A ceramic tube end connector member and a method of manufacturing the same

Abstract

The application discloses a ceramic pipe end connecting body member and a manufacturing method thereof, wherein the ceramic pipe end connecting body member comprises an oxide ceramic layer, an inorganic material layer, a single element layer, an alloy layer and a metal layer which are sequentially stacked, the oxide ceramic layer has a dense or porous structure, the inorganic material layer has a cation exchange function, the single element layer is a metal single element corresponding to metal ions capable of ion exchange with the inorganic material layer, and the alloy layer is capable of respectively undergoing wetting phenomena with the single element layer and the metal layer. The single element layer of the application can be ion exchanged with the inorganic material layer, sealed by atomic-level fusion to enhance the sealing connection stability, and meanwhile, the inorganic film layer between the inorganic material layer and the metal layer is transitioned to the sealing connection of the metal layer and the metal layer which is easy to realize, and then the alloy layer is used to wet and seal the single element layer and the metal layer, so that the sealing effect is ensured.

Description

Technical Field

[0001] This invention relates to the field of ceramic tube connection technology, and in particular to a ceramic tube end connector component and its manufacturing method. Background Technology

[0002] Ceramics are inorganic materials with dense or porous structures (such as alumina and titanium dioxide), typically possessing superior properties such as high-temperature resistance, corrosion resistance, and wear resistance. However, when used alone, they are limited in their resistance to thermal stress and have a single function. Combining ceramic tubes with inorganic functional materials and connecting them to metal tubular materials can be used for chemical separation, such as the separation of organic solvents and water.

[0003] The connection between ceramic tubes and inorganic functional materials, and metals, can be achieved by introducing rubber O-rings or rubber heat shrink tubing, which deforms to achieve a sealed connection between the ceramic material and the metal component. Traditional rubber O-ring seals or rubber heat shrink tubing seals are prone to mechanical damage, chemical corrosion, and deformation in high-temperature, high-pressure, high-concentration organic solvents, and radiant atmospheres. This process can lead to a series of problems in chemical production, such as material leakage, production safety, and environmental pollution. In addition to traditional O-ring connections or rubber heat shrink tubing seals, ceramics and metals can be connected by introducing a metal alloy layer. The diffusion bonding method utilizes the principle of atomic thermal motion to achieve the connection. This method typically requires high temperature and high vacuum conditions (Simulation of I-II mixed mode crack propagation of titanium alloy based on ABAQUS. 2018 International Academic Conference for Graduates, NUAA, Nanjing, 2018.10.). The self-propagating high-temperature bonding method utilizes the heat released by the reaction between the components of the external coating layer to achieve the connection. The process is relatively simple, but the formulation of the coating layer material is difficult to develop and the applicable range is small (J Chin Ceram Soc, 2020, 48(9): 1–11). In addition, an alloy with a melting point lower than that of ceramics and metals is used. The alloy, ceramic and metal components are heated to the melting temperature of the alloy at the same time, and the alloy is used to fill the gap between the solid workpieces to connect the metal. At present, the main alloys for ceramic and stainless steel sealing are Ag-Cu-Ti alloy, copper alloy, TiC, TiCuNb, 06Cr19Ni10, etc., with operating temperatures that are too high, generally greater than 600℃, and some even reaching 1000℃. Low-temperature alloys are mainly tin alloys. Tin alloys have poor wetting of ceramics and cannot effectively connect metals and ceramics (CN115041813A; Journal of the European Ceramic Society, 2021, 41(3): 2076-2084).

[0004] Therefore, there is an urgent need to develop connector components suitable for connecting ceramics and metals. Summary of the Invention

[0005] The purpose of this invention is to provide a ceramic tube end connector component and its manufacturing method, so as to solve the technical problem that the sealing effect of the ceramic tube and metal connection in the prior art cannot be guaranteed.

[0006] This invention provides a ceramic tube end connector component, comprising an oxide ceramic layer, an inorganic material layer, an elemental layer, an alloy layer, and a metal layer stacked sequentially. The oxide ceramic layer has a dense or porous structure, the inorganic material layer has cation exchange function, the elemental layer is a metallic element corresponding to a metal ion that can exchange ions with the inorganic material layer, and the alloy layer can wet the elemental layer and the metal layer respectively.

[0007] As described above, the oxide ceramic layer of the ceramic tube end connector includes an alumina ceramic layer or a titanium oxide ceramic layer.

