A curable getter paste

Abstract

The present application belongs to the technical field of getter materials, and particularly relates to a solidified getter slurry, which comprises the following components and weight percentages: 50-90% of non-activated getter powder, 5-20% of adhesive material, 5-20% of solvent, 0.1-2% of surfactant, and 0.05-0.1% of initiator. The core-shell type getter material is zirconium-iron coated with palladium or nickel, zirconium-iron coated with palladium or nickel, zirconium-vanadium-iron coated with palladium or nickel, and / or titanium-molybdenum coated with palladium or nickel. The solidified getter slurry can be attached to the surface of a device by printing, spraying, coating and the like, and is suitable for small-volume and complex-shaped devices, and does not need high-temperature activation and heating circuit during use, and has a small occupied volume.

Description

Technical Field

[0001] This invention belongs to the field of air-absorbing material technology, specifically relating to a cured air-absorbing slurry. Background Technology

[0002] Getter materials are widely used in vacuum electronic devices, photocathodes, nuclear reactors, controlled nuclear fusion devices, gas lasers, rare gas purification, and high vacuum generation. They can effectively maintain a high vacuum environment, improve device stability, and extend device lifespan.

[0003] In recent years, with the trend of device miniaturization and integration, there is a need for more flexible and versatile getter materials to improve and maintain the vacuum quality inside devices. Traditional getter elements are difficult to apply directly to micro vacuum packaging devices due to their large size and high activation temperature. Thin-film getter materials require complex and expensive coating equipment and have high requirements for the target material. Summary of the Invention

[0004] To address the problems of existing technologies, this invention provides a curable getter slurry, overcoming the drawbacks of traditional getter elements (large size, requiring activation), and the high manufacturing cost of thin-film getter materials. Specifically, this invention includes the following:

[0005] A curable getter slurry comprises, by weight percentage: 50%–90% non-activating getter powder, 5%–20% binder, 5%–20% solvent, 0.1%–2% surfactant, and 0.05%–0.1% initiator.

[0006] Preferably, its components and weight percentages include: 65%–80% non-activating getter powder, 10%–15% binder, 9%–19% solvent, 0.5%–1% surfactant, and 0.06%–0.08% initiator.

[0007] Preferably, the non-activation getter powder is a core-shell getter material powder.

[0008] Preferably, the core-shell getter material is palladium or nickel coated zirconium iron, palladium or nickel coated zirconium iron niobium, palladium or nickel coated zirconium vanadium iron, and / or palladium or nickel coated titanium molybdenum; the thickness of the shell layer of the core-shell getter material is 10 nm to 1 μm.

[0009] Preferably, the adhesive material is one or a mixture of molybdenum-modified epoxy resin resistant to instantaneous high temperatures above 300°C, palladium-modified bisphenol A epoxy acrylate resistant to instantaneous high temperatures above 300°C, soluble TPU polyurethane resin 55D resistant to instantaneous high temperatures above 300°C, or a metal with a melting point below 300°C; the instantaneous high temperature means the high temperature time is ≤10min.

[0010] Preferably, the metal with a melting point below 300°C is nano-silver and / or copper.

[0011] Preferably, the solvent is a polymerizable 1-3 functional monomer.

[0012] Preferably, the solvent is one or a mixture of divinylbenzene, pentaerythritol triacrylate, and hydroxyethylacrylamide.

[0013] Preferably, the surfactant is one or a mixture of oxalic acid, palmitic acid, lauric acid, dodecylamine, and octamethylsiloxane.

[0014] Preferably, the initiator is one or a mixture of peracetic acid, benzoyl peroxide, ferrocene, phthalic anhydride, and glycidyl methacrylate.

[0015] Preferably, the curing temperature of the curable air-absorbing slurry is 50-300℃, and the curing time is 1-3 hours; when Pg = 4.0 × 10⁻⁶. -4 At Pa, the hydrogen absorption capacity of the cured gas-absorbing slurry in 2 hours is not less than 3500 Pa·ml·cm. -2 .

[0016] The beneficial effects of this invention are:

[0017] The curable getter paste of the present invention can be adhered to the surface of the device by means of printing, spraying, coating, etc. It is suitable for small-volume and complex-shaped devices. The process does not require high-temperature activation, does not require heating, and occupies a small volume.

