A method for preparing titanium powder and titanium sintered felt in an integrated manner

Abstract

The application relates to the technical field of titanium sintered felt, and provides a preparation method of titanium powder titanium sintered felt integration; the titanium powder titanium sintered felt integration is obtained by adopting the following steps: laying, stacking and high-temperature sintering of titanium fibers, and then coating glue on the sintered felt and covering titanium powder; the titanium powder titanium sintered felt prepared by the application has excellent gas-liquid transmission capacity, better mechanical strength and toughness, and is a good conductor with low cost; the titanium powder titanium sintered felt prepared by the application can simultaneously have the advantages of titanium felt and titanium powder by covering 1-5 microns of titanium powder on the surface of the titanium felt, and the performance is more superior; the release agent prepared by taking titanium organometallic as raw material has low surface tension, good chemical stability and thermal stability; the release agent obtained by compounding the titanium organometallic and polyethylene wax can adapt to the high-temperature processing and manufacturing process of the titanium sintered felt, and better release effect and production benefit are provided.

Description

Technical Field

[0001] This invention relates to the field of titanium sintered felt technology, and in particular to a method for preparing an integrated titanium powder and titanium sintered felt. Background Technology

[0002] The porous transport layer (PTL) is a crucial component of the PEMWE electrolyzer, located between the catalyst layer and the bipolar plates. It is also known as the gas diffusion layer (GDL), liquid / gas diffusion layer (LGDL), or current collector (CC). Compared to the carbon-based anode PTL in proton exchange membrane fuel cells (PEMWE), carbon-based PTLs, including those made of carbon paper and carbon cloth, corrode due to carbon oxidation in the environment of higher anode overpotential (~2V), lower pH (<2), and the accumulation of water and oxygen at the anode. Due to its excellent stability, titanium (Ti) is currently the mainstream material for preparing PEMWE anode PTLs. However, in the harsh operating environment of PEMWE, the titanium in the titanium-based porous transport layer (Ti-PTL) passivates to TiO2, resulting in a significant increase in ohmic resistance.

[0003] Titanium felt is made by thermally sintering uniformly distributed titanium fibers. Due to its excellent gas-liquid transport capability, good mechanical strength and toughness, it is the preferred anode titanium-based porous transport layer (Ti-PTL) for current 100 kW and megawatt fuel cell stacks. However, current commercially available titanium felt is not designed for PEMWE anode PTLs, so the advantages of titanium felt as a PEMWE anode PTL are not significantly realized.

[0004] Chinese Patent CN201110435903.9 discloses a method for processing metallic titanium materials. The metallic titanium material is sintered porous titanium, titanium felt, titanium mesh, or foamed titanium. The processing method is as follows: surface purification of the titanium material; anodic oxidation using the purified material as an anode; electrodeposition of a catalyst layer or coating with a catalyst precursor on its surface followed by high-temperature calcination to obtain a highly catalytically active titanium material. The prepared catalytically active titanium material can be used as a diffusion layer or as an electrode. This invention has advantages such as simple preparation method, high catalytic activity, significantly reduced electrolysis voltage, and improved energy utilization. This invention is not limited to application in hydrobromic acid electrolyzers but can also be used as a diffusion layer or electrode in hydrogen bromine fuel cells and hydrogen bromine renewable energy storage batteries.

[0005] Chinese Patent CN202210958592.2 relates to a method for preparing a metal-based conductive porous transport layer and its application in an electrolytic water battery. The method includes at least the following steps: S1, dissolving phenolic resin or phenolic epoxy resin and a dispersant in an organic solvent, then adding metal-based conductive material powder, uniformly dispersing the powder in the organic solvent to obtain slurry a. The mass ratio of resin to metal-based conductive material is 1:18-22, and the mass fraction of the dispersant in slurry a is 1-5%. S2, taking a cleaned titanium felt, and coating the surface of the titanium felt with slurry a obtained in step S1. S3, drying the coated titanium felt to obtain the metal-based conductive porous transport layer. The prepared metal-based conductive porous transport layer overcomes the problems of rough surface, large thickness deviation, insufficient flatness leading to high interfacial contact resistance, low performance, severe attenuation, and puncture of the proton exchange membrane. The technical solution of this invention has simple steps, strong operability, and is easy to repeat.