[0008] The inorganic material layer of the ceramic tube end connector as described above includes a zeolite layer or an organometallic framework layer.

[0009] In the ceramic tube end connector component described above, the single-element layer includes a copper layer, a silver layer, or a nickel layer.

[0010] The present invention also provides a method for manufacturing a ceramic tube end connector component, comprising the following steps:

[0011] A ceramic tube with an inorganic material layer having cation exchange function is coated on the surface of the ceramic tube to obtain a ceramic tube with an inorganic material layer.

[0012] The ceramic tube with the inorganic material layer and the metal end cap are placed in deionized water for ultrasonic cleaning, and then dried.

[0013] The dried end of the ceramic tube with the inorganic material layer is directly contacted with the chemical plating solution for chemical plating. The inorganic material layer and the chemical plating solution undergo cation exchange to form a single layer, resulting in a ceramic tube with a single layer at the end.

[0014] The dried metal end cap is connected to a ceramic tube with a single layer, and a low-temperature alloy and auxiliary agent are filled into the gap between the metal end cap and the single layer to obtain a connecting component.

[0015] The method for manufacturing a ceramic tube end connector as described above, comprising the steps of connecting the dried metal end cap to a ceramic tube having a single layer, and filling the gap between the metal end cap and the single layer with a low-temperature alloy and an auxiliary agent to obtain the connector, includes:

[0016] Low-temperature alloys and additives are filled into the gap between the single layer and the metal head to obtain a connector between the ceramic tube and the metal head;

[0017] The end of the connector filled with the cryogenic alloy and auxiliary agent is heated until the cryogenic alloy and auxiliary agent reach a molten state.

[0018] The heated connector is allowed to cool naturally at room temperature to obtain the connector component.

[0019] In the manufacturing method of the ceramic tube end connector as described above, the low-temperature alloy includes a solder alloy, and the auxiliary agent is a reducing organic compound.

[0020] The manufacturing method of the ceramic tube end connector as described above involves heating the end of the connector filled with a low-temperature alloy and an auxiliary agent using induction heating.

[0021] In the manufacturing method of the ceramic tube end connector as described above, the heating power is 1 to 100 W, the heating time is 30 to 180 s, and the temperature is 120 to 200 °C in the induction heating method.

[0022] In the method for manufacturing the ceramic tube end connector as described above, the chemical plating solution contains copper ions or nickel ions, the reaction temperature of the chemical plating is 20-50°C, and the reaction time of the chemical plating is 1 min-60 min.

[0023] In the method for manufacturing the ceramic tube end connector as described above, silver nitrate, palladium nitrate, or cerium nitrate is injected as an initiator for the chemical plating reaction.

[0024] In the manufacturing method of the ceramic tube end connector as described above, the pH of the chemical plating solution is above 11, and the chemical plating solution is a mixed solution containing formaldehyde and copper sulfate. The concentration of formaldehyde in the chemical plating solution ranges from 15 ml / L to 30 ml / L, the concentration of copper sulfate ranges from 4 g / L to 15 g / L, the concentration of sodium hydroxide ranges from 6 g / L to 20 g / L, and the concentration of the complexing agent ranges from 10 g / L to 20 g / L.

[0025] In the manufacturing method of the ceramic tube end connector as described above, the electroless plating solution can also be a mixed solution containing nickel sulfate hexahydrate, sodium dihydrogen phosphate monohydrate, and tetrasodium pyrophosphate. The concentration range of nickel sulfate hexahydrate in the electroless plating solution is 10 g / L to 35 g / L, the concentration range of sodium dihydrogen phosphate monohydrate is 10 g / L to 35 g / L, and the concentration range of tetrasodium pyrophosphate is 30 g / L to 70 g / L.

[0026] In the manufacturing method of the ceramic tube end connector as described above, in step S3, the thickness of the single layer obtained after chemical plating is 2μm to 30μm, and the length of the single layer is 5mm to 50mm.

[0027] Implementing the embodiments of the present invention will have the following beneficial effects:

[0028] The ceramic tube end connector of the present invention has an inorganic material layer with ion exchange function covering the surface of the ceramic tube, and then a single element layer is set on the inorganic material layer. The single element layer can exchange ions with the inorganic material layer to achieve atomic-level fusion and sealing between the inorganic material layer and the single element layer, thereby enhancing the stability of the sealing connection between the two. At the same time, the inorganic film layer and metal connection between the inorganic material layer and the metal layer are transitioned to an easily achievable metal layer-to-metal sealing connection. Finally, the single element layer and the metal layer are sealed by the impregnation of the alloy layer to ensure the sealing effect. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0030] Figure 1 A schematic diagram of the structure of a ceramic tube end connector component;

[0031] Figure 2 This is an enlarged view of the connection part of the ceramic tube end connector component.

