing resolution of the paste are improved, the paste has good sintering matching property with a ceramic substrate, high flatness and strong adhesive force, and other multilayer ceramic process requirements such as lamination, lamination and raw cutting can be met.

Description

Technical Field

[0001] The present invention relates to the technical field of high-temperature co-fired ceramic slurries, and in particular to an alumina ceramic composite colloidal metallized tungsten slurry, a preparation method thereof, and applications thereof. Background Art

[0002] With the rapid advancement of electronics technology, the research and application of high-temperature co-fired ceramics (HTCCs) in materials science and electronic engineering have garnered widespread attention. Electrostatic chuck manufacturing, a cutting-edge technology in HTCCs, achieves stable clamping through precise electrostatic adsorption, significantly improving machining accuracy and production efficiency while reducing scrap rates. This provides solid technical support for the development and production of high-performance chips.

[0003] In recent years, domestic electrostatic chucks have made significant progress in technological innovation and market application. The patents for the new generation of electrostatic chucks involve the design of high-efficiency electrodes, intelligent control systems, and the application of new wear-resistant materials, which significantly enhance the clamping force and stability. The introduction of intelligent control technology makes real-time monitoring and simplified operation possible, adapting to the high-precision needs of the microelectronics and optoelectronics industries. In addition, with the rapid development of the semiconductor and precision processing markets, domestic electrostatic chucks have gradually replaced imported products, enhancing the industry's independent control capabilities. With the vigorous development of 5G communications, the Internet of Things, and smart devices, the demand for high-performance domestic chip materials continues to increase, further promoting the innovation and progress of electrostatic chuck technology and putting forward higher industry requirements.

[0004] The key to electrostatic chuck manufacturing lies in the co-firing of ceramic and conductive slurry. This process requires effective control of the interfacial reaction and diffusion between the ceramic and metal slurries to ensure a good match between the ceramic material and the slurry. To achieve this, the densification rate, sintering shrinkage, and thermal expansion rate of the interface layer must be kept consistent to minimize the risk of defects such as delamination, warping, and cracking. The result is an electrostatic chuck with low sintered surface roughness, good slurry adhesion, and stable sheet resistance.

[0005] Conductive tungsten paste is widely used in electronic devices and sensors due to its superior conductivity and high-temperature resistance. However, in practical applications, conductive tungsten paste faces issues such as stability and dispersibility, which significantly impact its performance and reliability. First, conductive tungsten paste lacks stability, making it prone to delamination and sedimentation, especially during long-term storage or transportation. This not only leads to uneven slurry composition, affecting conductivity, but can also cause inconsistent quality of the finished product during production. Furthermore, tungsten particles in conductive tungsten paste often aggregate, resulting in poor dispersion. This aggregation leads to uneven conductive paths, thereby reducing the overall performance of the electrode or sensor. Second, as the high-temperature sintering process progresses, tungsten particle oxidation and aggregation become increasingly prominent, further impacting the performance of the conductive tungsten paste. These issues urgently need to be addressed to promote the widespread application of conductive tungsten paste in electrostatic chuck manufacturing. Therefore, in-depth research on the stability and dispersibility of conductive tungsten paste will provide important support for improving the performance of high-temperature ceramic materials and the development of new electronic devices. Summary of the Invention

[0006] In response to the above problems, the present invention provides an alumina ceramic composite colloidal metallized tungsten paste, which can not only solve the problems of insufficient adhesion and unstable conductivity in common printed tungsten pastes on the market, but also ensure that the conductive tungsten paste has good printing performance.

[0007] The first aspect of the present invention provides an alumina ceramic composite colloidal metallized tungsten slurry, characterized in that, by mass percentage, comprising: 70% to 90% conductive metal tungsten powder, 1% to 15% inorganic binder phase, 5% to 25% organic vehicle A, 1% to 10% organic vehicle B;

[0008] Wherein, the organic carrier A comprises: 10% to 25% of an organic binder, 5% to 40% of a plasticizer, 5% to 90% of a solvent, and 1% to 5% of modified montmorillonite;

[0009] The organic carrier B comprises: 5% to 20% of an organic binder, 10% to 60% of a plasticizer and 5% to 90% of a solvent;

[0010] The modified montmorillonite is polyether polyol modified montmorillonite.