[0018] The curable getter slurry of this invention uses core-shell structured getter powders, with a palladium or nickel layer thickness of 10nm to 1μm to protect the internal getter powders from poisoning and prevent the shell from peeling off from the powder surface after gas absorption. Low-melting-point nano-silver and / or copper are used as binders. During low-temperature sintering, it is in a semi-sintered state, with powder particles connected by sintering necks. Numerous pores within the powder serve as gas pathways, facilitating gas diffusion to the getter material surface. This adhesive material also features low-temperature sintering and high-temperature service capability, sintering at 150–300℃ with a theoretical remelting temperature not lower than 600℃.

[0019] The curable getter slurry of the present invention avoids the poisoning of the getter material by adding addition monomers as solvents during the curing process. At the same time, the multifunctional polymeric monomers have a large number of pores after volume expansion during polymerization, which is conducive to the diffusion of gas to the surface of the getter material. Attached Figure Description

[0020] Figure 1 This is an electron microscope image of the non-activation getter powder described in this invention;

[0021] Figure 2 Electron micrograph of a semi-sintered low-melting-point metal;

[0022] Figure 3 Electron micrograph of a core-shell structured gas-absorbing powder whose shell was too thick and subsequently detached after hydrogen absorption. Detailed Implementation

[0023] The following is in conjunction with the appendix Figure 1-3 The present invention will be described in detail below with reference to specific embodiments. The embodiments shown below are not intended to limit the scope of the invention as described in the claims. Furthermore, the complete contents of the configurations shown in the embodiments below are not limited to those necessary for the solution of the invention as described in the claims.

[0024] A curable getter slurry comprises, by weight percentage: 50%–90% (e.g., 55%, 60%, 65%, 70%, 75%, 80%, 85%, etc.) of non-activating getter powder, 5%–20% (e.g., 6%, 8%, 10%, 12%, 14%, 16%, 18%, etc.) of binder material, 5%–20% (e.g., 6%, 8%, 10%, 12%, 14%, 16%, 18%, etc.) of solvent, 0.1%–2% (e.g., 0.2%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, etc.) of surfactant, and 0.05%–0.1% (e.g., 0.06%, 0.07%, 0.08%, 0.09%, etc.) of initiator. The non-activation getter powder is a core-shell getter material powder. The core-shell getter material is palladium or nickel-coated zirconium iron, palladium or nickel-coated zirconium iron, palladium or nickel-coated zirconium vanadium iron, and / or palladium or nickel-coated titanium molybdenum. The thickness of the core-shell getter material shell layer (i.e., the palladium or nickel coating layer) is 10 nm to 1 μm (e.g., 50 nm, 100 nm, 200 nm, 400 nm, 600 nm, 800 nm, etc.). The adhesive material is a molybdenum-modified epoxy resin resistant to instantaneous high temperatures above 300°C, palladium-modified bisphenol A epoxy acrylate resistant to instantaneous high temperatures above 300°C, soluble TPU polyurethane resin 55D resistant to instantaneous high temperatures above 300°C, or one or more mixtures of metals with melting points below 300°C. The instantaneous high temperature refers to a high-temperature time ≤ 10 min, and the low-melting-point metal is nano-silver and / or copper. The solvent is a polymerizable 1-3 functional monomer, specifically one or a mixture of divinylbenzene, pentaerythritol triacrylate, and hydroxyethylacrylamide. The surfactant is one or a mixture of oxalic acid, palmitic acid, lauric acid, dodecylamine, and octamethylsiloxane. The initiator is one or a mixture of peracetic acid, benzoyl peroxide, ferrocene, phthalic anhydride, and glycidyl methacrylate. The curing temperature of the curable getter slurry of this invention is 50-300℃, and the curing time is 1-3 hours, when Pg = 4.0 × 10⁻⁶. -4 At Pa, the hydrogen absorption capacity of the cured gas-absorbing slurry in 2 hours is not less than 3500 Pa·ml·cm. -2 .

[0025] A curable air-getter slurry, the preparation method of which includes the following steps:

[0026] (1) Preparation of getter-free powder: Take 50g of -300 mesh zirconium vanadium iron alloy into a 1L beaker, add dilute hydrochloric acid solution with pH 4-5, sonicate for 2 minutes, add 5ml of 0.05-0.2mol / L selenite chloride solution, stir mechanically for 10 minutes, and then filter to separate, which is the activated zirconium vanadium iron alloy. Add palladium chloride to ammonia water and heat until completely dissolved, and adjust the pH to 9-11 with ammonia water. Add sodium ethylenediaminetetraacetate to further stabilize the palladium solution, wherein the molar ratio of sodium ethylenediaminetetraacetate to palladium ions is 2:1. Add the activated zirconium vanadium iron alloy to the palladium solution and reduce by adding hydrazine hydrate dropwise in an ice-water bath. Control the mass ratio of palladium to zirconium vanadium iron alloy to be 3:100-8:100, where the palladium plating effect of 3:100, 4:100, 5:100, 6:100, and 8:100 is shown in the figure below. Figure 1 (a)-(e).