[0032] The layers are: 1. Oxide ceramic layer; 2. Inorganic material layer; 3. Elemental layer; 4. Alloy layer; 5. Metal layer. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] like Figure 1 and Figure 2This invention provides a ceramic tube end connector component, comprising, in sequence, an oxide ceramic layer 1, an inorganic material layer 2, an elemental layer 3, an alloy layer 4, and a metal layer 5. The oxide ceramic layer 1 has a dense or porous structure. The inorganic material layer 2 has cation exchange functionality. The elemental layer 3 is a metallic element corresponding to a metal ion capable of ion exchange with the inorganic material layer 2. The alloy layer 4 can wet both the elemental layer 3 and the metal layer 5. The inorganic material layer 2 has ion exchange and selective separation effects, making it suitable for chemical separation processes. The elemental layer 3 is a chemically plated metal layer that can exchange ions with the inorganic material layer 2 to achieve a tight connection between the two layers. Simultaneously, it transitions the inorganic film layer between the inorganic material layer 2 and the metal layer to an easily achievable metal-to-metal sealing connection. The alloy layer 4 is a low-temperature alloy layer; by heating and melting the low-temperature alloy, it can achieve a tight connection with the metal, resulting in a good sealing effect.

[0035] Among them, oxide ceramic layer 1 includes alumina ceramic layer or titanium oxide ceramic layer; inorganic material layer 2 includes zeolite layer or organometallic framework layer, specifically, zeolite layer can be NaA layer or NaY layer, organometallic framework layer can be ZIF-8 layer; elemental layer 3 includes copper layer, silver layer or nickel layer; alloy layer 4 can be solder alloy, or other low temperature alloy with good wetting effect with metal; metal layer 5 can be 304, 316 stainless steel, etc.

[0036] The manufacturing method of the ceramic tube end connector as described above includes the following steps:

[0037] A ceramic tube material is coated with an inorganic material layer on its surface through in-situ chemical synthesis, resulting in a ceramic tube with an inorganic material layer. This inorganic material layer is a functional film. The in-situ synthesis methods specifically include microwave heating synthesis and hydrothermal synthesis. The synthesis process can employ either a one-step or two-step method. The two-step method involves first synthesizing seed crystals on the ceramic substrate using hydrothermal or microwave heating to facilitate the subsequent growth of the functional film, followed by further synthesis using microwave heating or hydrothermal methods to complete the functional film synthesis.

[0038] The ceramic tube with the inorganic material layer and the metal end cap are placed in deionized water for ultrasonic cleaning, and then dried.

[0039] The dried end of the ceramic tube with the inorganic material layer is directly contacted with a chemical plating solution for chemical plating. The inorganic material layer undergoes cation exchange with the chemical plating solution to form a single layer, resulting in a ceramic tube with a single layer at the end. Specifically, the chemical plating solution contains copper or nickel ions, the temperature of the chemical plating solution is 20-50°C, the contact reaction time is 1 min-60 min, and silver nitrate, palladium nitrate, or cerium nitrate is added to the chemical plating solution as a reducing agent. The strong reducing agent reduces the copper or nickel ions in the chemical plating solution to copper or nickel, which are then deposited on the surface of the ceramic tube to form a dense coating. This coating is the single layer. The thickness of the single layer obtained after chemical plating is 2 μm-30 μm, and the length of the single layer is 5 mm-50 mm.

[0040] The dried metal end cap is connected to a ceramic tube with a single layer, and a low-temperature alloy and auxiliary agent are filled into the gap between the metal end cap and the single layer to obtain a connecting component. Specifically, the low-temperature alloy can be a solder alloy or other low-temperature alloys with good wetting effect with metals, and the auxiliary agent can be abietic acid, neoabietic acid, L-pilosolic acid, D-pilosolic acid, iso-D-pilosolic acid, dehydroabietic acid, longleaf abietic acid, santalinic acid, dihydroabietic acid, or other reducing organic compounds.