[0011] The particle size of the conductive metal tungsten powder is 0.5 μm to 2.5 μm.

[0012] The polyether polyol in the polyether polyol-modified montmorillonite is selected from one or more of PTMEG-1000, PEG-2000, PEG-4000, PEG-6000 or PEG-8000, and more preferably PEG-4000 or PEG-6000.

[0013] The amount of the polyether polyol modified montmorillonite is preferably 2% to 3%.

[0014] The organic binder in the organic carrier A comprises: a mixture of one or more of acrylic resin, phenolic resin and epoxy resin.

[0015] The organic binder in the organic carrier B includes: a mixture of one or more of ethyl cellulose, polyvinyl alcohol, and polyvinyl butyral.

[0016] The inorganic bonding phase comprises: 92% to 99% of Al2O3 powder and 1% to 8% of a sintering aid.

[0017] The organic solvent is selected from one or more mixtures of methanol, ethanol, acetone, benzyl alcohol, diethylene glycol butyl ether acetate, ethylene glycol diacetate, terpineol and butyl carbitol.

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned alumina ceramic composite colloidal metallized tungsten slurry, comprising the following steps:

[0019] (1) Preparation of inorganic binder phase: Al2O3 powder and sintering aid are weighed in proportion and placed in a ball mill. An appropriate amount of dispersant and pure water are added and ball milled for 2 to 6 hours. After ball milling, the slurry is poured into a tray and freeze-dried in a vacuum freeze dryer. After freeze-drying, the powder is vibrated and sieved through a 200-300 mesh sieve for later use.

[0020] (2) Preparation of organic carrier A: weigh the organic binder, modified montmorillonite, plasticizer and solvent in proportion, add the solvent and plasticizer into a stirring and dissolving container and stir evenly, set the heating temperature to 50℃~100℃, and the stirring speed to 150r / min~500r / min, add the organic binder and modified montmorillonite while stirring until they are completely dissolved and evenly dispersed, cool and seal for storage;

[0021] (3) Preparation of organic carrier B: weigh the organic binder, plasticizer and solvent in proportion and add them to a stirring and dissolving container. First add the solvent and plasticizer and stir evenly. Set the heating temperature to 50℃~100℃ and the stirring speed to 150r / min~500r / min. Add the organic binder while stirring until it is completely dissolved and evenly dispersed. Cool and seal the container for storage.

[0022] (4) Preparation of conductive metal tungsten powder mixture: The inorganic binder phase and conductive tungsten powder obtained in step (1) are weighed in proportion and placed in a ball mill, and then an appropriate amount of dispersant and acetone are added to the ball mill and ball milled for 4 h to 24 h; then the organic carrier A in step (2) is weighed in proportion and placed in the ball mill, and ball milled again for 2 to 6 h;

[0023] (5) Preparation of metallized tungsten slurry: After the ball milling in step (4) is completed, the mixture is passed through a 100-200 mesh screen and placed in a vacuum mixer for heating and stirring. The heating temperature is set at 50°C to 100°C. The acetone and other ball milling media are removed by vacuum distillation to obtain a uniform tungsten slurry.

[0024] (6) The organic carrier B in step (3) is weighed in proportion, added to the tungsten slurry obtained in step (5), and then rapidly stirred in a high shear mixer to form a mixed slurry, wherein the stirring speed is 500 r / min to 10,000 r / min and the stirring time is 0.5 h to 1 h; the mixed slurry is then rolled multiple times using a three-axis rolling mill, and the rolling spacing is gradually reduced until the required printing viscosity is met, thereby obtaining the required composite colloidal metallized tungsten electronic slurry for printing.