[0006] Chinese Patent CN202111370120.7, belonging to the field of proton exchange membrane electrolyzer technology, discloses a method for preparing a modified porous titanium-based current collector. Specifically, the method involves: degreasing and acid treatment of a titanium substrate with an organic solvent, followed by washing with deionized water and drying; and then performing constant-potential electrochemical nitriding treatment on the treated titanium substrate to form a nitriding film on the surface of the titanium substrate, thereby obtaining a modified porous titanium-based current collector. The beneficial effects of this invention are: the method of this invention improves the corrosion resistance and conductivity of the titanium felt by forming a dense and uniform conductive coating on the surface of the titanium felt through constant-potential electrochemical nitriding in an acidic nitrate solution. It possesses excellent conductivity and corrosion resistance, and has broad application prospects for improving the durability of current collectors in future proton exchange membrane electrolyzers.

[0007] However, existing patents and technologies have drawbacks such as relatively large pore size of titanium felt, moderate water flow rate, and poor surface finish compared to titanium powder. Titanium powder is finer, has better electrical conductivity, poor toughness, and insufficient water flow rate. Summary of the Invention

[0008] Therefore, the technical problem that this invention aims to solve is that the titanium felt prepared in the prior art has a relatively large pore size, poor mechanical strength and gas-liquid transmission capacity, and its conductivity and powder fineness are not as good as titanium powder.

[0009] Therefore, the present invention provides the following technical solution:

[0010] A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps:

[0011] S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench. Align the two plates by passing positioning pins through their positioning holes. Evenly spray a 10-20% (w / w) water-based release agent emulsion onto the inner wall of the cavity, applying it at a concentration of 0.05-1 kg / m³. 2 The amount of spray used;

[0012] S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity.

[0013] S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold.

[0014] S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 30-50Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature.

[0015] S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt;

[0016] S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt.

[0017] Preferably, the length of the short fiber is 50-60 mm.

[0018] Preferably, the heating process is divided into two stages: the first stage is to raise the temperature from room temperature to 700-800℃ for 100-150 minutes; the second stage is to raise the temperature to 1000-1100℃ for 80-120 minutes and hold the temperature for 180-300 minutes.

[0019] Preferably, the sintering time is 40-120 min.

[0020] Preferably, at the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 90-100 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling speed. The process continues until the temperature drops to 250-350°C, at which point the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

[0021] Preferably, the adhesive is commercially available HY-T160 adhesive.

[0022] Preferably, the titanium powder has a particle size of 1-5 μm.

[0023] Preferably, the method for preparing the release agent is as follows:

[0024] B1: By weight, 3-7 parts of titanium chloride and 4-9 parts of 5-amino-1,2,3-benzenetricarboxylic acid are placed in 100-120 parts of organic solvent and transferred to a reaction vessel with a polytetrafluoroethylene liner. The mixture is heated to 80-100°C and stirred for 1-3 hours. Then, 0.03-0.3 parts of dioctadecylamine, 20-30 parts of octadecyl polyoxyethylene methacrylate, and 0.5-2 parts of triethylamine are added. The mixture is heated to 100-120°C and stirred for 50-100 minutes. The solvent is removed by distillation to obtain the titanium organometallic co-emulsifier.

[0025] B2: Mix 30-40 parts of polyethylene wax, 0.03-0.3 parts of titanium organometallic co-emulsifier, and 3-8 parts of octadecyl alcohol in a stirrer at a speed of 200-300 r / min. Slowly heat to 70℃-80℃ and keep the temperature constant for 1-3 hours. After the reaction is complete, cool to room temperature to obtain the release agent.

[0026] Preferably, the molecular weight of the polyethylene wax is between 2000 and 10000.

[0027] Preferably, the organic solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, or diethylformamide.