[0041] Further, the step of connecting the dried metal end cap to a ceramic tube with a single layer, and filling the gap between the metal end cap and the single layer with a low-temperature alloy and an auxiliary agent to obtain a connecting component includes: filling the gap between the single layer and the metal end cap with a low-temperature alloy and an auxiliary agent to obtain a connecting component between the ceramic tube and the metal end cap; heating the end of the connecting component filled with the low-temperature alloy and the auxiliary agent until the low-temperature alloy and the auxiliary agent reach a molten state, specifically, using induction heating to heat the end of the connecting component filled with the low-temperature alloy and the auxiliary agent, with a heating power of 1-100W, a heating time of 30s-180s, and a heating temperature of 120-200℃; and allowing the heated connecting component to cool naturally at room temperature to obtain the connecting component.

[0042] Furthermore, the pH of the electroless plating solution is above 11. The electroless plating solution is a mixed solution containing formaldehyde and copper sulfate. The concentration of formaldehyde in the electroless plating solution ranges from 15 ml / L to 30 ml / L, the concentration of copper sulfate ranges from 4 g / L to 15 g / L, the concentration of sodium hydroxide ranges from 6 g / L to 20 g / L, and the concentration of complexing agent ranges from 10 g / L to 20 g / L.

[0043] The electroless plating solution can also be a mixed solution containing nickel sulfate hexahydrate, sodium dihydrogen phosphate monohydrate, and tetrasodium pyrophosphate. The concentration range of nickel sulfate hexahydrate in the electroless plating solution is 10 g / L to 35 g / L, the concentration range of sodium dihydrogen phosphate monohydrate is 10 g / L to 35 g / L, and the concentration range of tetrasodium pyrophosphate is 30 g / L to 70 g / L.

[0044] Example 1:

[0045] An alumina ceramic tube is coated with a NaA layer with cation exchange function by in-situ chemical synthesis, resulting in a ceramic tube with a NaA layer.

[0046] The ceramic tube with the NaA layer was placed in a pervaporation apparatus and set to 60°C to test the water flux and selectivity. After the test, the ceramic tube with the NaA layer and the metal end cap were ultrasonically cleaned in deionized water for 30 minutes, and then dried in an electrically heated drying oven.

[0047] After drying, the ceramic tube was sensitized. Approximately 20mm of the end of the ceramic tube was immersed in 0.01M silver nitrate for 10 seconds, removed, and air-dried. Then, it was placed in concentrated ammonia water for 10 seconds, removed, rinsed with deionized water for 1 minute, and air-dried. The sensitized ceramic tube end was then transferred to a chemical plating solution for copper plating for 10 minutes. The chemical plating solution contained 22ml / L formaldehyde, 7g / L copper sulfate, 31g / L sodium tartrate, 11g / L sodium hydroxide, 0.1mg / L dipyridine, and 15g / L disodium EDTA. The copper-plated ceramic tube end was polished evenly with 1000-grit sandpaper until shiny, then rinsed with deionized water and set aside for later use.

[0048] Add 1g of Sn-Pb (63 / 37, melting point 183℃) alloy and 0.1g of rosin additive to the metal end cap. Precisely heat the end cap using induction heating, setting the voltage to 5V and the current to 3A. Heat the brazing filler metal to a molten state, immerse the copper-plated ceramic tube end cap in the molten alloy, and heat for 70 seconds. After stopping heating, allow it to cool naturally to room temperature to complete the connection.

[0049] Connect the other end of the ceramic tube following the steps described above.

[0050] Take two more brand-new ceramic tubes and, following the steps above, complete the sealing of the ceramic tubes and metal end caps, ready for testing.

[0051] One of the connector components was treated in N-methylpyrrolidone (NMP) at 150℃ for 140 h. The other connector component was treated under 1000 μSv / h radiation for 140 h. The performance results of the connector components are shown in Table 1. As can be seen from Table 1, the performance of the component obtained by the above method remains basically unchanged after high-temperature NMP and radiation treatment, indicating that the connector of the component has good resistance to high temperature, organic solvents and radiation.

[0052] Table 1 Comparison of Pervaporation Performance of Copper-Plated Connecting Components

[0053]

[0054]

[0055] Example 2:

[0056] A ceramic tube with a ZIF-8 layer is coated on its surface by in-situ chemical synthesis, resulting in a ceramic tube with a ZIF-8 layer.