[0025] A third aspect of the present invention provides a use of the above-mentioned alumina ceramic composite colloidal metallized tungsten slurry in an electrostatic chuck.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] The present invention improves the fluidity, thixotropy and printing resolution of the alumina ceramic composite colloidal metallized tungsten slurry by compounding the organic carrier A and the organic carrier B. It has good sintering matching with the ceramic substrate, high flatness and strong adhesion, and can meet other multi-layer ceramic process requirements such as stacking, lamination and raw cutting. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Composite colloidal metallized tungsten paste screen printing pattern prepared in Example 12

[0029] Figure 2 Composite colloidal metallized tungsten paste screen printing pattern prepared in Example 8

[0030] Figure 3 Composite colloidal metallized tungsten paste screen printing pattern prepared in comparative example 3 DETAILED DESCRIPTION

[0031] Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments including the following examples, and various modifications can be made within the scope that can achieve the object of the invention and does not depart from the gist of the invention.

[0032] In the following examples, unless otherwise specified, the raw materials, reagents or processing techniques used are all commercially available raw materials or conventional processing techniques commonly used in the art.

[0033] The first aspect of the present invention provides an alumina ceramic composite colloidal metallized tungsten slurry, characterized in that, by mass percentage, it comprises: 70% to 90% conductive metal tungsten powder, 1% to 25% inorganic binder phase, 5% to 15% organic vehicle A, 1% to 10% organic vehicle B;

[0034] Wherein, the organic carrier A comprises: 10% to 25% of an organic binder, 5% to 40% of a plasticizer, 5% to 90% of a solvent, and 1% to 5% of modified montmorillonite;

[0035] The organic carrier B comprises: 5% to 20% of an organic binder, 10% to 60% of a plasticizer and 5% to 90% of a solvent;

[0036] The modified montmorillonite is polyether polyol-modified montmorillonite. The long chains of the polyether polyol form a hydrophilic protective layer on the montmorillonite surface, reducing particle agglomeration in the slurry. The polyether polyol-modified montmorillonite acts as a highly effective thixotropic agent, allowing the slurry to quickly regain high viscosity after printing, preventing pattern diffusion and deformation and ensuring high-precision image transfer.

[0037] This invention utilizes both organic carriers A and B, primarily through complementary functions to address core challenges such as process stability, dispersibility, and adhesion that cannot be addressed by a single carrier. Organic carrier A leverages its thixotropy and high-temperature stability to control printing morphology and strengthen the sintered structure; while organic carrier B optimizes process adaptability and adhesion through its fluidity and interfacial wettability.

[0038] In the embodiment of the present invention, the particle size of the conductive metal tungsten powder is 0.5 μm to 2.5 μm.

[0039] <Modified montmorillonite>

[0040] In an embodiment of the present invention, the preparation method of the modified montmorillonite includes: weighing 1-20g of dry montmorillonite and adding it to a solvent, ultrasonically treating it at 50-100°C for 10-90min (power 200-500W), then adding 0.01-5g of polyether polyol, and stirring it at 50-100°C for 2-10h under nitrogen protection; obtaining a mixed solution; centrifuging and washing the mixed solution until it is neutral, vacuum drying, grinding the obtained modified montmorillonite, sieving it, and vacuum drying it for 12 hours for later use.

[0041] In an embodiment of the present invention, the polyether polyol is selected from one or more of PTMEG-1000, PEG-2000, PEG-4000, PEG-6000 or PEG-8000.

[0042] In the embodiment of the present invention, the amount of the polyether polyol is 1-5% of the mass of the montmorillonite.

[0043] <Inorganic Adhesive Phase>

[0044] In the present invention, the inorganic bonding phase comprises: 92% to 99% of Al2O3 powder and 1% to 8% of a sintering aid.

[0045] The sintering aid comprises a rare earth oxide and an alkali metal oxide. Preferably, the rare earth oxide is Y2O3, the alkali metal oxide is MgO, and the sintering aid further comprises talc. The sintering aid comprises 0.25% to 2.5% Y2O3, 0.3% to 5.5% MgO, and 0.05% to 1.5% talc, respectively.

[0046] Preparation method: Al2O3 powder and sintering aid are weighed in proportion and placed in a ball mill, and an appropriate amount of dispersant and pure water are added and ball milled for 2 to 6 hours. After the ball milling is completed, the slurry is poured into a tray and vacuum freeze-dried using a vacuum freeze dryer. After freeze-drying, the powder is vibrated and sieved through a 200-300 mesh sieve for later use.