[0028] The reaction mechanism of the release agent in this invention is as follows:

[0029] 1. Titanium chloride and 5-amino-1,2,3-benzenetricarboxylic acid form an amino-titanium organometallic complex;

[0030] 2. The amino-titanium organometallic complex undergoes an amino-acrylate addition reaction with octadecyl polyoxyethylene methacrylate, and the bis(octadecylamine) further undergoes an amino-acrylate addition reaction with octadecyl polyoxyethylene methacrylate to obtain a titanium organometallic co-emulsifier.

[0031] 3. Polyethylene wax, titanium organometallic emulsifier, and octadecyl alcohol are combined to obtain a release agent.

[0032] The technical solution of this invention has the following advantages:

[0033] 1. The titanium powder sintered felt prepared by this invention has excellent gas-liquid transport capability, good mechanical strength and toughness, low cost, and is a good conductor.

[0034] 2. The titanium powder sintered felt prepared by the present invention can simultaneously possess the advantages of titanium felt and titanium powder by coating the surface of titanium felt with 1-5μm of titanium powder, resulting in superior performance.

[0035] 3. The release agent prepared by the present invention using titanium organometallic as raw material has low surface tension, which helps to reduce the adhesion between the material and the mold and improve the release effect; it has good chemical stability and thermal stability, and can be used at high temperature without easily decomposing or deteriorating; therefore, the release agent obtained by compounding titanium organometallic with polyethylene wax can adapt to the high-temperature processing and manufacturing process of titanium sintered felt, providing better release effect and production efficiency. Detailed Implementation

[0036] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0037] In the embodiments of this invention, the titanium powder titanium sintered felt was prepared using an Instron 5967 universal testing machine, and the tensile properties of the titanium fiber felt were tested according to GB / T228.1-2021 standard for tensile testing of metallic materials. The tensile test speed was 10. -3 mm / s.

[0038] Example 1

[0039] A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps:

[0040] S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench. Align the two plates by passing positioning pins through their positioning holes. Evenly spray a 10% (w / w) water-based release agent emulsion onto the inner wall of the cavity, applying it at a rate of 0.05 kg / m³. 2 The amount of spray used;

[0041] S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity.

[0042] S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold.

[0043] S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 30Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature.

[0044] S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt;

[0045] S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt.

[0046] The short fiber has a length of 50 mm.

[0047] The heating process is divided into two stages. The first stage is to raise the temperature from room temperature to 700°C for 100 minutes. The second stage is to raise the temperature to 1000°C for 80 minutes and then hold the temperature for 180 minutes.

[0048] The sintering time is 40 minutes.

[0049] At the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 90 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling speed. The process continues until the temperature drops to 250°C, at which point the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

[0050] The adhesive mentioned is commercially available HY-T160 adhesive.

[0051] The titanium powder has a particle size of 1 μm.

[0052] The method for preparing the release agent is as follows:

[0053] B1: 3g of titanium chloride and 4g of 5-amino-1,2,3-benzenetricarboxylic acid were placed in 100g of organic solvent and transferred to a reaction vessel with a polytetrafluoroethylene liner. The mixture was heated to 80°C and stirred for 1 hour. Then, 0.03g of bis(octadecylamine), 20g of octadecyl polyoxyethylene methacrylate, and 0.5g of triethylamine were added. The mixture was heated to 100°C and stirred for 50 minutes. The solvent was removed by distillation to obtain a titanium organometallic co-emulsifier.

[0054] B2: Mix 30g polyethylene wax, 0.03g titanium organometallic co-emulsifier, and 3g octadecyl alcohol in a stirrer at 200r / min, slowly heat to 70℃, and keep the temperature constant for 1 hour. After the reaction is complete, cool to room temperature to obtain the release agent.

[0055] The polyethylene wax has a molecular weight of 2000.

[0056] The organic solvent is N,N-dimethylformamide.

[0057] In this example, the tensile strength of the prepared titanium powder sintered felt is 48 MPa, and the demolding rate is 99.6%.

[0058] Example 2

[0059] A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps:

[0060] S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench. Align the two plates by passing positioning pins through their positioning holes. Evenly spray a 15% (w / w) water-based release agent emulsion onto the inner wall of the cavity, applying it at a rate of 0.3 kg / m³. 2 The amount of spray used;

[0061] S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity.