[0057] The ceramic tube with the ZIF-8 layer was placed in a pervaporation apparatus and set to 60°C to test water flux and selectivity. After testing, the ceramic tube with the ZIF-8 layer and the metal end cap were ultrasonically cleaned in deionized water for 30 minutes, and then dried in an electrically heated drying oven.

[0058] After drying, the ceramic tube was sensitized. Approximately 20mm of the end of the ceramic tube was immersed in 0.01M silver nitrate solution for 10 seconds, removed, and air-dried. Then, it was placed in concentrated ammonia solution for 10 seconds, removed, rinsed with deionized water for 1 minute, and air-dried. The sensitized ceramic tube end was then transferred to a chemical plating solution containing 25g / L nickel sulfate hexahydrate, 25g / L sodium dihydrogen phosphate monohydrate, and 50g / L tetrasodium pyrophosphate. The nickel-plated end was polished evenly with 1000-grit sandpaper until shiny, then rinsed with deionized water and set aside for later use.

[0059] Add 1g of Sn-Pb (63 / 37, melting point 183℃) alloy and 0.1g of rosin additive to the metal end cap. Precisely heat the end cap using induction heating, setting the voltage to 5V and the current to 3A. Heat the brazing filler metal to a molten state, then immerse the nickel-plated ceramic tube end cap in the molten filler metal for 70 seconds. After stopping heating, allow it to cool naturally to room temperature to complete the connection.

[0060] Connect the other end of the ceramic tube following the steps described above.

[0061] Take two more brand-new ceramic tubes and, following the steps above, complete the sealing of the ceramic tubes and metal end caps, ready for testing.

[0062] One of the connector components was treated in N-methylpyrrolidone (NMP) at 150℃ for 140 h. The other connector component was treated under 1000 μSv / h radiation for 140 h. The performance results of the connector components are shown in Table 2. As can be seen from Table 2, the membrane module obtained by the above method has basically unchanged performance after high-temperature NMP and radiation treatment, indicating that the capping layer is a NaA molecular sieve membrane and the nickel-plated connector component has good resistance to high temperature, organic solvents and radiation.

[0063] Table 2 Comparison of Pervaporation Performance of Nickel-Plated Connecting Components

[0064]

[0065] Example 3:

[0066] An alumina ceramic tube is coated with a NaY layer with cation exchange function by in-situ chemical synthesis, resulting in a ceramic tube with a NaY layer.

[0067] The ceramic tube with the NaY layer was placed in a pervaporation apparatus and set to 60°C to test the water flux and selectivity. After the test, the ceramic tube with the NaY layer and the metal end cap were ultrasonically cleaned in deionized water for 30 minutes, and then dried in an electrically heated drying oven.

[0068] After drying, the ceramic tube was sensitized. Approximately 20mm of the end of the ceramic tube was immersed in 0.01M silver nitrate for 10 seconds, removed, and air-dried. Then, it was placed in concentrated ammonia water for 10 seconds, removed, rinsed with deionized water for 1 minute, and air-dried. The sensitized ceramic tube end was then transferred to a chemical plating solution for copper plating for 10 minutes. The chemical plating solution contained 22ml / L formaldehyde, 7g / L copper sulfate, 31g / L sodium tartrate, 11g / L sodium hydroxide, 0.1mg / L dipyridine, and 15g / L disodium EDTA. The copper-plated end was polished evenly with 1000-grit sandpaper until shiny, then rinsed with deionized water and set aside for later use.

[0069] Add 1g of Sn-Pb (63 / 37, melting point 183℃) alloy and 0.1g of rosin additive to the metal end cap. Precisely heat the end cap using induction heating, setting the voltage to 5V and the current to 3A. Heat the brazing filler metal to a molten state, immerse the copper-plated ceramic tube end cap in the molten alloy, and heat for 70 seconds. After stopping heating, allow it to cool naturally to room temperature to complete the connection.

[0070] Connect the other end of the ceramic tube following the steps described above.

[0071] Take two more brand-new ceramic tubes and, following the steps above, complete the sealing of the ceramic tubes and metal end caps, ready for testing.

[0072] One of the connector components was treated in N-methylpyrrolidone (NMP) at 150℃ for 140 h. The other connector component was treated under radiation at 1000 μSv / h for 140 h. The performance results of the connector components are shown in Table 3. As can be seen from Table 3, the membrane module obtained by the above method has basically unchanged performance after high-temperature NMP and radiation treatment, indicating that the capping layer is ZIF-8 and the copper-plated connector has good resistance to high temperature, organic solvents and radiation.