[0047] The present invention adopts vacuum freeze-drying technology. For spherical or quasi-spherical alumina powder, good particle morphology has a crucial influence on the overall bulk density and dispersibility of the slurry. Since micro cracks are inevitable on the surface of the alumina particles during the ball milling dispersion process, the present invention solves the problem of alumina crystal breakage during the high-temperature drying process of the common slurry preparation process on the market, thereby improving the overall dispersibility and adhesion of the slurry.

[0048] <Organic Carrier A>

[0049] In the embodiment of the present invention, the organic binder in the organic vehicle A comprises a mixture of one or more of acrylic resin, phenolic resin, and epoxy resin. These resins have low cracking temperatures and low carbon residue rates during sintering, thereby improving electrical conductivity and interface reliability.

[0050] In an embodiment of the present invention, the plasticizer comprises: a mixture of one or more of dibutyl phthalate, di-n-butyl adipate, dioctyl phthalate, and dioctyl succinate.

[0051] In an embodiment of the present invention, the organic solvent is selected from one or more mixtures of methanol, ethanol, acetone, benzyl alcohol, diethylene glycol butyl ether acetate, ethylene glycol diacetate, terpineol and butyl carbitol.

[0052] Preparation method: Weigh the organic binder, modified montmorillonite, plasticizer and solvent in proportion, first add the solvent and plasticizer into a stirring and dissolving container and stir evenly, set the heating temperature to 50℃~100℃, and the stirring speed to 150r / min~500r / min, add the organic binder and modified montmorillonite while stirring until they are completely dissolved and evenly dispersed, dissolve for 4~6h, cool and seal for storage.

[0053] <Organic Carrier B>

[0054] In the embodiment of the present invention, the organic binder in the organic carrier B includes: a mixture of one or more of ethyl cellulose, polyvinyl alcohol, and polyvinyl butyral.

[0055] In an embodiment of the present invention, the plasticizer comprises: a mixture of one or more of dibutyl phthalate, di-n-butyl adipate, dioctyl phthalate, and dioctyl succinate.

[0056] In an embodiment of the present invention, the organic solvent is selected from one or more mixtures of methanol, ethanol, acetone, benzyl alcohol, diethylene glycol butyl ether acetate, ethylene glycol diacetate, terpineol and butyl carbitol.

[0057] Preparation method: Weigh the organic binder, plasticizer and solvent in proportion, add them into a stirring and dissolving container, add the solvent and plasticizer first and stir evenly, set the heating temperature to 50℃~100℃, and the stirring speed to 150r / min~500r / min, add the organic binder while stirring until it is completely dissolved and evenly dispersed, cool and seal for storage.

[0058] A second aspect of the present invention provides a method for preparing an alumina ceramic composite colloidal metallized tungsten slurry, comprising the following steps:

[0059] (S1) Preparation of a conductive metal tungsten powder mixture: The inorganic binder and conductive tungsten powder are weighed in appropriate proportions and placed in a ball mill. An appropriate amount of dispersant and acetone are then added to the mill and ball milled for 4 to 24 hours. An organic carrier A is then weighed in appropriate proportions and placed in the mill, and ball milled again for 2 to 6 hours.

[0060] (S2) Preparation of metallized tungsten slurry: After the ball-milled mixture in step (S1) is passed through a 100-200 mesh screen, it is placed in a vacuum mixer and heated and stirred at a temperature of 50°C to 100°C. The acetone and other ball-milling media are removed by vacuum distillation to obtain a uniform tungsten slurry;

[0061] (S3) Weighing an organic carrier B in proportion, adding it to the tungsten slurry obtained in step (S2), and rapidly stirring it in a high shear mixer to form a mixed slurry, wherein the stirring speed is 500 r / min to 10,000 r / min, and the stirring time is 0.5 h to 1 h; then the mixed slurry is rolled multiple times using a three-axis rolling mill, and the rolling spacing is gradually reduced until the required printing viscosity is met, thereby obtaining the required composite colloidal metallized tungsten electronic slurry for printing.