[0062] S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold.

[0063] S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 35Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature.

[0064] S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt;

[0065] S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt.

[0066] The short fiber has a length of 50 mm.

[0067] The heating process is divided into two stages. The first stage is to raise the temperature from room temperature to 750°C for 120 minutes. The second stage is to raise the temperature to 1050°C for 90 minutes and then hold the temperature for 220 minutes.

[0068] The sintering time is 65 minutes.

[0069] At the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 95 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling speed. The process continues until the temperature drops to 280°C, at which point the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

[0070] The adhesive mentioned is commercially available HY-T160 adhesive.

[0071] The titanium powder has a particle size of 3μm.

[0072] The method for preparing the release agent is as follows:

[0073] B1: 4g of titanium chloride and 6g of 5-amino-1,2,3-benzenetricarboxylic acid were placed in 105g of organic solvent and transferred to a reaction vessel with a polytetrafluoroethylene liner. The mixture was heated to 85°C and stirred for 2 hours. Then, 0.1g of bis(octadecylamine), 24g of octadecyl polyoxyethylene methacrylate, and 1g of triethylamine were added. The mixture was heated to 105°C and stirred for 70 minutes. The solvent was removed by distillation to obtain a titanium organometallic co-emulsifier.

[0074] B2: Mix 34g of polyethylene wax, 0.1g of titanium organometallic co-emulsifier, and 5g of octadecyl alcohol in a stirrer at 250r / min, slowly heat to 75℃, and keep the temperature constant for 2 hours. After the reaction is complete, cool to room temperature to obtain the release agent.

[0075] The molecular weight of the polyethylene wax is between 5000 and 6000.

[0076] The organic solvent is N,N-dimethylacetamide.

[0077] In this example, the tensile strength of the prepared titanium powder sintered felt was 49 MPa, and the demolding rate was 99.7%.

[0078] Example 3

[0079] A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps:

[0080] S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench. Align the two plates by passing positioning pins through their positioning holes. Evenly spray a 15% (w / w) water-based release agent emulsion onto the inner wall of the cavity, applying it at a rate of 0.8 kg / m³.2 The amount of spray used;

[0081] S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity.

[0082] S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold.

[0083] S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 40Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature.

[0084] S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt;

[0085] S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt.

[0086] The short fiber has a length of 55 mm.

[0087] The heating process is divided into two stages. The first stage is to raise the temperature from room temperature to 750°C in 140 minutes. The second stage is to raise the temperature to 1050°C in 110 minutes and hold the temperature for 260 minutes.

[0088] The sintering time is 90 minutes.

[0089] At the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 95 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling speed. The process continues until the temperature drops to 330°C, at which point the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

[0090] The adhesive mentioned is commercially available HY-T160 adhesive.

[0091] The titanium powder has a particle size of 4μm.

[0092] The method for preparing the release agent is as follows:

[0093] B1: 6g of titanium chloride and 7g of 5-amino-1,2,3-benzenetricarboxylic acid were placed in 115g of organic solvent and transferred to a reaction vessel with a polytetrafluoroethylene liner. The mixture was heated to 95°C and stirred for 3 hours. Then, 0.2g of bis(octadecylamine), 28g of octadecyl polyoxyethylene methacrylate, and 1.5g of triethylamine were added. The mixture was heated to 115°C and stirred for 90 minutes. The solvent was removed by distillation to obtain a titanium organometallic co-emulsifier.

[0094] B2: Mix 38g of polyethylene wax, 0.2g of titanium organometallic co-emulsifier, and 7g of octadecyl alcohol in a stirrer at 250r / min, slowly heat to 75℃, and keep the temperature constant for 2 hours. After the reaction is complete, cool to room temperature to obtain the release agent.

[0095] The polyethylene wax has a molecular weight of 8000.

[0096] The organic solvent is N,N-dimethylacetamide.