[0073] Table 3 Comparison of pervaporation performance of copper-plated connectors covered with ZIF-8 layer

[0074]

[0075] Comparative Example 1:

[0076] The alumina ceramic tube is connected to the zeolite film NaA layer by in-situ chemical synthesis to form the first layer on the surface.

[0077] The ceramic tube with the NaA layer was placed in a pervaporation apparatus and set to 60°C to test the water flux and selectivity. After the test, the ceramic tube and the metal end cap were ultrasonically cleaned in deionized water for 30 minutes and then dried in an electrically heated drying oven.

[0078] Pass the dried ceramic tube through a nut with a narrow opening at one end and a wide opening with a groove at the other, with the wide opening of the nut facing outwards. Then, insert an O-ring into the ceramic tube and guide it into the groove of the nut. Install another nut, with a threaded end and a sealing end, onto the ceramic tube and tighten it together with the nut already on the ceramic tube to complete the seal.

[0079] Connect the other end of the ceramic tube following the steps described above.

[0080] Take two more brand-new ceramic tubes and, following the steps above, complete the sealing of the ceramic tubes and metal end caps, ready for testing.

[0081] One of the connector components was treated with N-methylpyrrolidone (NMP) at 150℃ for 140 h. The other connector component was treated with radiation at 1000 μSv / h for 140 h. The test results of the zeolite membrane are shown in Table 4. It can be seen from Table 4 that the performance of the component obtained by conventional O-ring sealing decreased after high-temperature NMP and radiation treatment. In particular, the O-ring cracked after radiation treatment, indicating that the conventional O-ring connection has poor resistance to high temperature, organic solvents, and radiation.

[0082] Table 4 Comparison of pervaporation performance of traditional O-ring connection components

[0083]

[0084] Comparative Example 2:

[0085] The alumina ceramic tube was coated with a first layer and a zeolite film NaA layer by in-situ chemical synthesis.

[0086] The ceramic tube with the NaA layer was placed in a pervaporation apparatus and set to 60°C to test the water flux and selectivity. After the test, the ceramic tube and the metal end cap were ultrasonically cleaned in deionized water for 30 minutes and then dried in an electrically heated drying oven.

[0087] Referring to the method provided in Chinese Patent CN 101238316A, one end of a ceramic tube with a NaA layer is inserted into one end of a fluororubber heat shrink tube, and a roughly cylindrical component is inserted into the other end of the fluororubber heat shrink tube. The axial directions of the ceramic tube and the cylindrical component are aligned, and the fluororubber heat shrink tube covers 10mm on each side from their connection point. Then, hot air is used to heat the fluororubber heat shrink tube, causing it to shrink.

[0088] Another Teflon heat shrink tube is inserted into the component tube and the generally cylindrical part, and arranged to cover the fluororubber heat shrink tube by 13mm on each side from the connection point. Then, the Teflon heat shrink tube is heated with hot air to heat shrink it. This fixes and seals the fluororubber heat shrink tube, the generally cylindrical part, and the ceramic tube with zeolite film.

[0089] Connect the other end of the ceramic tube following the steps described above.

[0090] Take two more brand-new ceramic tubes and, following the steps above, complete the sealing of the ceramic tubes and metal end caps, ready for testing.

[0091] One of the connector components was treated in N-methylpyrrolidone (NMP) at 150°C for 140 hours. The other connector component was treated under radiation at 1000 μSv / h for 140 hours. The performance results of the zeolite membrane obtained from the tests are shown in Table 5. As can be seen from Table 5, the sealing method provided by this patent exhibits a slight decrease in performance after high-temperature NMP treatment, and a more significant decrease in performance after radiation treatment. In particular, the fluororubber heat shrink tube ruptured after radiation treatment, indicating that the connection method has poor resistance to high temperatures, organic solvents, and radiation.

[0092] Table 5 Comparison of pervaporation performance of zeolite membranes with sealed connections in patent CN 101238316A

[0093]

[0094] Comparative Example 3:

[0095] The alumina ceramic tube is connected to the zeolite film NaA layer by in-situ chemical synthesis to form the first layer on the surface.

[0096] The ceramic tube with the NaA layer was placed in a pervaporation apparatus and set to 60°C to test water flux and selectivity. After the ceramic was tested, it and the metal end cap were ultrasonically cleaned in deionized water for 30 minutes and then dried in an electrically heated drying oven.