[0027] (2) Using the above-mentioned non-activation getter powder, the ingredients are mixed and slurryed according to the proportions described in this invention to obtain the solidified getter slurry.

[0028] The preparation methods of other non-activation getter powders described in this invention refer to the above step (1).

[0029] Example 1

[0030] A curable getter slurry comprises, by weight percentage: 82% palladium-plated, non-activating getter powder, 8% binder, 10% solvent, 0.5% surfactant, and 0.06% initiator. The non-activating getter powder is palladium-coated zirconium iron. The binder is a low-emission, high-temperature resistant molybdenum-modified epoxy resin. The solvent is divinylbenzene. The surfactant is oxalic acid. The initiator is peracetic acid.

[0031] Experiments have verified that the curing temperature of the curing-type air-absorbing slurry described in this embodiment is 50℃ and the curing time is 2 hours, when Pg = 4.0 × 10⁻⁶. -4 The amount of hydrogen absorbed in 2 hours at Pa is 3820 Pa·ml·cm. -2 .

[0032] Example 2

[0033] A curable getter slurry comprises, by weight percentage: 72% of a palladium-plated, non-activation-requiring getter powder (4%), 12% of a binder, 15% of a solvent, 1% of a surfactant, and 0.08% of an initiator. The non-activation-requiring getter powder is a core-shell getter powder, specifically nickel-coated zirconium vanadium iron. The binder is palladium-modified bisphenol A epoxy acrylate. The solvent is pentaerythritol triacrylate. The surfactant is palmitic acid. The initiator is benzoyl peroxide.

[0034] Experiments have verified that the curing temperature of the air-absorbing slurry described in this embodiment is 150℃ and the curing time is 1.5h, when Pg = 4.0 × 10⁻⁶. -4 The amount of hydrogen absorbed in 2 hours at Pa is 3623 Pa·ml·cm. -2 .

[0035] Example 3

[0036] A curable getter slurry comprises, by weight percentage: 60% of a palladium-plated, non-activating getter powder (8%), 18% of a binder, 20% of a solvent, 2% of a surfactant, and 0.1% of an initiator. The non-activating getter powder is a core-shell getter material powder, specifically palladium-coated titanium-molybdenum. The binder is nano-silver. The solvent is hydroxyethylacrylamide. The surfactant is octamethylsiloxane. The initiator is glycidyl methacrylate.

[0037] Experiments have verified that the curing temperature of the air-absorbing slurry described in this embodiment is 200℃ and the curing time is 3 hours, when Pg = 4.0 × 10⁻⁶. -4 The amount of hydrogen absorbed in 2 hours at Pa is 3510 Pa·ml·cm. -2 .

[0038] Example 4

[0039] A curable getter slurry comprises, by weight percentage: 50%–90% unactivated getter powder, 5%–20% binder, 5%–20% solvent, 0.1%–2% surfactant, and 0.05%–0.1% initiator. The unactivated getter powder is a zirconium-vanadium-iron alloy plated with 3% palladium. The binder is a molybdenum-modified epoxy resin. The solvent is divinylbenzene. The surfactant is palmitic acid. The initiator is peracetic acid.

[0040] Experiments have verified that the curing temperature of the air-absorbing slurry described in this embodiment is 50℃ and the curing time is 3 hours, when Pg = 4.0 × 10⁻⁶. -4 The hydrogen absorption rate at Pa for 2 hours is 2500–4160 Pa·ml·cm. -2 .

[0041] Example 5

[0042] A curable getter slurry comprises, by weight percentage: 50%–90% unactivated getter powder, 5%–20% binder, 5%–20% solvent, 0.1%–2% surfactant, and 0.05%–0.1% initiator. The unactivated getter powder is a zirconium-vanadium-iron alloy plated with 6% palladium. The binder is nano-silver. The solvent is hydroxyethyl acrylamide. The surfactant is lauric acid. The initiator is peracetic acid.