[0097] In this example, the tensile strength of the prepared titanium powder sintered felt is 53 MPa, and the demolding rate is 99.8%.

[0098] Example 4

[0099] A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps:

[0100] S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench. Align the two plates by passing positioning pins through their positioning holes. Evenly spray a 20% (w / w) water-based release agent emulsion onto the inner wall of the cavity, applying it at a concentration of 1 kg / m³. 2 The amount of spray used;

[0101] S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity.

[0102] S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold.

[0103] S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 50Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature.

[0104] S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt;

[0105] S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt.

[0106] The short fiber has a length of 60 mm.

[0107] The heating process is divided into two stages. The first stage is to raise the temperature from room temperature to 800℃, with a heating time of 150 minutes. The second stage is to raise the temperature to 1100℃, with a heating time of 120 minutes, and then hold the temperature for 300 minutes.

[0108] The sintering time is 120 minutes.

[0109] At the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 100 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling speed. The process continues until the temperature drops to 350°C, at which point the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

[0110] The adhesive mentioned is commercially available HY-T160 adhesive.

[0111] The titanium powder has a particle size of 5 μm.

[0112] The method for preparing the release agent is as follows:

[0113] B1: 7g of titanium chloride and 9g of 5-amino-1,2,3-benzenetricarboxylic acid were placed in 120g of organic solvent and transferred to a reaction vessel with a polytetrafluoroethylene liner. The mixture was heated to 100°C and stirred for 3 hours. Then, 0.3g of bis(octadecylamine), 30g of octadecyl polyoxyethylene methacrylate, and 2g of triethylamine were added. The mixture was heated to 120°C and stirred for 100 minutes. The solvent was removed by distillation to obtain a titanium organometallic co-emulsifier.

[0114] B2: Mix 40g of polyethylene wax, 0.3g of titanium organometallic co-emulsifier, and 8g of octadecyl alcohol in a stirrer at 300r / min, slowly heat to 80℃, and keep the temperature constant for 3h. After the reaction is complete, cool to room temperature to obtain the release agent.

[0115] The polyethylene wax has a molecular weight of 10,000.

[0116] The organic solvent is diethylformamide.

[0117] In this example, the tensile strength of the prepared titanium powder sintered felt is 51 MPa, and the demolding rate is 99.7%.

[0118] Comparative Example 1

[0119] A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps:

[0120] S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench, and use positioning pins to pass through the positioning holes of the two plates to align the two plates.

[0121] S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity.

[0122] S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold.

[0123] S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 30Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature.

[0124] S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt;

[0125] S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt.

[0126] The short fiber has a length of 50 mm.

[0127] The heating process is divided into two stages. The first stage is to raise the temperature from room temperature to 700°C for 100 minutes. The second stage is to raise the temperature to 1000°C for 80 minutes and then hold the temperature for 180 minutes.

[0128] The sintering time is 40 minutes.

[0129] At the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 90 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling speed. The process continues until the temperature drops to 250°C, at which point the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

[0130] The adhesive mentioned is commercially available HY-T160 adhesive.

[0131] The titanium powder has a particle size of 1 μm.

[0132] In this example, the tensile strength of the prepared titanium powder sintered felt is 33 MPa, and the demolding rate is 80.4%.

[0133] Comparative Example 2

[0134] A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps:

[0135] S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench. Align the two plates by passing positioning pins through their positioning holes. Evenly spray a 10% (w / w) water-based release agent emulsion onto the inner wall of the cavity, applying it at a rate of 0.05 kg / m³. 2 The amount of spray used;

[0136] S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity.

[0137] S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold.

[0138] S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 30Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature.

[0139] S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt;

[0140] S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt.

[0141] The short fiber has a length of 50 mm.

[0142] The heating process is divided into two stages. The first stage is to raise the temperature from room temperature to 700°C for 100 minutes. The second stage is to raise the temperature to 1000°C for 80 minutes and then hold the temperature for 180 minutes.

[0143] The sintering time is 40 minutes.

[0144] At the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 90 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling speed. The process continues until the temperature drops to 250°C, at which point the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

[0145] The adhesive mentioned is commercially available HY-T160 adhesive.