[0097] The dried ceramic tube and metal end cap were connected, and the gap was filled with Sn-Pb (63 / 37, melting point 183℃) cryogenic alloy and 0.1g of rosin as an auxiliary agent. The end cap was precisely heated using induction heating at 5V and 3A until the alloy reached a molten state. The end cap of the membrane tube (10mm) was then immersed in the molten cryogenic alloy for 70 seconds. After heating was stopped, the membrane tube was allowed to cool naturally to room temperature, completing the sealing component.

[0098] Connect the other end of the ceramic tube following the steps described above.

[0099] Take two more brand-new ceramic tubes and, following the steps above, complete the sealing of the ceramic tubes and metal end caps, ready for testing.

[0100] One of the connector components was treated in N-methylpyrrolidone (NMP) at 150°C for 140 h. The other connector component was treated under radiation at 1000 μSv / h for 140 h. The performance results of the connector components are shown in Table 6. As can be seen from Table 6, the alloy connector components have very poor selectivity and permeability, and cannot achieve a sealing connection.

[0101] Table 6 Comparison of pervaporation properties of direct alloy connection components

[0102]

[0103] The above description discloses only preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. Therefore, equivalent variations made in accordance with the claims of the present invention are still within the scope of the present invention.

Claims

1. A ceramic tube end connector component, characterized in that, The material comprises an oxide ceramic layer (1), an inorganic material layer (2), an elemental layer (3), an alloy layer (4), and a metal layer (5) stacked sequentially. The oxide ceramic layer (1) has a dense or porous structure. The inorganic material layer (2) has cation exchange function. The elemental layer (3) is a metallic element corresponding to a metal ion that can exchange ions with the inorganic material layer (2). The alloy layer (4) can wet the elemental layer (3) and the metal layer (5) respectively. The inorganic material layer (2) includes a zeolite layer or an organometallic framework layer; The elemental layer (3) includes a copper layer, a silver layer, or a nickel layer.

2. The ceramic tube end connector component according to claim 1, characterized in that, The oxide ceramic layer (1) includes an alumina ceramic layer or a titanium oxide ceramic layer.

3. A method for manufacturing a ceramic tube end connector as described in claim 1 or 2, characterized in that, Includes the following steps: A ceramic tube with an inorganic material layer having cation exchange function is coated on the surface of the ceramic tube to obtain a ceramic tube with an inorganic material layer. The ceramic tube with the inorganic material layer and the metal end cap are placed in deionized water for ultrasonic cleaning, and then dried. The dried end of the ceramic tube with the inorganic material layer is directly contacted with the chemical plating solution for chemical plating. The inorganic material layer and the chemical plating solution undergo cation exchange to form a single layer, resulting in a ceramic tube with a single layer at the end. The dried metal end cap is connected to a ceramic tube with a single layer, and a low-temperature alloy and auxiliary agent are filled into the gap between the metal end cap and the single layer to obtain a connecting component.

4. The method for manufacturing the ceramic tube end connector component according to claim 3, characterized in that, The steps of connecting the dried metal end cap to a ceramic tube with a single layer, and filling the gap between the metal end cap and the single layer with a low-temperature alloy and an auxiliary agent to obtain a connecting component include: Low-temperature alloys and additives are filled into the gap between the single layer and the metal head to obtain a connector between the ceramic tube and the metal head; The end of the connector filled with the cryogenic alloy and auxiliary agent is heated until the cryogenic alloy and auxiliary agent reach a molten state. The heated connector is allowed to cool naturally at room temperature to obtain the connector component.

5. The method for manufacturing the ceramic tube end connector component according to claim 4, characterized in that, The low-temperature alloy includes a solder alloy, and the auxiliary agent is a reducing organic compound.

6. The method for manufacturing the ceramic tube end connector component according to claim 4, characterized in that, The end of the connector filled with low-temperature alloy and additives is heated by induction heating.

7. The method for manufacturing the ceramic tube end connector component according to claim 6, characterized in that, In the induction heating method, the heating power is 1~100 W, the heating time is 30 s~180 s, and the temperature is 120~200 ℃.

8. The method for manufacturing the ceramic tube end connector component according to claim 3, characterized in that, The electroless plating solution contains copper or nickel ions, the reaction temperature of the electroless plating is 20~50 ℃, and the reaction time of the electroless plating is 1 min~60 min.

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