[0062] Example

[0063] The present invention will be described in detail below with reference to specific embodiments. In the following examples, unless otherwise specified, the raw materials, reagents or processing techniques used are all commercially available raw materials or conventional processing techniques commonly used in the art.

[0064] <Preparation of modified montmorillonite>

[0065] Preparation Example 1

[0066] 10 g of dried sodium montmorillonite was weighed and added to 200 mL of N,N-dimethylformamide (DMF). The mixture was ultrasonically treated at 80°C for 30 min (power 300 W), and then 0.5 g of PTMEG-1000 was added. The mixture was stirred at 80°C for 4 h under nitrogen protection to obtain a mixed solution. The mixed solution was centrifuged and washed until neutral, and vacuum-dried at 80°C for 12 h. The modified montmorillonite was ground, sieved with a 300-mesh filter, and vacuum-dried for 12 h for later use, i.e., modified montmorillonite A.

[0067] Preparation Example 2

[0068] 10 g of dried sodium montmorillonite was weighed and added to 200 mL of N,N-dimethylformamide (DMF). The mixture was ultrasonically treated at 80°C for 30 min (power 300 W), and then 0.5 g of PEG-2000 was added. The mixture was stirred at 80°C for 4 h under nitrogen protection to obtain a mixed solution. The mixed solution was centrifuged and washed until neutral, and vacuum-dried at 80°C for 12 h. The modified montmorillonite was ground, sieved with a 300-mesh filter, and vacuum-dried for 12 h for later use, i.e., modified montmorillonite B.

[0069] Preparation Example 3

[0070] 10 g of dried sodium montmorillonite was weighed and added to 200 mL of N,N-dimethylformamide (DMF). The mixture was ultrasonically treated at 80°C for 30 min (power 300 W), and then 0.5 g of PEG-4000 was added. The mixture was stirred at 80°C for 4 h under nitrogen protection to obtain a mixed solution. The mixed solution was centrifuged and washed until neutral, and then vacuum-dried at 80°C for 12 h. The modified montmorillonite obtained was ground, sieved with a 300-mesh filter, and vacuum-dried for 12 h for later use, i.e., modified montmorillonite C.

[0071] Preparation Example 4

[0072] 10 g of dried sodium montmorillonite was weighed and added to 200 mL of deionized water. The mixture was ultrasonically treated at 80°C for 60 min (power 300 W), and then 0.5 g of PEG-6000 was added. The mixture was stirred at 80°C for 2 h under nitrogen protection to obtain a mixed solution. The mixed solution was centrifuged and washed until neutral, and then vacuum-dried at 80°C for 12 h. The modified montmorillonite obtained was ground, sieved through a 300-mesh filter, and vacuum-dried for 12 h for later use, i.e., modified montmorillonite D.

[0073] Preparation Example 5

[0074] 10 g of dried sodium montmorillonite was weighed and added to 200 mL of deionized water. The mixture was ultrasonically treated at 80°C for 60 min (power 300 W), and then 0.5 g of PEG-8000 was added. The mixture was stirred at 80°C for 2 h under nitrogen protection to obtain a mixed solution. The mixed solution was centrifuged and washed until neutral, and vacuum-dried at 80°C for 12 h. The modified montmorillonite obtained was ground, sieved with a 300-mesh filter, and vacuum-dried for 12 h for later use, i.e., modified montmorillonite E.

[0075] <Preparation of Metallized Tungsten Slurry>

[0076] Example 1

[0077] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 90%, inorganic bonding phase is 4%, organic vehicle A is 5%; organic vehicle B is 1%.

[0078] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0079] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0080] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite C;

[0081] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0082] Example 2

[0083] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 70%, inorganic bonding phase is 5%, organic vehicle A is 20%; organic vehicle B is 5%.

[0084] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0085] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0086] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite C;

[0087] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0088] Example 3

[0089] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0090] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0091] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0092] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite C;

[0093] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0094] Example 4

[0095] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 5%; organic vehicle B is 10%.