[0146] The titanium powder has a particle size of 1 μm.

[0147] The method for preparing the release agent is as follows:

[0148] B1: 3g of titanium chloride and 4g of 5-amino-1,2,3-benzenetricarboxylic acid were placed in 100g of organic solvent and transferred to a reaction vessel with a polytetrafluoroethylene liner. The mixture was heated to 80°C and stirred for 1 hour. Then, 0.03g of bis(octadecylamine), 20g of octadecyl polyoxyethylene methacrylate, and 0.5g of triethylamine were added. The mixture was heated to 100°C and stirred for 50 minutes. The solvent was removed by distillation to obtain a titanium organometallic co-emulsifier.

[0149] B2: Mix 0.03g of titanium organometallic co-emulsifier and 3g of octadecyl alcohol in a stirrer at 200r / min, slowly heat to 70℃, and keep the temperature constant for 1h. After the reaction is complete, cool to room temperature to obtain the release agent.

[0150] The organic solvent is N,N-dimethylformamide.

[0151] In this example, the tensile strength of the prepared titanium powder sintered felt is 37 MPa, and the demolding rate is 90.3%.

[0152] Comparative Example 3

[0153] A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps:

[0154] S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench. Align the two plates by passing positioning pins through their positioning holes. Evenly spray a 10% (w / w) water-based release agent emulsion onto the inner wall of the cavity, applying it at a rate of 0.05 kg / m³. 2 The amount of spray used;

[0155] S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity.

[0156] S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold.

[0157] S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 30Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature.

[0158] S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt;

[0159] S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt.

[0160] The short fiber has a length of 50 mm.

[0161] The heating process is divided into two stages. The first stage is to raise the temperature from room temperature to 700°C for 100 minutes. The second stage is to raise the temperature to 1000°C for 80 minutes and then hold the temperature for 180 minutes.

[0162] The sintering time is 40 minutes.

[0163] At the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 90 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling speed. The process continues until the temperature drops to 250°C, at which point the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

[0164] The adhesive mentioned is commercially available HY-T160 adhesive.

[0165] The titanium powder has a particle size of 1 μm.

[0166] The method for preparing the release agent is as follows:

[0167] B1: 3g of titanium chloride and 4g of 5-amino-1,2,3-benzenetricarboxylic acid were placed in 100g of organic solvent and transferred to a reaction vessel with a polytetrafluoroethylene liner. The mixture was heated to 80°C and stirred for 1 hour. Then, 0.03g of bis(octadecylamine), 20g of octadecyl polyoxyethylene methacrylate, and 0.5g of triethylamine were added. The mixture was heated to 100°C and stirred for 50 minutes. The solvent was removed by distillation to obtain a titanium organometallic co-emulsifier.

[0168] B2: Mix 30g of polyethylene wax and 0.03g of titanium organometallic co-emulsifier, stir in a stirrer at 200r / min, slowly heat to 70℃, and keep the temperature constant for 1h. After the reaction is complete, cool to room temperature to obtain the release agent.

[0169] The polyethylene wax has a molecular weight of 2000.

[0170] The organic solvent is N,N-dimethylformamide.

[0171] In this example, the tensile strength of the prepared titanium powder sintered felt is 39 MPa, and the demolding rate is 93.7%.

[0172] By comparing the data from the above embodiments and comparative examples, the titanium powder sintered felt prepared by the present invention has good mechanical strength and toughness; the release agent prepared by the present invention has good release effect and can improve production efficiency.