[0043] Experiments have verified that the curing temperature of the air-absorbing slurry described in this embodiment is 200℃ and the curing time is 2 hours, when Pg = 4.0 × 10⁻⁶. -4 The hydrogen absorption rate at Pa for 2 hours is 3500–4830 Pa·ml·cm⁻¹ -2 .

[0044] Example 6

[0045] A curable getter slurry comprises, by weight percentage: 50%–90% unactivated getter powder, 5%–20% binder, 5%–20% solvent, 0.1%–2% surfactant, and 0.05%–0.1% initiator. The unactivated getter powder is a zirconium-vanadium-iron alloy plated with 6% palladium. The binder is soluble TPU polyurethane resin 55D. The solvent is pentaerythritol triacrylate. The surfactant is dodecylamine. The initiator is benzoyl peroxide and phthalic anhydride.

[0046] Experiments have verified that the curing temperature of the curing-type air-absorbing slurry described in this embodiment is 120℃ and the curing time is 2 hours, when Pg = 4.0 × 10⁻⁶. -4 The hydrogen absorption rate at Pa for 2 hours is 3000–4370 Pa·ml·cm. -2 The inhalation effect is as follows.

[0047] The air absorption effect of the slurries described in Examples 4-6 was characterized, and the detailed components and effects are listed in Table 1.

[0048] Table 1. Composition and air absorption performance data of the slurries in Examples 4-6

[0049]

[0050]

[0051] Figure 1 This is an electron microscope image of the non-activation getter powder described in this invention. It can be seen from the image that a palladium / nickel shell layer is coated on the surface of the getter powder, forming a core-shell structure that isolates the core getter powder from contact with oxygen in the air. Figure 2Semi-sintered electron microscope image of low melting point metal. The image shows that the powder particles are connected by sintering necks and there are a large number of pores inside as gas passages, which is conducive to gas diffusion to the surface of the gas-absorbing material. Figure 3 The image shows an electron microscope image of a core-shell getter material with a shell thickness exceeding 1 μm after hydrogen absorption. This demonstrates that when the shell thickness exceeds 1 μm, the shell of the core-shell getter material will peel off after hydrogen absorption, losing its protective function for the core getter material.

[0052] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A curing-type air-absorbing slurry, characterized in that, Its components and weight percentages include: 50%~90% unactivated getter powder, 5%~20% binder, 5%~20% solvent, 0.1%~2% surfactant, and 0.05~0.1% initiator. The unactivated getter powder is a core-shell getter material powder, which is palladium or nickel-coated zirconium iron, palladium or nickel-coated zirconium iron niobium, palladium or nickel-coated zirconium vanadium iron, and / or palladium or nickel-coated titanium molybdenum. The solvent is a polymerizable 1-3 functional monomer, polymerized by addition polymerization. The shell thickness of the core-shell getter material is 10nm~1μm. The initiator is one or a mixture of peracetic acid, benzoyl peroxide, ferrocene salts, phthalic anhydride, and glycidyl methacrylate. The curing temperature of the curable getter slurry is 50-300℃, and the curing time is 1-3h. When Pg=4.0 × 10⁻⁶ -4 At Pa, the amount of hydrogen absorbed in 2 hours should not be less than 3500 Pa·ml·cm⁻¹. -2 .

2. The curable air-absorbing slurry according to claim 1, characterized in that, Its components and weight percentages include: 65%~80% non-activating getter powder, 10%~15% binder, and solvent. 9%~19%, surfactant 0.5%~1%, initiator 0.06%~0.08%.

3. The curable air-absorbing slurry according to claim 1, characterized in that, The adhesive material is one or more of the following: molybdenum-modified epoxy resin resistant to temperatures above 300°C, palladium-modified bisphenol A epoxy acrylate resistant to temperatures above 300°C, soluble TPU polyurethane resin 55D resistant to temperatures above 300°C, or a metal with a melting point below 300°C.

4. The curable air-absorbing slurry according to claim 3, characterized in that, The metal with a melting point below 300°C is nano-silver and / or copper.

5. The curable air-absorbing slurry according to claim 1, characterized in that, The solvent is one or a mixture of divinylbenzene, pentaerythritol triacrylate, and hydroxyethylacrylamide.

6. The curable air-absorbing slurry according to claim 1, characterized in that, The surfactant is one or a mixture of oxalic acid, palmitic acid, lauric acid, dodecylamine, and octamethylsiloxane.

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