[0096] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0097] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0098] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite C;

[0099] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0100] Example 5

[0101] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0102] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0103] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0104] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite A;

[0105] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0106] Example 6

[0107] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0108] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0109] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0110] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite B;

[0111] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0112] Example 7

[0113] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0114] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0115] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0116] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite D;

[0117] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0118] Example 8

[0119] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0120] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0121] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0122] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite E;

[0123] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0124] Example 9

[0125] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0126] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0127] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0128] The organic vehicle A: by mass percentage, 10% acrylic resin organic binder, 10% dioctyl phthalate, 78% terpineol, 2% modified montmorillonite C;

[0129] The organic carrier B comprises, by mass percentage, 5% of ethyl cellulose organic binder, 15% of dibutyl phthalate, 60% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0130] Example 10

[0131] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0132] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0133] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0134] The organic vehicle A: by mass percentage, 25% of an acrylic resin organic binder, 20% of dioctyl phthalate, 53% terpineol, 2% of modified montmorillonite C;

[0135] The organic carrier B comprises, by mass percentage, 20% of ethyl cellulose organic binder, 5% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0136] Example 11

[0137] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0138] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0139] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0140] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 59% terpineol, 1% of modified montmorillonite C;

[0141] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0142] Example 12

[0143] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0144] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0145] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0146] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 57% terpineol, 3% of modified montmorillonite C;

[0147] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0148] Example 13

[0149] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0150] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0151] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0152] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 56% terpineol, 4% of modified montmorillonite C;

[0153] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0154] Example 14

[0155] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0156] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0157] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0158] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 55% terpineol, 5% of modified montmorillonite C;

[0159] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0160] Example 15

[0161] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0162] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0163] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0164] The organic vehicle A: by mass percentage, 15% of an epoxy resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite C;

[0165] The organic carrier B comprises, by mass percentage, 10% of polyvinyl butyral organic binder, 25% of dibutyl phthalate, 25% of benzyl alcohol and 40% of ethylene glycol diacetate.

[0166] Example 16

[0167] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0168] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0169] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0170] The organic carrier A: by mass percentage, 15% of a phenolic resin organic binder, 25% of dioctyl phthalate, 58% terpineol, 2% of modified montmorillonite C;

[0171] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0172] Comparative Example 1

[0173] Composition of metallized tungsten slurry: by mass percentage, conductive metal tungsten powder is 80%, inorganic bonding phase is 5%, organic vehicle A is 10%; organic vehicle B is 5%.

[0174] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0175] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0176] The organic vehicle A: by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 60% terpineol;

[0177] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0178] Comparative Example 2

[0179] The composition of the metallized tungsten slurry is as follows: by mass percentage, the conductive metal tungsten powder is 80%, the inorganic bonding phase is 5%, and the organic vehicle A is 15%.

[0180] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0181] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0182] The organic carrier A comprises, by mass percentage, 15% of an acrylic resin organic binder, 25% of dioctyl phthalate, 58% of terpineol, and 2% of modified montmorillonite C.

[0183] Comparative Example 3

[0184] The composition of the metallized tungsten slurry is as follows: by mass percentage, the conductive metal tungsten powder is 80%, the inorganic bonding phase is 5%, and the organic vehicle B is 15%.

[0185] The particle size of the conductive metal tungsten powder is 1.5 μm to 2 μm;

[0186] The inorganic bonding phase includes: 95% Al2O3 powder, 5% sintering aid (1% Y2O3, 3.5% MgO, 0.5% talc powder).

[0187] The organic carrier B comprises, by mass percentage, 10% of ethyl cellulose organic binder, 25% of dibutyl phthalate, 45% of diethylene glycol butyl ether acetate and 20% of ethylene glycol diacetate.

[0188] Performance testing:

[0189] <Composite colloidal metallized tungsten paste printing performance test>

[0190] The metallized tungsten slurries obtained in Examples 1-16 and Comparative Examples 1-3 were thoroughly mixed to ensure uniformity and free of bubbles, and allowed to stand for at least 5 minutes before use. The viscosity and thixotropic index were tested using a Brookfield-DV2T viscometer, a No. 14 rotor, and a rotor barrel at a constant temperature of 25°C at 1 RPM, 10 RPM, and 30 RPM. The thixotropic index = viscosity (1 RPM) / viscosity (10 RPM). The metallized tungsten slurries obtained in Examples 1-16 and Comparative Examples 1-3 were used as printing test samples. Each metallized tungsten slurry was screen-printed onto an electrostatic chuck alumina green ceramic sheet. The printing properties of the slurries were observed using a high-power microscope. The results are shown in Table 1.