[0173] Those skilled in the art should understand that the above embodiments are merely exemplary embodiments, and various changes, substitutions, and modifications can be made without departing from the spirit and scope of the present invention. All obvious changes or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A method for preparing an integrated titanium powder and titanium sintered felt, comprising the following steps: S1: Place the base plate and cavity plate of the stacked sintering mold on a horizontal workbench. Align the two plates by passing positioning pins through their positioning holes. Evenly spray a 10-20% (w / w) water-based release agent emulsion onto the inner wall of the cavity, applying it at a concentration of 0.05-1 kg / m³. 2 The amount of spray used; S2: Cut the titanium fiber into short fibers and lay them evenly into the cavity of the mold layer by layer. Each layer of fiber needs to be fully spread out to fill the entire cavity area. After filling, use a pressure block with the same cross-section as the cavity to compact the fiber. Then lay the next layer of fiber. When the fiber layer is thick, use a pressure plate to compact it. Repeat this process until the fiber evenly fills the entire cavity. S3: Symmetrical holes for bolts are provided on the base plate, cavity plate, and pressure plate. They are stacked together, bolts are installed, and nuts are tightened to clamp the entire mold in a vise. According to the principle of symmetrical mold locking, a certain torque is applied to the bolts and nuts with a wrench to tighten the pressure plate and base plate, thereby achieving the shaping of the entire fiber and the locking of the mold. S4: Place the locked mold into the furnace chamber of the vacuum sintering furnace. When the vacuum degree in the furnace reaches 30-50Pa, start heating. After sintering is completed, stop the heat preservation in the vacuum furnace and cool down to room temperature. S5: After sintering, remove the mold from the furnace, demold and remove the titanium sintered felt; S6: Apply glue to the titanium sintered felt and spray titanium powder with a spray gun to obtain titanium powder titanium sintered felt; The method for preparing the release agent is as follows: B1: By weight, 3-7 parts of titanium chloride and 4-9 parts of 5-amino-1,2,3-benzenetricarboxylic acid are placed in 100-120 parts of organic solvent and transferred to a reaction vessel with a polytetrafluoroethylene liner. The mixture is heated to 80-100°C and stirred for 1-3 hours. Then, 0.03-0.3 parts of dioctadecylamine, 20-30 parts of octadecyl polyoxyethylene methacrylate, and 0.5-2 parts of triethylamine are added. The mixture is heated to 100-120°C and stirred for 50-100 minutes. The solvent is removed by distillation to obtain the titanium organometallic co-emulsifier. B2: Mix 30-40 parts of polyethylene wax, 0.03-0.3 parts of titanium organometallic co-emulsifier, and 3-8 parts of octadecyl alcohol in a stirrer at a speed of 200-300 r / min. Slowly heat to 70℃-80℃ and keep the temperature constant for 1-3 hours. After the reaction is complete, cool to room temperature to obtain the release agent.

2. The preparation method of the integrated titanium powder and titanium sintered felt according to claim 1, characterized in that: The short fibers have a length of 50-60 mm.

3. The method for preparing an integrated titanium powder and titanium sintered felt according to claim 1, characterized in that: The heating process is divided into two stages. The first stage is to raise the temperature from room temperature to 700-800℃, with a heating time of 100-150 minutes. The second stage is to raise the temperature to 1000-1100℃, with a heating time of 80-120 minutes, and then hold the temperature for 180-300 minutes.

4. The preparation method of integrated titanium powder and titanium sintered felt according to claim 1, characterized in that: The sintering time is 40-120 min.

5. The method for preparing an integrated titanium powder and titanium sintered felt according to claim 1, characterized in that: At the beginning of the cooling process, argon gas needs to be introduced into the vacuum furnace. When the pressure inside the furnace reaches 90-100 kPa, the gas introduction is stopped, and the cooling fan is turned on to accelerate the cooling rate. The process continues until the temperature drops to 250-350°C. Then, the vacuum sintering furnace is turned off and the furnace is air-cooled to room temperature.

6. The method for preparing an integrated titanium powder and titanium sintered felt according to claim 1, characterized in that: The adhesive mentioned is commercially available HY-T160 adhesive.

7. The preparation method of an integrated titanium powder and titanium sintered felt according to claim 1, characterized in that: The titanium powder has a particle size of 1-5 μm.

8. The preparation method of an integrated titanium powder and titanium sintered felt according to claim 1, characterized in that: The molecular weight of the polyethylene wax is between 2000 and 10000.

9. The method for preparing an integrated titanium powder and titanium sintered felt according to claim 1, characterized in that: The organic solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, or diethylformamide.