[0191] Table 1 Printing performance test results of composite colloidal metallized tungsten paste

[0192]

[0193] Among them, the effect levels of the printed visual appearance are: clear pattern with good resolution > clear pattern > clear pattern with slight texture > complete pattern > complete pattern with slight texture > complete pattern with obvious overflow.

[0194] <Sintering Matching Test of Composite Colloidal Metallized Tungsten Slurry>

[0195] Verification of the co-firing compatibility of the slurry: The metallized tungsten slurries obtained in Examples 1-16 and Comparative Examples 1-3 were respectively printed on the surface of a 96% Al2O3 white porcelain strip with a thickness of 0.6 mm and a size of 100×100 mm, and printed into a 20×20 mm square pattern. After drying, the strip was placed in an atmosphere sintering furnace and sintered at 1500°C to 1600°C for 2 hours in a wet hydrogen atmosphere. After sintering, the test sample was removed and the roughness of the alumina substrate was measured at multiple points on the printed surface, for example 40 to 50 points, using a desktop roughness meter.

[0196] Slurry adhesion test: The metallized tungsten paste printed sintered sheets obtained in Examples 1-16 and Comparative Examples 1-3 were electroplated with nickel layer, with a nickel layer thickness of 5-7 μm. The welding surface was measured by hanging weight method. 2 , the maximum tensile force that a lead bent 90° can withstand in 10s;

[0197] Slurry square resistance test: The metallized tungsten pastes obtained in Examples 1-14 and Comparative Examples 1-3 were respectively printed on the surface of a 96% Al2O3 white porcelain raw tape with a thickness of 0.6 mm and a size of 100×100 mm, printed into a 20×20 mm square pattern. After drying, the tape was placed in an atmosphere sintering furnace and sintered at 1500°C to 1600°C for 2 hours in a nitrogen and hydrogen atmosphere. After sintering, the test sample was taken out and measured using a four-probe square resistance tester. The square resistance value of the slurry was calculated.

[0198] The sintering matching test results of the composite colloidal metallized tungsten slurry are shown in Table 2:

[0199]

[0200] It can be found from Table 1 and Table 2 that when the polyether polyol in Examples 3 and 5-8 is selected from PEG-4000 or PEG-6000, the prepared composite colloidal metallized tungsten slurry has good comprehensive effects such as thixotropic index, printing performance, adhesion, and square resistance. In addition, by comparing Examples 3 and 11-14, it can be found that the amount of modified montmorillonite is preferably 2%-3%.

[0201] The above description is only a preferred specific embodiment of the present invention, and the scope of protection of the present invention is not limited thereto. Any simple change or equivalent replacement of the technical solution that can be obviously obtained by any technician familiar with this technical field within the technical scope disclosed in the present invention falls within the scope of protection of the present invention.

Claims

1. An alumina ceramic composite colloidal metallized tungsten slurry, characterized in that: By mass percentage, including: 70% to 90% conductive metal tungsten powder, 1% to 15% inorganic binder phase, 5% to 25% organic vehicle A, 1% to 10% organic vehicle B; Wherein, the organic carrier A comprises: 10% to 25% of an organic binder, 5% to 40% of a plasticizer, 5% to 90% of a solvent, and 1% to 5% of modified montmorillonite; The organic carrier B comprises: 5% to 20% of an organic binder, 10% to 60% of a plasticizer and 5% to 90% of a solvent; The modified montmorillonite is polyether polyol modified montmorillonite.

2. The alumina ceramic composite colloidal metallized tungsten slurry according to claim 1, characterized in that: The particle size of the conductive metal tungsten powder is 0.5 μm to 2.5 μm.

3. The alumina ceramic composite colloidal metallized tungsten slurry according to claim 1, characterized in that: The polyether polyol in the polyether polyol-modified montmorillonite is selected from one or more of PTMEG-1000, PEG-2000, PEG-4000, PEG-6000 or PEG-8000, and more preferably PEG-4000 or PEG-6000.

4. The alumina ceramic composite colloidal metallized tungsten slurry according to claim 1, characterized in that: The usage of the polyether polyol modified montmorillonite is 2% to 3%.

5. The alumina ceramic composite colloidal metallized tungsten slurry according to claim 1, characterized in that: The organic binder in the organic carrier A comprises: a mixture of one or more of acrylic resin, phenolic resin and epoxy resin.

6. The alumina ceramic composite colloidal metallized tungsten slurry according to claim 1, characterized in that: The organic binder in the organic carrier B includes: a mixture of one or more of ethyl cellulose, polyvinyl alcohol, and polyvinyl butyral.

7. The alumina ceramic composite colloidal metallized tungsten slurry according to any one of claims 1 to 6, characterized in that: The inorganic bonding phase comprises: 92% to 99% of Al2O3 powder and 1% to 8% of a sintering aid.

8. The alumina ceramic composite colloidal metallized tungsten slurry according to any one of claims 1 to 6, characterized in that: The solvent is selected from one or more mixtures of methanol, ethanol, acetone, benzyl alcohol, diethylene glycol butyl ether acetate, ethylene glycol diacetate, terpineol and butyl carbitol.

9. A method for preparing the alumina ceramic composite colloidal metallized tungsten slurry according to claim 1, characterized in that: The steps include: (1) Preparation of inorganic binder phase: Al2O3 powder and sintering aid are weighed in proportion and placed in a ball mill. An appropriate amount of dispersant and pure water are added and ball milled for 2 to 6 hours. After ball milling, the slurry is poured into a tray and freeze-dried in a vacuum freeze dryer. After freeze-drying, the powder is vibrated and sieved through a 200-300 mesh sieve for later use. (2) Preparation of organic carrier A: weigh the organic binder, modified montmorillonite, plasticizer and solvent in proportion, add the solvent and plasticizer into a stirring and dissolving container and stir evenly, set the heating temperature to 50℃~100℃, and the stirring speed to 150r / min~500r / min, add the organic binder and modified montmorillonite while stirring until they are completely dissolved and evenly dispersed, cool and seal for storage; (3) Preparation of organic carrier B: weigh the organic binder, plasticizer and solvent in proportion and add them to a stirring and dissolving container. First add the solvent and plasticizer and stir evenly. Set the heating temperature to 50℃~100℃ and the stirring speed to 150r / min~500r / min. Add the organic binder while stirring until it is completely dissolved and evenly dispersed. Cool and seal the container for storage. (4) Preparation of a conductive metal tungsten powder mixture: The inorganic binder phase and conductive tungsten powder obtained in step (1) are weighed in proportion and placed in a ball mill, and then an appropriate amount of dispersant and acetone are added to the ball mill and ball milled for 4 h to 24 h; then the organic carrier A in step (2) is weighed in proportion and placed in the ball mill, and ball milled again for 2 h to 6 h; (5) Preparation of metallized tungsten slurry: After the ball milling in step (4) is completed, the mixture is passed through a 100-200 mesh screen and placed in a vacuum mixer for heating and stirring. The heating temperature is set at 50°C to 100°C. The acetone and other ball milling media are removed by vacuum distillation to obtain a uniform tungsten slurry. (6) The organic carrier B in step (3) is weighed in proportion, added to the tungsten slurry obtained in step (5), and then rapidly stirred in a high shear mixer to form a mixed slurry, wherein the stirring speed is 500 r / min to 10,000 r / min and the stirring time is 0.5 h to 1 h; the mixed slurry is then rolled multiple times using a three-axis rolling mill, and the rolling spacing is gradually reduced until the required printing viscosity is met, thereby obtaining the required composite colloidal metallized tungsten electronic slurry for printing.

10. Use of the alumina ceramic composite colloidal metallized tungsten slurry according to any one of claims 1 to 8 in an electrostatic chuck.

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